JP2010249995A - Toner for electrostatic charge image development and method for forming image of the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer excellent in low temperature fixability, heat-resistant storage properties and durability, and excellent in chargeability while being environmentally friendly; and to provide an image forming method. <P>SOLUTION: The toner for electrostatic charge image development contains a binder resin containing a polyester resin, a colorant, and a charge controlling agent, and is characterized in that: the charge controlling agent is a cyclic phenol sulfide selected from thiacalixarene, sulfinylated thiacalixarene and sulfonylated thiacalixarene; the polyester resin is obtained by condensation polymerization of an alcohol component comprising an aliphatic polyhydric alcohol with a carboxylic acid component; and the toner does not substantially contain a tin element. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner used in an electrophotographic image forming method and an image forming method thereof.

  In recent years, electrophotographic image forming apparatuses have been used as ordinary copying machines and printers for printing office documents or as simple copies, to the field of producing printed materials for office use, specifically electronic data. Since variable information can be printed easily, the application has expanded to the on-demand printing (POD) market, which is a light printing area, and several copiers and printers have been installed in the office. As a whole, the amount of power consumption has increased.

  In the POD market, since a value is required for the printed matter, not for copying, it is required to form a high-quality image as the printed matter.

  A polyester resin system has been used as a binder resin for toners as an effective means for achieving both low-temperature fixability and heat-resistant storage. Conventionally, an aliphatic polyhydric alcohol compound is used as a polyhydric alcohol component constituting the polyester resin. It is known that fixing properties at low temperatures can be improved while maintaining crush resistance, which is an essential requirement of physical properties that improve durability by using the main component. On the other hand, the toner using the polyester resin has poor rise in chargeability, and particularly has poor toner scattering and fogging performance on the image during durability, high temperature and high humidity, and low temperature and low humidity. The problem is that the uniformity of density tends to deteriorate (see, for example, Patent Documents 1 to 3).

  In recent years, from the viewpoint of safety, tin compound catalysts have been used in the conventional polycondensation reactions of polyester resins. However, since they contain a heavy metal called tin, they have recently become unsuitable for environmental policy requirements. The alternative is desired.

JP-A-1-223469 Japanese Patent Laid-Open No. 2-161467 Japanese Patent Laid-Open No. 1-204062

  The present invention has been made based on the circumstances as described above, and its purpose is to provide a developer that is excellent in low-temperature fixability, heat-resistant storage and durability, and also excellent in chargeability including the environment. There is to do. It is another object of the present invention to provide a developer excellent in environmental safety and to provide a toner capable of obtaining a high-quality image and an image forming method thereof.

  As a result of investigations by the present inventors, an aliphatic polyhydric alcohol compound as a main component as an aliphatic alcohol component constituting the polyester resin, and a charge control agent having a specific structure is contained in the toner particles. This improves the above-mentioned problems.

  That is, the present invention is achieved by having the following configuration.

  1. A binder resin containing at least a polyester resin, a colorant, and a charge control agent. The thiacalixarene, sulfinylated thiacalixarene, and sulfonylated thiacalix represented by the following general formula (1) A cyclic phenol sulfide selected from arenes, wherein the polyester resin is obtained by polycondensing an alcohol component containing an aliphatic polyhydric alcohol and a carboxylic acid component, and substantially contains tin element in the toner. A toner for developing an electrostatic charge image, which is not contained.

(Wherein, X represents S, SO or SO _2, Z is .n represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group is an integer of 3-9, Y is a hydrocarbon group, a halogenated hydrocarbon group, a halogen atom, —SO ₄ R ¹ or —SO ₃ R ² , R ¹ and R ² represent a hydrogen atom, a hydrocarbon group, or a metal element, Y may be the same or different.)
2. 2. The toner according to 1 above, wherein the toner has a volume-based median diameter of 2.0 μm or more and 8.0 μm or less and an average circularity of 0.920 to 0.995.

  3. 3. The toner according to 1 or 2 above, wherein the toner has a softening point temperature of 121 ° C. or lower and a glass transition temperature of 55 ° C. or lower.

  4). An image forming method for forming a toner image using at least a black toner and a color toner, wherein the toner is the toner described in any one of 1 to 3 above.

  According to the toner of the present invention, the toner particles constituting the toner are made of a polyester resin containing an aliphatic polyhydric alcohol as a main component, and have excellent low-temperature fixability while maintaining friability during durability. On the other hand, the toner using the polyester resin has a poor charge rising property, and particularly has poor toner scattering and fogging performance on the image at the time of durability, high temperature and high humidity, and low temperature and low humidity, and the image density. However, by including a specific charge control agent in addition to the polyester resin, these problems are remarkably improved, and stable chargeability and high uniformity can be obtained. High-quality images can be obtained stably.

1 is a schematic diagram illustrating an example of a non-magnetic one-component developing type image forming apparatus. FIG. 2 is a cross-sectional view of a developing device that can be mounted on a non-magnetic one-component developing type image forming apparatus. 1 is a schematic diagram illustrating an example of a two-component developing type image forming apparatus.

  Hereinafter, the present invention will be specifically described.

  The toner of the present invention contains at least a binder resin containing a polyester resin, a colorant, and a charge control agent, and the charge control agent is a thiacalixarene or sulfinylated thiacalix represented by the following general formula (1). A cyclic phenol sulfide selected from arenes and sulfonylated thiacalixarenes, wherein the polyester resin is obtained by condensation polymerization of an alcohol component containing an aliphatic polyhydric alcohol and a carboxylic acid component, and in the toner It is characterized by containing substantially no tin element.

(Wherein, X represents S, SO or SO _2, Z is .n represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group is an integer of 3-9, Y is a hydrocarbon group, a halogenated hydrocarbon group, a halogen atom, —SO ₄ R ¹ or —SO ₃ R ² , R ¹ and R ² represent a hydrogen atom, a hydrocarbon group, or a metal element, Y may be the same or different.)
First, the cyclic polyphenol compound represented by the general formula (1) contained as a charge control agent will be described.

  Specific examples of the hydrocarbon group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, Isohexyl, 3-methylpentyl, ethylptyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, 1-methyloctyl, ethylheptyl , N-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethylnonyl, n-dodecyl, n-tetradecyl, n-hebutadecyl, alkyl groups such as n-octadecyl group, and polymers of ethylene, propylene and butylene Or their copolymers Ri hydrocarbon group made.

  Suitable specific examples of the unsaturated aliphatic hydrocarbon group include, for example, vinyl, aryl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, 3-methyl- Examples thereof include alkenyl such as 3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl and decenyl groups, alkynyl groups, and groups composed of polymers of acetylene, butadiene and isopropylene or copolymers thereof. Specific examples of the alicyclic hydrocarbon group include, for example, cyclobrovir, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-methylcyclooctyl, Examples thereof include cycloalkyl such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 4-methylcyclohexenyl, 4-ethylcyclohexenyl group, cycloalkenyl, cycloalkynyl group and the like.

  Suitable specific examples of the alicyclic monoaliphatic hydrocarbon group include, for example, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexylpropyl, 4-methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl, cyclopropenylbutyl, cyclobutenylethyl, cyclopentenylethyl, cyclohexenylmethyl, cycloheptenylmethyl, cyclooctenylethyl, 4-methylcyclohexyl Alkyl, alkenyl, alkynyl groups, etc. substituted with cycloalkyl, cycloalkenyl, cycloalkynyl groups, etc. such as ceninolepropyl, 4-ethylcyclohexenylpentyl group, etc. It is below.

  Suitable examples of the aromatic hydrocarbon group include aryl groups such as phenyl and naphthyl groups, 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n -Butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl, Examples include alkylaryl such as dodecylphenyl group, alkenylaryl, alkynylaryl group and the like. The alkyl part of the alkyl aryl group, the alkenyl part of the alkenyl aryl group, and the alkynyl part of the alkynyl aryl group may have a cyclic structure.

Specific examples of the aromatic monoaliphatic hydrocarbon group include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6 Aralkyl such as -phenylhexyl, 1- (4-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl, 1,1-dimethyl-2-phenylethyl group, aralkenyl, aralkynyl group, etc. Can be mentioned. The alkyl part of the aralkyl group, the alkenyl part of the aralkenyl group, and the alkynyl part of the aralkynyl group may have a cyclic structure. The halogenated hydrocarbon is preferably one in which the above hydrocarbon group is substituted with a halogen, and the type of halogen may be any of a fluorinated product, a chlorinated product, a brominated product, and an iodinated product. The halogen atom may be any of a fluorinated product, a chlorinated product, a brominated product, and an iodinated product. R ¹ and R ² are a hydrogen atom or a hydrocarbon group. As the hydrocarbon group, the above hydrocarbon groups can be applied.

In the general formula (1), the metal of R ¹ and R ² , that is, the metal of the sulfate metal salt or the sulfonate metal salt of Y is not particularly limited, but an alkali metal is preferable. Examples of the alkali metal include sodium, potassium, rubidium, cesium, frangium and the like, but sodium is preferable. Moreover, in General formula (1), n is an integer of 4-6, However, Preferably it is 4. The cyclic phenol sulfide of the general formula (1) is a thiacalixarene in which X in the general formula (1) is S, a sulfinylated thiacalixarene in which X in the general formula (1) is SO, or the general formula (1 ) Is a sulfonylated thiacalixarene in which X is SO2.

  The cyclic phenol sulfide represented by the general formula (1) is generally referred to as thiacalixarene, and can be produced by a known method (Tetrahedron, 53, 10689 (1997), Tetrahedron Lett. 38, 3971. (1997), JP-A-9-227553, JP-A-10-77282, JP-A-10-81680, JP-A-10-168078, JP-A-11-49770, JP-A-11-255766. JP, 2001-181278, JP 2000-273096, and Japanese Patent No. 3323570). Further, the residue Z in the general formula (1) can be introduced by reacting these calixarenes with an alkylating agent, an acylating agent or an alkoxycarbonylating agent in the presence of a base catalyst (Japanese Patent Laid-Open No. Hei. 10-1608078 and JP-A-11-152284). Sulfinylated thiacalixarenes as well as sulfonylated thiacalixarenes can also be produced by known methods (see WO 98/9959). In the present invention, only one type of charge control agent represented by the general formula (1) may be used, or two or more types may be used in combination.

