JP2006284614A - Toner for electrostatic image development, developer, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner excellent in both low-temperature fixing property and hot-offset resistance. <P>SOLUTION: The toner for electrostatic image development used in an image forming method in which it is fixed by at least heating uses at least two resins which exist in the toner state without forming a stereo-complex and form a stereo-complex during or after fixing, so