  The charge control agent is preferably used by adjusting the volume average particle diameter to 0.05 to 5 μm.

  In particular, when used in a wet granulation method such as suspension polymerization or emulsion polymerization aggregation method, it is used at 0.05 to 1 μm, more preferably 0.05 to 0.5 μm.

  The addition amount is 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass with respect to the toner particles. It may be contained in the entire toner particle or may be localized on the surface.

  Next, specific examples of the charge control agent are shown in Table 1 below.

  Next, the polyester resin contained in the toner according to the present invention will be described. In the present invention, the toner constituting the toner contains the charge control agent, and the binder resin contains a polyester resin mainly composed of an aliphatic polyhydric alcohol compound as a polyhydric alcohol component. The above problems are improved.

  The content of the aliphatic polyhydric alcohol is 30 to 100 mol%, preferably 50 to 100 mol% in the alcohol component from the viewpoint of durability.

  As aliphatic polyhydric alcohol, C2-C18 aliphatic polyhydric alcohol, those C2-C4 alkylene oxide (addition mole number 1-16) adduct, etc. are mentioned. From the viewpoint of durability, an aliphatic polyhydric alcohol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms is preferable.

  Examples of the aliphatic polyhydric alcohol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Examples include diols such as diol, neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, 1,8-octanediol, and polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane. Of these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable.

  The alcohol component may contain a polyhydric alcohol component other than the aliphatic polyhydric alcohol having 2 to 8 carbon atoms. As the polyhydric alcohol component, polyoxypropylene (2.2) -2,2 -Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average number of moles added) such as bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1-10) Divalent aromatic alcohols such as adducts.

  As carboxylic acid components, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids and alkyls of these acids (1 carbon atom) -8) Esters and the like.

In addition, a carboxylic acid component containing fumaric acid-modified rosin and / or maleic acid-modified rosin is also preferably used. A resin derived from fumaric acid / maleic acid-modified rosin is preferable because it can be fixed at an extremely low temperature and the storage stability is improved. “Fumaric acid / maleic acid-modified rosin-derived resin” includes i) fumaric acid having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a fumaric acid-modified rosin modified with fumaric acid. A resin derived from a modified rosin, ii) a resin derived from a maleic acid modified rosin having a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a maleic acid modified rosin modified with maleic acid, and iii) Resin derived from fumaric acid / maleic acid modified rosin having a polyester unit obtained by condensation polymerization of alcohol component and fumaric acid modified rosin and carboxylic acid component containing maleic acid modified rosin is included. A resin derived from fumaric acid-modified rosin is preferred. (JP 2007-322932 A)
The fumaric acid-modified rosin preferably used in the present invention is a rosin modified with fumaric acid, and is abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, It is obtained by addition reaction of fumaric acid to rosin containing repopimaric acid as the main component, and specifically, repopimaric acid, abietic acid, neoabieticin having a conjugated double bond among the main components of rosin. It can be obtained through a Diels-Alder reaction under heating with acids and parastrinic acid and fumaric acid.

  The maleic acid-modified rosin that can be suitably used in the present invention is a rosin modified with maleic acid or maleic anhydride, and, like the fumaric acid-modified rosin, abietic acid, neoabietic acid, parastolic acid, pimaric acid, isopimar It is obtained by addition reaction of maleic acid or maleic anhydride to rosin containing acid, sandaracopimaric acid, dehydroabietic acid, repopimaric acid, etc. as a main component. It can be obtained through Diels-Alder reaction under heating with maleic acid or maleic anhydride with lepopimaric acid, abietic acid, neoabietic acid and parastrinic acid having a conjugated double bond.

  From the viewpoint of chargeability, the carboxylic acid component preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable.

  From the viewpoint of fixability, the raw material monomer preferably contains a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound. The content is preferably from 0.1 to 20 mol%, more preferably from 1 to 15 mol%, in the raw material monomer.

  The polyester resin can be produced, for example, by subjecting an alcohol component and a carboxylic acid component to condensation polymerization at a temperature of 180 to 250 ° C. in an inert gas atmosphere, if necessary, using an esterification catalyst.

  The softening point of the polyester resin is preferably 70 to 140 ° C, and more preferably 70 to 125 ° C. The glass transition point is preferably 35 to 65 ° C, more preferably 35 to 55 ° C.

  The acid value of the polyester resin is preferably 5 to 70 mgKOH / g, and the hydroxyl value is preferably 5 to 70 mgKOH / g. The hydroxyl value (OHv) is usually preferably 1 to 40 KOH mg / g, more preferably 1 to 35 KOH mg / g.

  In the toner of the present invention, as the binder resin, a resin other than polyester obtained by using a specific amount of aliphatic polyhydric alcohol as the raw material monomer described above, a styrene-acrylic resin, a mixed resin of polyester and styrene acrylic, An epoxy resin or the like may be contained. In that case, the content of the polyester resin obtained by using a specific amount of aliphatic polyhydric alcohol as a raw material monomer is more preferably 30 to 100% by mass and particularly preferably 50 to 100% by mass in the binder resin.

  Conventionally, tin compound catalysts have been used for polycondensation reactions of polyester resins, but since they contain a heavy metal called tin, they have recently become unsuitable for environmental measures, and an alternative is desired. .

  In the present invention, the specific catalyst compound replacing the tin compound catalyst includes an organometallic compound, a metal oxide, and the like, particularly an organometallic compound having a metal alcoholate skeleton. Specifically, as the specific catalytic metal element, Titanium compounds for supplying titanium include titanium alkoxides such as tetranormal butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl titanate, tetramethyl titanate, tetrastearyl titanate; titanium acylates such as polyhydroxy titanium stearate; titanium Examples thereof include titanium chelates such as tetraacetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate, and titanium triethanolaminate.

  Moreover, germanium dioxide etc. can be mentioned as a germanium compound which supplies germanium. Furthermore, examples of the aluminum compound that supplies aluminum include oxides such as polyaluminum hydroxide, aluminum alkoxide, and the like, and examples thereof include tributyl aluminate, trioctyl aluminate, and tristearyl aluminate. You may use these individually by 1 type or in combination of 2 or more types.

  As the usage-amount of a specific catalyst compound, 0.001-5.000 mass% is preferable with respect to the sum total of the polyhydric ol component and polyhydric carboxylic acid component which should form a polyester segment.

  The specific catalyst compound may be added at the start of the polycondensation reaction, or may be added during the polycondensation reaction.

  By adding a specific catalyst compound in the middle of the polycondensation reaction, the content of the specific catalytic metal element in the obtained toner can be adjusted.

  The glass transition temperature (Tg) of the obtained polyester segment is preferably 20 to 90 ° C, and particularly preferably 35 to 65 ° C.

  Moreover, it is preferable that the softening point temperature of this aromatic diol origin polyester segment is 80-220 degreeC, and it is especially preferable that it is 80-150 degreeC.

  In particular, it is preferable to use a titanium compound catalyst from the viewpoint of charging environment stability under high temperature and high humidity and low temperature and low humidity of the toner. Further, from the viewpoint of further improvement, it is preferable to use titanium alcoholates and metal alcoholates such as alkali and alkaline earth metal alkoxides, and titanium alcoholates are particularly preferable.

  A polycondensation resin composition containing a titanium compound catalyst is obtained by polycondensing a raw material monomer of a polycondensation resin in the presence of a titanium compound having high reaction activity as a catalyst.

  The content of the titanium compound catalyst in the condensation polymerization resin composition is preferably 0.005 to 4% by mass, more preferably 0.05 to 3% by mass, and particularly preferably 0.1 to 2% by mass.

  Therefore, the polycondensation resin composition in the present invention is preferably a polyester resin composition containing a titanium compound catalyst obtained by polycondensation of an alcohol component and a carboxylic acid component in the presence of a titanium compound.

The titanium compound catalyst in the present invention is not particularly limited as long as it acts as a catalyst for the polycondensation reaction of the polycondensation resin, but a titanium compound having a Ti-O bond is preferable, and the alkoxy having a total carbon number of 1 to 28 is preferred. More preferred is a compound having a group, an alkenyloxy group or an acyloxy group, which has the formula (I): Ti (X) _n (Y) _m (I)
Wherein X is a substituted amino group having 1 to 28 carbon atoms, Y is an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group or an acyloxy group, preferably an alkoxy group, and n and m are integers of 1 to 3. And the sum of n and m is 4)
And a titanium compound represented by formula (II):
Ti (Z) ₄ (II)
A titanium compound represented by (Z is an alkoxy group having 1 to 28 carbon atoms in total, an alkenyloxy group or an acyloxy group, preferably an alkoxy group, and four kinds of Z may be the same or different) is particularly preferable. The titanium compounds may be used alone or in combination.

  In the formula (I), the total number of carbon atoms of the substituted amino group represented by X is preferably 2 to 10, more preferably 4 to 8, and particularly preferably 6. The substituted amino group in the present invention is a group having a nitrogen atom that can be directly bonded to a titanium atom, and examples thereof include an alkylamino group that may have a hydroxyl group, but also a quaternary cation group. Included in the amino group, preferably a quaternary cationic group. Such an amino group can be generated, for example, by reacting titanium halide with an amine compound. Examples of such amine compounds include alkanolamine compounds such as monoalkanolamine compounds, dialkanolamine compounds, trialkanolamine compounds, and trialkyls. Examples include alkylamine compounds such as amines, among which alkanolamines are preferred, and trialkanolamines are more preferred.

  Moreover, 1-6 are preferable and, as for the total carbon number of group represented by Y, 2-5 are more preferable.

  Furthermore, from the viewpoint of the effect of the present invention, the group represented by X preferably has a larger total carbon number than the group represented by Y, and the difference in the total carbon number is preferably 1 to 6, more preferably Is 2-4.

Specific examples of the titanium compound represented by the formula (I) include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate. bis diethanol aminate _{[Ti (C 4 H 10 O 2} N) 2 (C 3 H 7 O) 2 ], titanium dipentylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 5 H 11 O) ₂ ], titanium diethylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₂ H ₅ O) ₂ ], titanium dihydroxyoctylate bistriethanolamate [Ti (C ₆ H _{14 O 3 N) 2 (OHC 8} H 16 O) 2 ], titanium distearate bis triethanolaminate _[Ti (C _{6 H 14 3 N) 2 (C 18 H} 37 O) 2 ], titanium triisopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris ( Triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamine Nate and titanium dipentylate bistriethanolamate are preferred, and these are also available, for example, as commercial products from Matsumoto Trading Co., Ltd.

  In the formula (II), the total carbon number of the group represented by Z is preferably 8 to 28, more preferably 12 to 24, and particularly preferably 16 to 20.

  In formulas (I) and (II), the group represented by Y and the group represented by Z may have a substituent such as a hydroxyl group or a halogen, but are unsubstituted or substituted with a hydroxyl group. Those based on groups are preferred, and unsubstituted ones are more preferred.

  The four groups represented by Z may be the same or different, but are preferably the same group from the viewpoint of reaction activity and hydrolysis resistance.

Specific examples of the titanium compound represented by the formula (II) include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetra Stearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate Are preferred over DOO, it, for example, titanium halides can also be obtained by reacting a corresponding alcohol.

  The toner used in the present invention will be further described.

  The toner used in the present invention preferably has a volume-based median diameter (D50v) of 2 μm or more and 8 μm or less. By setting the volume reference median diameter in the above range, for example, it is possible to faithfully reproduce a very minute dot image at a level of 1200 dpi (dpi; number of dots per inch (2.54 cm)).

  By setting the volume-based median diameter to a small diameter within the above range, it is possible to faithfully reproduce the dot image constituting the photographic image and the like, so that a high-definition color photographic image equivalent to or higher than the printed image is formed. be able to. In particular, in the printing field called “on-demand printing” where print orders are received at several hundred to several thousand levels, full-color high-quality prints containing high-definition photographic images can be quickly delivered to users. .

  The volume-based median diameter (D50v diameter) of the toner can be measured and calculated using an apparatus in which a computer system for data processing is connected to “Multisizer 3 (manufactured by Beckman Coulter)”.

  As a measurement procedure, 0.02 g of toner is blended with 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is poured into a beaker containing “ISOTONII” (manufactured by Beckman Coulter) in the sample stand with a pipette until the measured concentration reaches 5 to 10%, and the measuring machine count is set to 2500 pieces. To measure. The aperture diameter of “Multisizer 3” is 50 μm.

  The toner used in the present invention preferably has a coefficient of variation (CV value) in the volume-based particle size distribution of 2% to 21%, more preferably 5% to 15%.

  The coefficient of variation (CV value) in the volume-based particle size distribution represents the degree of dispersion in the particle size distribution of the toner particles on the volume basis, and is defined by the following equation.

CV value (%) = (standard deviation in number particle size distribution) / (median diameter (D50v) in number particle size distribution) × 100
The smaller the CV value, the sharper the particle size distribution, and the larger the toner particle size. In other words, since toners with uniform sizes can be obtained, it is possible to reproduce a fine dot image and fine lines required for digital image formation with higher accuracy. Further, when printing a photographic image, it is possible to create a high-quality photographic image having an image quality produced by printing ink or higher by using small-diameter toner having a uniform size.

  Further, the toner according to the present invention preferably has an average circularity (average value of shape factor) represented by the following formula of 0.920 to 0.995, preferably 0.930 to 0.985.

Average circularity = (circle circumference calculated from equivalent circle diameter) / (perimeter of particle projection image)
The method for measuring the average circularity is not particularly limited. For example, the toner particles are magnified 500 times with an electron microscope, a photograph is taken, and an image analysis apparatus is used from the electron micrograph image. The average circularity can be calculated by measuring the circularity of 500 toner particles and calculating the arithmetic average value thereof.

  The toner according to the present invention preferably has an average circularity of 0.920 to 0.995. More preferably, when 0.930 to 0.985, the shape of the toner used for image formation is uniform to some extent. Therefore, due to the shape of the toner particles, the chargeability is easily uniformized. Thus, the image quality is improved. That is, since the toner particles have the same shape, the developability and transferability are improved, and there is no variation in the melting and fixing of the toner at the time of fixing, and the adhesion of the external additive is also equalized and the external additive particles are used. The effect can be made uniform. Furthermore, the durability against stress during image formation is also made uniform. With these effects, it is expected that a good quality toner image with no variation in color tone or density can be obtained.

  The toner according to the present invention preferably has a softening point temperature of 121 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower.

  By setting the softening point of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, and environmentally friendly image formation that realizes reduction in power consumption is enabled. Further, it is also preferable for developing stable fixing performance even in the POD field where the present invention can be suitably used.

The softening point of the toner can be controlled by, for example, the following methods alone or in combination. That is,
(1) The type and composition ratio of monomers used for resin formation are adjusted.
(2) The molecular weight of the resin is adjusted according to the type and amount of chain transfer agent.
(3) Adjust the type and amount of wax.

Further, the method for measuring the softening point temperature of the toner is specifically “Flow Tester CFT-500 (manufactured by Shimadzu Corporation)”, molded into a columnar shape with a height of 10 mm, and at a heating rate of 6 ° C./min. While being heated, a pressure of 1.96 × 10 ⁶ Pa is applied from the plunger, and the pressure is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm. Thereby, a curve between the plunger drop amount and temperature of the flow tester (softening flow curve) ), And the temperature at the first outflow is the melting start temperature, and the temperature for the drop of 5 mm is the softening point temperature.

  The toner according to the present invention preferably has a glass transition temperature (Tg) of 55 ° C. or lower, more preferably 35 to 50 ° C.

  By setting the glass transition temperature of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, and environmentally friendly image formation that realizes a reduction in power consumption is enabled. Further, it is also preferable for developing stable fixing performance even in the POD field where the present invention can be suitably used.

  The glass transition temperature of the toner of the present invention can be measured using a DSC-7 differential scanning calorimeter (manufactured by PerkinElmer) or a TAC7 / DX thermal analyzer controller (manufactured by PerkinElmer).

  As a measurement procedure, toner 4.5 mg to 5.0 mg is precisely weighed to two decimal places, sealed in an aluminum pan (KITNO.0219-0041), and set in a DSC-7 sample holder. The reference used an empty aluminum pan. The measurement conditions were a measurement temperature of 0 ° C. to 200 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Analysis was performed based on the data in Heat.

  The glass transition temperature draws an extension of the baseline before the rise of the first endothermic peak and a tangent line indicating the maximum slope between the rise of the first peak and the peak apex, and the intersection is taken as the glass transition point. Show.

  Next, a toner manufacturing method according to the present invention will be described.

  The toner used in the present invention is composed of particles (hereinafter also referred to as colored particles) containing at least a resin and a colorant. The colored particles constituting the toner used in the present invention (base particles before the external addition treatment) are not particularly limited, and can be prepared by a conventional toner manufacturing method. . That is, a toner manufacturing method by a so-called pulverization method in which a toner is prepared through a kneading, pulverization, and classification process, an emulsion aggregation method in which polyester latex fine particles are created and aggregated to form particles while simultaneously controlling the shape and size. Further, there are a suspension granulation method in which a polyester resin is dissolved in a solvent and dispersed and granulated in an aqueous system, and a polyester elongation method by a so-called polymerization method.

A production example of a polyester latex when used in the emulsion aggregation method will be described.
(Melt dispersion method)
While maintaining the polyester resin at a temperature above the softening point (for example, the melting temperature), it may be dispersed in an aqueous medium by mechanical means, or the polyester resin may be softened under pressure in an aqueous medium as necessary. You may disperse | distribute by a mechanical means, after heating to the temperature more than a point (for example, melting temperature).

  As the mechanical means, for example, a high-speed rotation type continuous emulsification in which a ring-shaped stator having a slit and a ring-shaped rotor having a slit are coaxially provided so as to mesh with each other while maintaining a slight gap. It is preferred to use a disperser. In controlling the particle size of the particles, the particle size can be controlled to an arbitrary particle size by appropriately adjusting the number of revolutions of the disperser, the time, the heating temperature of the aqueous medium, the temperature of the resin itself, and the like. In the aqueous medium, the above-mentioned surfactant may be appropriately added for dispersion stabilization.

In order to disperse the particles stably, the surfactant or basic substance can be added to the aqueous medium or the resin melt. From the viewpoint of the charging characteristics of the toner and the stability of the resin particles. It is preferable to add a basic substance to the aqueous medium. Examples of the basic substance include inorganic basic compounds such as ammonia, potassium hydroxide, sodium hydroxide, and lithium hydroxide, and organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine. The aqueous medium is preferably water, more preferably deionized water.
(Solution dispersion method)
The polyester resin is dissolved in an organic solvent, and the obtained solution is dispersed in a water-based medium under high-speed shearing with a mixing and stirring device such as a homogenizer, and the organic solvent is removed by heating.

  Organic solvents that can dissolve polyester resins and are insoluble in water are used, and depending on the components of the polyester, hydrocarbons such as toluene, xylene, hexane, etc., usually methylene chloride, chloroform, dichloroethane, etc. Halogenated hydrocarbons, alcohols such as ethanol, butanol, benzyl alcohol ether, tetrahydrofuran, ethers, esters such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, etc. Ketones. In the aqueous medium, the above-mentioned surfactant may be appropriately added for dispersion stabilization.

  The removal of the organic solvent may be performed under reduced pressure.

  Further, the charge control agent may be contained in the toner particles or may be localized on the surface. In the case of being localized on the surface, in the wet method, after the toner particles are formed, (1) only the charge control agent is formed in the surface layer, (2) together with the resin component, and (3) the resin containing the charge control agent. It is preferable to attach or fix the fine particles.

  In the dry method, it is preferable to fix the toner surface to the toner surface by a thermal force or a mechanical impact force. As a specific apparatus, a Henschel mixer, a hybridization system, a surfing system, a mechanofusion system, or the like can be preferably used.

  When the toner is produced by a pulverization method, it is preferable to produce the toner while maintaining the temperature of the kneaded material at 130 ° C. or lower. This is because when the temperature applied to the kneaded product exceeds 130 ° C., the colorant in the kneaded product may change in the agglomerated state due to the action of heat applied to the kneaded product, and the uniform aggregated state may not be maintained. Because. If variations occur in the aggregated state, the color tone of the produced toner varies, which may cause color turbidity.

  Next, the resin, wax, colorant and the like constituting the toner according to the present invention will be described with specific examples.

  First, the resin used in combination with the polyester resin according to the present invention is not particularly limited, but there is a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below. This is a typical example. The polymer constituting the resin that can be used in the present invention is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone. Or it is the polymer produced combining multiple types.

Specific examples of vinyl polymerizable monomers are shown below.
(1) Styrene or styrene derivatives Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc. (2) Methacrylate derivatives Methyl methacrylate, methacryl Ethyl acetate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethyl methacrylate (3) Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc. (4) olefins Ethylene, propylene, isobutylene, etc. (5) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (6) Vinyl ether (7) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. (8) N-vinyl compounds N-vinyl carbazole, N-vinyl indole N- vinylpyrrolidone (9) Other vinyl naphthalene, vinyl compounds such as vinyl pyridine, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide.

  In addition, as the vinyl polymerizable monomer constituting the binder resin of the toner used in the present invention, those having an ionic dissociation group shown below can be used. For example, there are those having a functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain of the monomer.

  First, those having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. Examples of those having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of those having a phosphoric acid group include acid phosphooxyethyl methacrylate. is there.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyls. Specific examples of polyfunctional vinyls are shown below.

  Divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like.

  Examples of the colorant that can be used for the toner include the following. Specific colorants are shown below.

  As the colorant for black toner, carbon black is used, and examples thereof include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black.

  As colorants for color toners, pigments or dyes made of organic compounds are used.

  Examples of the colorant for magenta or red include C.I. I. Pigment Red 1, 2, 3, 5, 6, 7, 15, 16, 48: 1, 53: 1, 57: 1, 60, 63, 64, the same 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 139, 144, 149, 150, 163, 166, 170, 177, 178, 184, 202, 206, 207, 209, 222, 238, 269, etc.

  Examples of the colorant for orange or yellow include C.I. I. Pigment Orange 31 and 43, C.I. I. Pigment Yellow 12, 14, 15, 17, 74, 83, 93, 94, 138, 155, 162, 180, 185, and the like.

  Further, as a colorant for green or cyan, C.I. I. Pigment Blue 2, 3, 15, 15, 15: 2, 15: 3, 15: 4, 16, 17, 17, 60, 62, 66, C.I. I. Pigment Green 7 etc.

  Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 2, 6, 14, 15, 16, 19, 21, 21, 33, 44, 56, 61, 77, 79, 80, 81, 82, the same 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc.

  These colorants can be used alone or in combination of two or more as required. The addition amount of the colorant is set in the range of 1 to 30% by mass, preferably 2 to 20% by mass with respect to the whole toner.

Next, the waxes contained in the toner used in the present invention include the following.
(1) Polyolefin wax Polyethylene wax, polypropylene wax, etc. (2) Long chain hydrocarbon wax, paraffin wax, sazol wax, etc. (3) Dialkyl ketone wax, distearyl ketone, etc. (4) Ester wax Carnauba wax, Montan Wax, trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecanediol di Stearate, trimellitic trimellitic acid, distearyl maleate, etc. (5) Amide wax Ethylenediamine dibehenyl amide, trimellitic acid triste The melting point of Riruamido such as wax is usually from 40 to 125 ° C., preferably from 50 to 120 ° C., more preferably from 60 to 90 ° C.. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature. Further, the wax content in the toner is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
(Description of external additive particles)
As the external additive usable in the present invention, various inorganic oxides, nitrides, borides and the like can be suitably used. Specifically, examples of the inorganic oxide include silica, alumina, titania, zirconia, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, manganese oxide, and boron oxide. . Examples of the carbide include silicon carbide, boron carbide, and titanium carbide. Examples of the nitride include silicon nitride, titanium nitride, and boron nitride. Particularly preferably usable are ultrafine silica, alumina, titania and composite oxide particles of 5 to 50 nm produced by a vapor phase method. The composite oxide particles preferably contain a silicon atom and at least one atom of a titanium atom, an aluminum atom, a zirconium atom, and a calcium atom. In addition, anatase type, rutile type, and amorphous titania particles produced by the sulfuric acid method or the like can also be suitably used. The addition amount is 0.1 to 5.0 parts by mass, preferably 0.5 to 3 parts by mass with respect to the toner.

  As the inorganic oxide, synthetic silica fine particles can be used. Synthetic silica is produced by combustion method silica obtained by burning a silane compound (ie fumed silica), deflagration silica obtained by explosively burning metal silicon powder, sodium silicate and mineral acid. Wet silica obtained by neutralization reaction (of which, synthesized under alkaline conditions is precipitated silica, and synthesized under acidic conditions is gel silica), sol-gel silica obtained by hydrolysis of hydrocarbyloxysilane (so-called Stober) Law). In the present invention, any type can be used. In particular, silica produced by a sol-gel method having a uniform particle size and shape can be preferably used. The addition amount is 0.1 to 8.0 parts by mass, preferably 0.5 to 5 parts by mass with respect to the toner.

  These external additive compounds are preferably surface-treated with a known treatment agent such as a coupling agent, and specific treatment agents for surface treatment include the following.

  Silane coupling agent, titanate coupling agent, silicone oil, silicone varnish, fluorine silane coupling agent, fluorine silicone oil, amino group / quaternary ammonium salt-containing coupling agent, modified silicone oil and the like.

  In order to further improve the cleaning property and transfer property, it is also possible to use a higher fatty acid metal salt called a so-called lubricant in combination. Specific examples of the higher fatty acid metal salt include the following. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid There are salts of zinc, calcium and the like, and zinc and calcium of ricinoleic acid.

  In addition, titanate compounds such as strontium titanate, calcium titanate, magnesium titanate, and barium titanate can be used in combination. Furthermore, organic particles can be used in addition to the inorganic particles. Specifically, small-diameter external additive particles made of a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used. In addition to the inorganic particles, it is also possible to use known organic fine particles having an average primary particle size of about 10 to 2000 nm, specifically, a small diameter made of a homopolymer such as styrene or methyl methacrylate or a copolymer thereof. External additive particles can be used.

The amount of these external additives added to the toner is preferably 0.3 to 10.0 parts by mass as the total amount of the above-mentioned external additives. More preferably, it is 0.5-5.0 mass%. Moreover, as an addition method of an external additive, the method of adding using various well-known mixing apparatuses, such as a Turbuler mixer, a Henschel mixer, a Nauta mixer, and a V-type mixer, is mentioned.
<Developer>
The toner of the present invention may be used, for example, as a one-component magnetic toner containing a magnetic material, as a two-component developer mixed with a so-called carrier, or as a non-magnetic toner alone. Any of these can be suitably used.

  In the toner of the present invention, when used as a two-component developer mixed with a carrier, it is possible to suppress the occurrence of toner filming (carrier contamination) on the carrier, and when used as a one-component developer, The occurrence of toner filming on the frictional charging member of the apparatus can be suppressed.

  As the carrier constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. It is particularly preferable to use ferrite particles.

  The carrier preferably has a volume average particle diameter of 15 to 100 μm, more preferably 20 to 50 μm. The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

As the carrier, it is preferable to use a carrier coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicon resin, ester resin, or fluorine-containing polymer resin is used. Moreover, it does not specifically limit as resin for comprising a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin etc. are used. be able to.
<Image forming method>
The above toner can be used in both the non-contact heating method and the contact heating method. Among these, it can be suitably used for an image forming method including a fixing step by a contact heating method. Specifically, as an image forming method, an electrostatic latent image formed electrostatically on, for example, an image carrier using the toner as described above, and a developer in a developing device by a friction charging member. By revealing the toner image by charging to obtain a toner image, transferring the toner image to the recording material, and then fixing the toner image transferred on the recording material to the recording material by a contact heating type fixing process, A visible image is obtained.
<Fixing method>
Examples of the contact heating method include a heat pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.

  In the fixing method of the hot roll fixing method, usually, an upper roller provided with a heat source inside a metal cylinder made of iron or aluminum whose surface is coated with fluororesin, etc., and a lower roller formed of silicon rubber or the like Is used.

  As the heat source, a linear heater is used, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. by this heater. A pressure is applied between the upper roller and the lower roller, and the lower roller is deformed by this pressure, so that a so-called nip is formed in the deformed portion. The width of the nip is 1 to 10 mm, preferably 1.5 to 7 mm. The fixing linear velocity is preferably 40 mm / sec to 600 mm / sec. If the nip width is too small, heat cannot be uniformly applied to the toner, and uneven fixing may occur. On the other hand, if the nip width is too large, it is contained in the toner particles. The melting of the polyester resin is accelerated, and there is a possibility that fixing offset occurs.

  According to the toner as described above, the toner particles constituting the toner are made of polyester resin, and have a specific small particle size, so that basically a high quality image can be obtained and a specific sharp particle size dispersion is obtained. By having a degree, it is possible to suppress the presence of toner particles having excessively small particle sizes or large toner particles, and high adhesion between toner particles can be obtained during fixing.

  Even in a state where power consumption is reduced, a high image density and a wide color reproduction range can be obtained, and a high-quality image can be obtained.

  The image forming method according to the present invention is an image forming method for forming a toner image using color toner and black toner. In other words, it is applied to a two-component developing type image forming method using a two-component developer mixed with a carrier and a one-component developing type color image forming method using a non-magnetic one-component developer not using a carrier. can do.

  Among these, in the image formation of the non-magnetic one-component development method in which image formation is performed without using a carrier, the toner is rubbed and pressed against the charging member and the developing roller surface during image formation to be charged. As described above, in the image formation by the non-magnetic one-component development system, since the dedicated means for charging the toner is not provided, the structure of the developing device can be simplified, which is advantageous for realizing a compact image forming apparatus. By using the configuration according to the present invention, a non-magnetic one-component development type image forming method using a compact full-color image forming apparatus can balance a black image and a color image even in a space-limited working environment. Full color prints can be produced.

  Also, in non-magnetic one-component development type image formation, toner is charged at the nip formed by the surface of the regulating member and the developing roller. When the nip width is narrowed, the time for friction charging is shortened accordingly. Therefore, efficient toner charging is required.

  Further, a strong pressing force is easily applied to the toner on the developing roller, and the toner particles are easily damaged and the external additive is easily peeled off.

  Further, the toner of the present invention makes it difficult for the toner particles to adhere to the developing roller and the toner layer thickness regulating member, so it is considered that contamination due to toner adhesion can also be prevented.

  Furthermore, as described above, the present invention can also be applied to a two-component image forming method using a two-component developer composed of a carrier and a toner, which is called a so-called hybrid developing method or trickle developing method. The present invention can also be applied to an image forming method in which a toner image is formed through a development method.

  FIG. 1 shows an example of an image forming apparatus that can carry out the image forming method according to the present invention. As described above, the image forming method according to the present invention is not realized only by the image forming apparatus having the configuration shown in FIG. The image forming apparatus shown in FIG. 1 is a full-color image forming apparatus in which the developing device 20 shown in FIG. 2 can be mounted. The image forming apparatus on which the developing device 20 shown in FIG. 2 can be mounted is not limited to that shown in FIG. For example, the present invention can be applied to an image forming apparatus called a tandem type having a structure in which developing devices 20 described later are arranged in series.

  The image forming apparatus shown in FIG. 1 has a needle electrode charging type charging device 16 that uniformly charges the surface of the photosensitive drum 15 to a predetermined potential around the photosensitive drum 15 that is rotationally driven, and residual toner on the photosensitive drum 15. A cleaner 17 to be removed is provided.

  The laser scanning optical system 18 scans and exposes the photosensitive drum 15 uniformly charged by the charging device 16 to form an electrostatic latent image on the photosensitive drum 15. The laser scanning optical system 18 includes a laser diode, a polygon mirror, and an fθ optical element, and print data for each of yellow, magenta, cyan, and black is transferred from the host computer to the control unit. Based on the print data of each color, a laser beam is sequentially output, and the photosensitive drum 15 is scanned and exposed to form an electrostatic latent image for each color.

  The developing device unit 30 containing the developing device 20 supplies each color toner to the photosensitive drum 15 on which the electrostatic latent image is formed to perform development. The developing device unit 30 is provided with four developing devices 20Y, 20M, 20C, and 20Bk each containing non-magnetic one-component toners of yellow, magenta, cyan, and black around the support shaft 33. Rotating to the center, each developing device 20 is guided to a position facing the photosensitive drum 15.

  The developing device unit 30 rotates around the support shaft 33 each time an electrostatic latent image of each color is formed on the photosensitive drum 15 by the laser scanning optical system 18 and stores the corresponding color toner. 20 is guided to a position facing the photosensitive drum 15. Then, each of the developing devices 20Y, 20M, 20C, and 20Bk sequentially supplies the charged color toners onto the photosensitive drum 15 to perform development.

  In the image forming apparatus shown in FIG. 1, an endless intermediate transfer belt 40 is provided downstream of the developing device unit 30 in the rotation direction of the photosensitive drum 15, and is driven to rotate in synchronization with the photosensitive drum 15. The intermediate transfer belt 40 comes into contact with the photosensitive drum 15 at a portion pressed by the primary transfer roller 41 and transfers the toner image formed on the photosensitive drum 15. Further, a secondary transfer roller 43 is rotatably provided so as to face the support roller 42 that supports the intermediate transfer belt 40, and the portion on the intermediate transfer belt 40 is opposed to the support roller 42 and the secondary transfer roller 43. The toner image is pressed and transferred onto the recording material S such as recording paper.

  A cleaner 50 that removes residual toner on the intermediate transfer belt 40 is provided between the developing device unit 30 and the intermediate transfer belt 40 so as to be able to contact and separate from the intermediate transfer belt 40.

  A paper feeding unit 60 that guides the recording material S to the intermediate transfer belt 40 includes a paper feeding tray 61 that houses the recording material S, and a paper feeding roller 62 that feeds the recording material S stored in the paper feeding tray 61 one by one. It comprises a timing roller 63 that feeds the fed recording material S to the secondary transfer site.

  The recording material S on which the toner image is pressed and transferred is conveyed to the fixing device 70 by a conveying means 66 constituted by an air suction belt or the like, and the toner image transferred by the fixing device 70 is fixed on the recording material S. After fixing, the recording material S is transported through the vertical transport path 80 and discharged onto the upper surface of the apparatus main body 100.

  Next, as an example of a developing device that can be used in the image forming method according to the present invention, a developing device of a non-magnetic one-component developing system shown in FIG. 2 will be described. The developing device 20 is also referred to as a “toner cartridge” and has a unit form in which constituent members such as a developing roller are integrally disposed in addition to a toner storage portion that stores toner, and the device is loaded into the image forming apparatus as it is. It is designed so that toner can be supplied.

  The developing device 20 includes a developing roller 10, a buffer chamber 22 provided on the left side of the developing roller 10, and a hopper 23 adjacent to the buffer chamber 22. The hopper 23 corresponds to the toner storage portion described above. The developing roller 10 is rotationally driven in a counterclockwise direction in the drawing by a motor (not shown), and contacts or approaches an image carrier that is incorporated in an image forming apparatus (not shown).

  In the buffer chamber 22, a blade 24 as a toner layer regulating member is disposed in pressure contact with the developing roller 10. Here, the blade 24 regulates the toner layer thickness and functions as a charge imparting member that charges the toner carried on the developing roller. Further, a supply roller 26 is pressed against the developing roller 10. The supply roller 26 supplies toner to the surface of the developing roller 10 by being driven to rotate in the same direction as the developing roller 10 (counterclockwise direction in the drawing) by a motor (not shown). The supply roller 26 has a conductive cylindrical substrate and a foam layer formed of urethane foam or the like on the outer periphery of the substrate.

  The blade 24 that is a toner layer regulating member regulates the charge amount and adhesion amount of the toner on the developing roller 10. In addition, an auxiliary blade 25 that assists in regulating the charge amount and adhesion amount of toner on the developing roller 10 can be further provided on the downstream side of the blade 24 with respect to the rotation direction of the developing roller 10.

  The blade 24 that also functions as a charge imparting member forms a uniform thin layer of toner on the developing roller and triboelectrically charges the toner. The blade 24 is made of a member having a certain degree of elasticity, and forms a thin layer of toner on the developing roller by contacting the developing roller. The blade 24, which is a toner layer regulating member, uses stainless steel or phosphor bronze as it is, and those whose surfaces are coated with a urethane resin or an epoxy resin, or an inorganic compound such as silica or titanic acid compound by a sol-gel method or the like. A coated one can be used. In addition, an elastic material having a hardness defined by JIS A, such as silicon rubber and urethane rubber, of 40 ° to 90 ° can also be used.

  The toner thin layer formed on the developing roller has a maximum thickness of 10 toner particles, preferably 5 or less. Specifically, the peripheral speed of the electrostatic latent image carrier 11 is 100 mm / sec, the peripheral speed of the developing roller 10 is 200 mm / sec, and the pressing force of the toner regulating member 24 to the developing roller 10 is 10 to 100 N / m. In this case, a layer having a thickness of about 1.5 toner particles can be formed.

  Further, the contact force of the blade 24 to the developing roller is preferably 100 mN / cm to 5 N / cm, and particularly preferably 200 mN / cm to 4 N / cm. By setting the contact force within this range, the toner can be conveyed without causing unevenness in conveyance, so that the occurrence of image defects such as white stripes can be avoided. Further, by setting the contact force within the above range, the toner layer can be formed on the developing roller and friction charging can be performed without deforming or crushing the toner.

  In this way, in the developing device 20, the developing roller 10 and the blade 24, which is a toner layer regulating member, are disposed so as to contact each other, and a thin layer of toner is formed on the developing roller by the toner layer regulating member. Then, the toner that is thinned on the developing roller and frictionally charged is supplied onto the image carrier, whereby the electrostatic latent image formed on the image carrier can be visualized.

  A hopper 23 constituting the developing device 20 contains toner T as a one-component developer. The hopper 23 is provided with a rotating body 27 for stirring the toner T. A film-like conveying blade is attached to the rotating body 27, and the toner T is conveyed by the rotation of the rotating body 27 in the direction of the arrow. The toner T conveyed by the conveying blades is supplied to the buffer chamber 22 through a passage 28 provided in a partition wall that separates the hopper 23 and the buffer chamber 22. The shape of the conveying blade is bent while conveying the toner T in front of the rotation direction of the blade as the rotating body 27 rotates, and returns to a straight state when the left end of the passage 28 is reached. In this way, the blades supply the toner T to the passage 28 by making the shape return straight after passing through the curved state.

  The passage 28 is provided with a valve 281 for closing the passage 28. This valve is a film-like member, one end of which is fixed to the upper side of the right side of the passage 28 of the partition wall. When the toner T is supplied from the hopper 23 to the passage 28, the valve 28 is pushed rightward by the pressing force from the toner T. Is supposed to open. As a result, the toner T is supplied into the buffer chamber 22.

  In addition, a regulating member 282 is attached to the other end of the valve 281. The regulating member 282 and the supply roller 26 are arranged so as to form a slight gap even when the valve 281 closes the passage 28. The regulating member 282 adjusts so that the amount of toner accumulated at the bottom of the buffer chamber 22 does not become excessive, so that a large amount of toner T collected from the developing roller 10 to the supply roller 26 does not fall to the bottom of the buffer chamber 22. Adjusted to

  In the developing device 20, the developing roller 10 is rotationally driven in the direction of the arrow during image formation, and the toner in the buffer chamber 22 is supplied onto the developing roller 10 by the rotation of the supply roller 26. The toner T supplied onto the developing roller 10 is charged and thinned by a blade 24 and an auxiliary blade 25, and then conveyed to a region facing the image carrier to develop an electrostatic latent image on the image carrier. To be served. The toner that has not been used for development returns to the buffer chamber 22 as the developing roller 10 rotates, and is scraped and collected from the developing roller 10 by the supply roller 26.

  The developing bias power supply 29 provided in the developing device 20 forms an alternating electric field (for example, Vpp is 2.0 kV, frequency 2 kHz) with a DC voltage power source that outputs a set value (for example, about 500 V) of the developing bias voltage Vb. It consists of an AC power supply. “Vpp” indicates a peak-to-peak voltage that is the difference between the peak and valley of the amplitude of the alternating voltage waveform.

  At the time of image formation, the electrostatic latent image carrier 11 is uniformly charged to a potential of, for example, about 800 V by a charging device (not shown), and then a predetermined portion is exposed by an optical head such as a laser. An electrostatic latent image is formed by being attenuated to a potential of about 100V.

In the developing region, the toner formed in a thin layer on the developing roller 10 flies from the circumferential surface of the developing roller 10 by the action of an electric field formed by the developing bias voltage Vb applied from the developing bias power supply device 29 and an alternating voltage. To become a cloud cloud. Then, by supplying toner onto the electrostatic latent image carrier on which the electrostatic latent image is formed, the electrostatic latent image is developed and a toner image is formed.
(Description of two-component development type image forming apparatus)
The image forming method according to the present invention can also be performed using a two-component developer composed of a toner and a carrier.

  FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus capable of forming a full-color image using a two-component developer.

  This image forming apparatus is called a tandem color image forming apparatus, and includes a plurality of sets of image forming units 20Y, 20M, 20C, and 20K, an endless belt-shaped intermediate transfer body unit 4 as a transfer unit, and a recording member P. It has an endless belt-shaped paper feeding and conveying means 21 for conveyance and a heat roll type fixing device 70 as a fixing means. A document image reading device SC is disposed above the main body A of the image forming apparatus.

  An image forming unit Y that forms a yellow image as one of the different color toner images formed on each photoconductor is arranged around a drum-shaped photoconductor 15Y as the first photoconductor and the photoconductor 15Y. The charging unit 16Y, the exposure unit 18Y, the developing unit 20Y, the primary transfer roll 41Y as the primary transfer unit, and the cleaning unit 50Y are included. In addition, an image forming unit M that forms a magenta image as one of toner images of different colors is a drum-shaped photoconductor 15M as a first photoconductor, and a charge disposed around the photoconductor 15M. Means 16M, exposure means 18M, development means 20M, primary transfer roll 41M as primary transfer means, and cleaning means 50M. In addition, an image forming unit C that forms a cyan image as one of toner images of different colors is a drum-shaped photoconductor 15C as a first photoconductor, and a charge disposed around the photoconductor 15C. Means 16C, exposure means 18C, development means 20C, primary transfer roll 41C as primary transfer means, and cleaning means 50C.

  Further, an image forming portion K that forms a black image as one of other different color toner images is disposed around a drum-shaped photoconductor 15K as a first photoconductor, and the photoconductor 15K. It has a charging means 16K, an exposure means 18K, a developing means 20K, a primary transfer roll 41K as a primary transfer means, and a cleaning means 50K.

  The endless belt-shaped intermediate transfer body unit 4 has an endless belt-shaped intermediate transfer body 40 as an intermediate transfer endless belt-shaped second image carrier that is wound around a plurality of rolls and is rotatably supported.

  The respective color images formed by the image forming units Y, M, C, and K are sequentially transferred onto the rotating endless belt-shaped intermediate transfer body 40 by the primary transfer rolls 41Y, 41M, 41C, and 41K to be combined. A colored image is formed. A recording member S such as a sheet as a transfer material accommodated in the sheet feeding cassette 60 is fed by a sheet feeding / conveying means 61, passes through a plurality of intermediate rolls 62A, 62B, 62C, 62D, and a registration roll 63, and then is secondary. It is conveyed to secondary transfer rolls 43A and 43B as transfer means, and color images are transferred onto the recording member S at once. The recording member S to which the color image has been transferred is fixed by the heat roll type fixing device 70, is sandwiched between the paper discharge rolls 75, and is placed on the paper discharge tray 76 outside the apparatus.

  On the other hand, after the color image is transferred to the recording member P by the secondary transfer rolls 43A and 43B, the residual toner is removed by the cleaning unit 48 from the endless belt-shaped intermediate transfer body 40 in which the recording member S is separated by curvature.

  During the image forming process, the primary transfer roll 41K is always in pressure contact with the photoreceptor 15K. The other primary transfer rolls 41Y, 41M, and 41C are in pressure contact with the corresponding photoreceptors 15Y, 15M, and 15C, respectively, only during color image formation.

  The secondary transfer rolls 43A and 43B are in pressure contact with the endless belt-shaped intermediate transfer body 40 only when the recording member S passes through the secondary transfer rolls 43A and 43B.

  In this way, a toner image is formed on the photoreceptors 15Y, 15M, 15C, and 15K by charging, exposure, and development, and the toner images of the respective colors are superimposed on the endless belt-shaped intermediate transfer body 40, and are collectively applied to the recording member P. The image is transferred and fixed by the fixing device 70 by pressing and heating. The photoconductors 15Y, 15M, 15C, and 15K after the toner image is transferred to the recording member S are cleaned by the cleaning device 50 after the toner remaining on the photoconductor is transferred, and then the charging, exposure, and development cycle described above. The next image formation is performed.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to said aspect, A various change can be added.

  Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples.

(Tiacalixarene: Preparation Example of Compound No. 50)
In a eggplant-shaped flask equipped with a reflux condenser, 100 g of the compound A obtained in Example 1 was dissolved in 3 L of chloroform, 5 L of acetic acid and 200 g of sodium perborate were added, and the mixture was stirred at 50 ° C. for 18 hours. After allowing to cool, the product was extracted from the resulting reaction solution with chloroform. The chloroform phase was washed with 2N hydrochloric acid, dried over anhydrous magnesium sulfate, and chloroform was distilled off to obtain a white powder. This was recrystallized from benzene-methanol to give 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrasulfonyl [1.9. 3.1.1 ^3,7 1 ^9.13 1 ^15,19 ] Octacosa-1 (25), 3, 5, 7 (28), 9, 11, 13 (27), 15, 17, 19 (26 ) 21,23-dodecaene (compound 50; in the general formula (1), X = SO ₂ , Y = tert-butyl, Z = H, n = 4) was obtained.

(Tiacalixarene: Preparation Example of Compound No. 40)
After washing 50 g of NaH (60 mass% mineral oil solution) with anhydrous n-hexane, 500 ml of anhydrous dimethylformamide was added and stirred. 100 g of the compound A obtained in Example 1 was dissolved in 5 L of anhydrous toluene, and this was dropped into the dispersion solution. After stirring at room temperature for 2 hours, 500 L of methyl iodide was added, and the mixture was further stirred at room temperature for 2 hours, then at 60 ° C. for 30 minutes, at 80 ° C. for 1 hour, and heated to reflux at 120 ° C. for 2 hours. After standing to cool, 5 L of 1N hydrochloric acid was added thereto and extracted with toluene. This solution was washed with a 10% by mass aqueous sodium thiosulfate solution and further with distilled water, and the solvent was distilled off to obtain 130 g of a reaction product. The reaction mixture was washed with methanol and then with acetone. The insoluble content of the residue was dissolved in chloroform, the insoluble content was removed by filtration, and the solvent was distilled off to obtain 113 g of white crystals. The crude product was further dissolved in chloroform, 5 L of acetone was added, and the precipitated crystals were filtered to obtain 5,11,17,23-tetra-tert-butyl-25,26,27,28- Tetramethoxy-2,8,14,20-tetrathia [1.9.3.1.1 ^3,7 1 ^9.13 1 ^15,19 ] octacosa-1 (25), 3,5,7 (28), 9, 11, 13 (27), 15, 17, 19 (26), 21,3-dodecaene (compound 40; in the general formula (1), X = S, Y = tert-butyl, Z = CH ₃ , n = 4) was obtained.
(1) Preparation of “external additive particles (a) to (su)” The following “small-diameter external additive particles (a) to (su)” were prepared. That is,
Small-diameter external additive particles (A); silica particles having a number average primary particle size of 7 nm Small-diameter external additive particles (A); silica particles having a number-average primary particle size of 13 nm Small-diameter external additive particles (U); Silica particles having a secondary particle size of 21 nm Small external additive particles (D); silica particles having a number average primary particle size of 40 nm The silica was hydrophobized with HMDS.

Small-diameter external additive particles (v); anatase-type titania particles having a number average primary particle size of 15 nm Small-diameter external additive particles (f); rutile-type hydrophobic titania having a number-average primary particle size of 35 nm Hydrophobization treatment was performed with butyltrimethoxysilane.

Large-diameter external additive particles (G); Number average primary particle size 55 nm hydrophobic silica Large-diameter external additive particles (K); Number-average primary particle size 80 nm hydrophobic silica Large-diameter external additive particles (K); Number average primary particle size 110 nm hydrophobic silica Large diameter external additive particles (co); Number average primary particle size 150 nm hydrophobic silica Large diameter external additive particles (sa); Number average primary particle size 250 nm hydrophobic silica As described above, the silica was hydrophobized with HMDS.

Large diameter external additive particles (f); number average primary particle size 120 nm calcium titanate Large diameter external additive particles (su); number average primary particle size 330 nm calcium titanate Above, calcium titanate is treated with silicone oil The hydrophobization treatment was performed.
(Example of production of 50 to 300 nm external additive)
(Preparation of silica particles)
In a glass reactor equipped with a stirrer, a dropping funnel, and a thermometer, 623.7 g of methanol, 41.4 g of water, and 49.8 g of 28 mass% aqueous ammonia were mixed. The resulting solution was adjusted to 35 ° C., and while stirring, 1163.7 g (7.65 mol) of tetramethoxysilane and 418.1 g of 5.4% by mass ammonia water were simultaneously added. Ammonia water was added dropwise over 6 hours over 6 hours. Even after the dropping was finished, the mixture was further stirred for 0.5 hours for hydrolysis to obtain a methanol-water dispersion of hydrophilic spherical silica particles.

The methanol-water dispersion was subjected to hydrophobic treatment by adding 484 g (3 mol) of hexamethyldisilazane at room temperature to obtain silica particles.
(Preparation of silica particles, ku, ko, sa)
By changing the dripping conditions in the production conditions of silica particles, hydrophobic silica, ki, k, k, and sa having primary particle average particle sizes of 55, 80, 150, and 250 nm were obtained.
(Production Examples A to F of polyester resin)
A reflux condenser that was passed through cold water with a carboxylic acid component other than the alcohol component, trimellitic anhydride, and esterification catalyst shown in Table 2, and a reflux condenser that was passed through cold water, and a fractionation pipe that passed warm water at 98 ° C., a nitrogen inlet pipe , Put into a 5 liter four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, and after condensation polymerization at 160 ° C. for 2 hours under a nitrogen atmosphere, the temperature was raised to 210 ° C. over 6 hours. Thereafter, the reaction treatment was performed at 66 kPa until the reaction rate reached 90%. Then, after cooling to 200 ° C., trimellitic anhydride shown in Table 2 is added, reacted at normal pressure (101 kPa) for 1 hour, then heated again to 210 ° C., and reaches a desired softening point at 40 kPa. Polymerization reaction was carried out to obtain polyester resins A to F having the physical properties described in Table 2.
(Production example of maleic acid-modified rosin)
Purified rosin 6084 g (18 mol) and maleic anhydride 529 g (5.4 mol) were added to a 10 L flask equipped with a fractionation tube, reflux condenser and receiver, and the temperature was raised from 160 ° C. to 220 ° C. over 8 hours. After warming and reacting at 220 ° C. for 2 hours, distillation was further performed at 220 ° C. under a reduced pressure of 5.3 kPa to obtain a maleic acid-modified rosin. The degree of maleic acid modification of maleic acid was 50.
(Production example of fumaric acid-modified rosin)
Purified rosin (5408 g, 16 mol), fumaric acid (928 g, 8 mol) and t-butylcatechol (0.4 g) were added to a 10 L flask equipped with a fractionation tube, a reflux condenser and a receiver. After heating for 2 hours and reacting at 200 ° C. for 2 hours, distillation was further performed under a reduced pressure of 5.3 kPa to obtain a fumaric acid-modified rosin. The degree of fumaric acid modification of the fumaric acid modified rosin was 100.

(Example of production of toner base particles)
(1) Preparation of “Cyan Toner Base Particles 1C to 5C” The following compounds were sufficiently mixed with a “Henschel mixer (Mitsui Miike Mining Co., Ltd.)” and then a twin-screw extrusion kneader “PCM-30 (Ikegai Iron Works Co., Ltd.) The product from which the discharge part of “made” was removed was melt-kneaded and then cooled.

Polyester resin A 100 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by mass Pentaerythritol behenate 6 parts by mass Charge control agent (Compound 29) 3 parts by mass The obtained kneaded product was cooled with a cooling belt and then coarsely pulverized with a feather mill. Thereafter, the pulverization is carried out with a mechanical pulverizer “KTM (manufactured by Kawasaki Heavy Industries, Ltd.)” to an average particle size of 9 to 10 μm. The pulverization and coarse powder classification were performed until the thickness became 9 μm. Then, using a rotor type classifier (Teplex type classifier type “100ATP (manufactured by Hosokawa Micron Corporation)) from the coarse powder classifier, the volume-based median diameter is 5.9 μm and the average circularity is 0.955. “Cyan toner base particles 1C” were prepared, and the “cyan toner base particles 1C” were prepared, and the conditions of pulverization and classification were changed. Mother particles 2C to 5C ”were prepared.

Preparation of “Cyan toner base particles 6C to 22C” In the toner base particle production example 1C, the charge control agent was changed to the following comparative compound 52 to prepare cyan toner base particles 21C. Toners 6C to 20C having physical properties shown in Table 3 were prepared in the same manner except that the compound shown in 3 was changed.

  Further, toner base particles 22C were obtained in the same manner except that no charge control agent was added.

Preparation of “Cyan toner base particles 23C to 27C” In the toner base particle production example 1C, toners 22C to 22 having physical properties shown in Table 3 are obtained in the same manner except that the resin A used is changed to B to F. 27C was created.
(2) Preparation of “Yellow toner base particles 1Y to 27Y” “C.I. Pigment Blue 15: 3” used in the preparation of “Cyan toner base particles 1C to 27C” was used instead of “C.I. “Yellow toner base particles 1Y to 27Y” having the physical properties shown in Table 4 were prepared in the same procedure except that “I. Pigment Yellow 180” was used.

(3) Preparation of “Magenta Toner Base Particles 1M to 27M” The same procedure except that colorant “CI Pigment Red 57: 1” was used in the preparation of “Cyan Toner Base Particles 1C to 27C”. “Magenta toner base particles 1M to 27M” having physical properties shown in Table 5 were prepared.

(4) Preparation of “Black toner base particles 1K to 27K” In the preparation of “Cyan toner base particles 1C to 27C”, the colorant “carbon black (Mogal L: manufactured by Cabot Corp.) 8 parts by mass” was used. By the same procedure, “black toner base particles 1K to 27K” having physical properties shown in Table 6 were produced.

(5) “Preparation of toner base particles 28C, 28Y, 28M, 28K”
To 100 parts of toner base particles 1C, 1Y, 1M, and 1K, 0.8 part by weight of hydrophobic silica was added, and a mixing process was performed for 90 seconds at a peripheral speed of 30 m / sec using a Henschel mixer. Each of the obtained toners was subjected to a surface treatment under the following conditions using a surface modification device (surfing system; manufactured by Nippon Pneumatic Industry Co., Ltd.), whereby toner base particles 28C, 28Y, and toner particles 28C, 28Y, 28M and 28K were obtained.

Surface conditions are: maximum temperature: 250 ° C., residence time: 0.5 seconds, powder dispersion concentration: 100 g / m ³ , cooling air temperature: 18 ° C., cooling water temperature: 20 ° C.
(6) “Preparation of toner base particles 29C, 29Y, 29M, 29K”
To 100 parts of the toner base particles 22C, 0.3 part by weight of hydrophobic silica and 0.5 part by weight of the charge control agent (compound 51) of the present invention are added, and a Henschel mixer is used for 90 seconds at a peripheral speed of 30 m / sec. A mixing process was performed. The obtained particles are subjected to a surface treatment at 6000 rpm for 3 minutes using a hybridization system (NHS-3 type; manufactured by Nara Machinery Co., Ltd.) to immobilize the charge control agent on the surface of the toner base material, and thus toner base particles 29C for toner. Got. Similarly, 29Y and 29M toner base particles shown in Tables 3 to 6 were obtained. For 29K, the toner base particles were prepared in the same manner as 29C, with the addition amount of the charge control agent being 1.0 parts by mass.
(7) “Preparation of toner base particles 30C, 30Y, 30M, and 30K”
(Preparation of resin fine particle dispersion)
In a 5-liter stainless steel kettle, 600 g of the above polyester A and 6 g of a nonionic surfactant [“Emulgen 430 (manufactured by Kao)”, polyoxyethylene oleyl ether (HLB: 16.2)], anionic 20 g of surfactant [“Neopelex G-15 (manufactured by Kao Corporation)”, sodium dodecylbenzenesulfonate (concentration: 15% by mass)] and 252 g of potassium hydroxide aqueous solution (concentration: 5% by mass) as a neutralizing agent In addition, the dispersion was carried out at 95 ° C. and normal pressure (101.3 kPa) under stirring at 250 r / min with a Kai-type stirrer. The contents were stirred for 2 hours after reaching 95 ° C., and then 1118 g of deionized water was added dropwise at a rate of 6 g / min with stirring at 200 r / min with a chi-type stirrer, and the volume average particle size was reduced to 200 nm. Resin fine particle dispersion 1 was obtained.
(Preparation of release agent particle dispersion)
Ester wax (WEP-5, manufactured by NOF Corporation) 50 parts by weight Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by weight Ion-exchanged water 200 parts by weight After heating to ℃ and sufficiently dispersing with IKA's Ultra Turrax T50, it was dispersed with a pressure discharge type homogenizer to obtain a release agent particle dispersion having a volume average particle size of 210 nm and a solid content of 20% by mass. .
(Preparation of charge control agent particle dispersion)
Compound 50 20 parts by weight Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by weight Ion-exchanged water 200 parts by weight Disperse the above components sufficiently with IKA Ultra Turrax T50 at room temperature After that, dispersion treatment was performed with a pressure discharge type homogenizer to obtain a release agent particle dispersion having a volume average particle size of 180 nm and a solid content of 10% by mass.
(Preparation of colorant dispersion)
80 parts by mass of an anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to 3200 parts by mass of ion-exchanged water, and this was stirred and dissolved to prepare a surfactant solution (aqueous medium). . The following colorant was gradually added while stirring the surfactant solution.

C. I. Pigment Blue 15: 3 400.0 parts by mass After adding the above colorant, using a stirrer “CLEARMIX (M Technique Co., Ltd.)”, a dispersion treatment is performed until the particle size of the colorant becomes 200 nm or less. A colorant dispersion was prepared. The resulting colorant dispersion is designated as “Colorant Dispersion C”. The volume-based median diameter was 132 nm.

  In place of “CI Pigment Blue 15: 3” used in the preparation of “Colorant Particle Dispersion C”, the yellow colorant “CI Pigment Yellow 74” was changed to 400 parts by mass. Prepared a yellow “colorant particle dispersion Y” by the same procedure. The volume-based median diameter was 152 nm.

  Also, instead of “CI Pigment Blue 15: 3” used in the preparation of the “Colorant Particle Dispersion C”, the magenta colorant “CI Pigment Red 122” is changed to 400 parts by mass. A magenta “colorant particle dispersion M” was prepared in the same manner as described above. The volume-based median diameter of the magenta colorant particle M was 154 nm.

Further, in the preparation of the “cyan colorant particle dispersion C”, 80 parts by mass of an anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are added to 120 parts by mass, “CI Pigment Blue 15: “Black colorant particle dispersion liquid K” was prepared by the same procedure except that carbon black “Regal 330R (manufactured by Cabot)” was changed to 800 parts by mass in place of “3”. The volume-based median diameter was 139 nm.
(Preparation of toner base particles 30C)
Resin fine particle dispersion 1 200 parts by mass (60 g)
Colorant particle dispersion C 38 parts by mass (4.1 g)
Release agent particle dispersion 60 parts by mass (12 g)
Polyaluminum chloride 0.4 parts by mass Ion-exchanged water 100 parts by mass After thoroughly mixing and dispersing the above ingredients in a round stainless steel flask using a stirrer “CLEAMIX (M Technique Co., Ltd.)” The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 70 parts by mass of the resin fine particle dispersion 1 was gently added thereto. Further, 5 g of the charge control agent particle dispersion was added. Then, after adjusting the pH in the system to 8.0 using an aqueous sodium hydroxide solution having a concentration of 0.5 mol / L, the stainless steel flask is sealed, and the stirring shaft seal is magnetically sealed while stirring is continued. Heat to 90 ° C. and hold for 3 hours. After completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times, and when the pH of the filtrate became neutral, No. 1 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner base particles 30C.

The matrix had a volume-based median diameter (D50v) of 5.6 μm and an average circularity of 0.985.
Preparation of “toner base particles 30M, 30Y, 30K” In place of “colorant particle dispersion C” used in the preparation of “cyan toner base particles 30C”, yellow “colorant particle dispersion Y” was used. A “yellow toner base particle 30Y” having a volume-based median diameter (D50v) of 5.5 μm and an average circularity of 0.985 was prepared in the same manner except that it was used. In addition, the same procedure was followed except that magenta “colorant particle dispersion M” was used in place of “colorant particle dispersion C” used in the preparation of “base toner particles 30C for cyan toner”. “Magenta toner base particles 30M” having a median diameter (D50v) of 5.4 μm and an average circularity of 0.987 were produced. Further, a volume-based median is obtained in the same procedure except that the black “colorant particle dispersion liquid K” is used in place of the “colorant particle dispersion liquid C” used in the production of the “cyan toner base particles 30C”. A “black toner base particle 30K” having a diameter (D50v) of 5.5 μm and an average circularity of 0.983 was produced.
(External processing)
Preparation of “Cyan toners 1 to 32, yellow toners 1 to 32, magenta toners 1 to 32, black toners 1 to 32” The external additives shown in Tables 3 to 6 were added to each “toner base particle for toner”. Then, by performing an external addition process according to the following procedure, cyan toners 1 to 32, yellow toners 1 to 32, magenta toners 1 to 32, and black toners 1 to 32 ”were produced.

  First, small-diameter external additive particles (A), small-diameter external additive (D), and small-diameter external additive particles (O) were added to the surface of the toner base particles as shown in Tables 3 to 6.

The toner base particles and the small-sized external additive particles are weighed and put into a Henschel mixer “FM10B (manufactured by Mitsui Miike Chemical Co., Ltd.)”, and the peripheral speed of the stirring blade is 40 m / sec at a temperature of 25 ° C. Processing was performed with the time set to 3 minutes. Furthermore, large-diameter external additive particles (co) were added as shown in Tables 3 to 6, and further, the peripheral speed of the stirring blade was set to 40 m / second and the processing time was set to 15 minutes. Toner particles were produced by removing coarse particles from the treated product using a sieve having an opening of 90 μm. The types and amounts of various external additives added to each toner are as shown in each table. The amount of each external additive is based on 100 parts by mass of the colored particles.
(Evaluation experiment)
(Evaluation experiment 1)
Using a commercially available non-magnetic one-component development type image forming apparatus, a color laser printer “magiccolor 5440DL (manufactured by Konica Minolta Business Technologies, Inc.)”, evaluation was performed under a condition that the fixing temperature was lowered by 20 ° C. from the normal setting. It was. The developing devices for yellow, magenta, cyan, and black toners for the image forming apparatus accommodated the toners in the combinations shown in Table 7, and these were mounted on the image forming apparatus.

  Changes in image quality under a high temperature and high humidity environment (temperature 30 ° C., humidity 85% RH) and a low temperature and low humidity environment (temperature 10 ° C., humidity 15% RH) were evaluated as described below. Outputs a color image composed of yellow, magenta, cyan, red, green, blue, and black with a pixel ratio of 1% in full color mode on A4 size paper, and outputs 10,000 sheets continuously in single sheet intermittent mode. To do. Image samples for evaluation were output before and after the printing of 10,000 sheets, and the image quality after output of 10,000 sheets was compared with the initial stage.

  The image sample for evaluation is a solid color image composed of 2 cm square patches of yellow, magenta, cyan, red, green, blue, and black, a solid white image, and a 50% halftone color image having the same configuration as the solid color image. There are three types. Each of these was output one by one on A4 size paper, and the fog density, solid color image and halftone color image uniformity were evaluated, and cleaning performance and PC noise were also evaluated.

<Evaluation of fog>
The fog density in the solid white image area was measured and evaluated. Using a reflection densitometer “RD-918 (manufactured by Macbeth)”, set the reflection density of the paper used for the output of the image sample to 0, and measure the reflection density at any 10 points from the solid white image area. The arithmetic average value was defined as the fog density. A fog density of 0.003 or less was evaluated as ◯, a fog density of 0.005 or less as Δ, these were passed, and those exceeding 0.005 were rejected (x).

<Image uniformity>
The 10,000 color image patches before and after continuous output were visually observed, and the hue and uniformity (density unevenness between color images) were evaluated based on the following criteria. ○ and △ are acceptable and × is unacceptable. That is,
○: No change in hue and uniformity was observed before and after continuous output for each color image, and uniformity was observed between color images after continuous output. Δ: Some hue was observed before and after continuous output for each color image. There is a change, but there is no problem. There is no problem before and after the continuous output and the color image after the continuous output for uniformity. ×: Hue and uniformity are clearly shown before and after the continuous output for each color image. There was a change. In addition, uniformity between color images after continuous output was not recognized.

  The results are shown in Table 7.

As shown in Table 7, it was confirmed that “Example 29” having the constituent features of the present invention obtained the results satisfying the regulations for all the evaluation items, and exhibited the effects of the present invention. On the other hand, in “Comparative Example 5” that does not satisfy the constituent requirements of the present invention, a result satisfying the regulation was not obtained, and it was confirmed that the effect of the present invention was not obtained.
(Evaluation experiment 2)
Each toner used in “Examples 1 to 28” and “Comparative Examples 1 to 4” is mixed with a methyl carrier and a ferrite carrier having a volume average particle diameter of 50 μm coated with a cyclohexyl methacrylate resin so that the toner concentration is 6%. A two-component developer was prepared. As described above, the two-component developer is added with the carrier and the toner so that the toner concentration is 6% by mass, and the rotation speed is measured using a “micro-type V-type mixer (Tsutsui Rikenki Co., Ltd.)”. It was prepared by mixing for 30 minutes at 45 rpm.

  The volume average particle diameter of the carrier is measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The fixing temperature was set to 20 ° C. from the normal setting using a commercially available color composite machine “bizhub 550 (manufactured by Konica Minolta Business Technologies, Inc.)” of a two-component developing system, with Examples and Comparative Examples composed of the above developers. Evaluation was performed under the lowered conditions, and the same evaluation was performed under the same image forming conditions as described above. The results are shown in Table 8.

  As shown in Table 8, the “Example” having the constitutional requirements of the present invention obtained a result that satisfies all the evaluation items, and the effects of the present invention can be obtained even in the image forming method of the two-component development system. Was confirmed to be expressed. On the other hand, it was confirmed that “comparative examples” that do not satisfy the constituent requirements of the present invention do not satisfy the regulations among the evaluation items, and cannot exhibit the effects of the present invention.

10 Developing roller 15 (15Y, 15M, 15C, 15K) Photosensitive drum 20 (20Y, 20M, 20C, 20K) Developing device 24 Blade (toner layer regulating member, charge imparting member)
30 Development device unit 4 Intermediate transfer body unit 40 Intermediate transfer belt 41Y, 41M, 41C, 41K Primary transfer roll 43A, 43B Secondary transfer roll 50 (50Y, 50M, 50C, 50K) Cleaner (cleaning device)
60 Paper feeder 70 Fixing device S Recording material

Claims (4)

A binder resin containing at least a polyester resin, a colorant, and a charge control agent. The thiacalixarene, sulfinylated thiacalixarene, and sulfonylated thiacalix represented by the following general formula (1) A cyclic phenol sulfide selected from arenes, wherein the polyester resin is obtained by polycondensing an alcohol component containing an aliphatic polyhydric alcohol and a carboxylic acid component, and substantially contains tin element in the toner. A toner for developing an electrostatic charge image, which is not contained.

(Wherein, X represents S, SO or SO _2, Z is .n represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group is an integer of 3-9, Y is a hydrocarbon group, a halogenated hydrocarbon group, a halogen atom, —SO ₄ R ¹ or —SO ₃ R ² , R ¹ and R ² represent a hydrogen atom, a hydrocarbon group, or a metal element, Y may be the same or different.) 2. The toner according to claim 1, wherein the toner has a volume-based median diameter of 2.0 μm to 8.0 μm and an average circularity of 0.920 to 0.995. The toner according to claim 1, wherein the toner has a softening point temperature of 121 ° C. or lower and a glass transition temperature of 55 ° C. or lower. An image forming method for forming a toner image using at least a black toner and a color toner, wherein the toner is the toner according to claim 1.

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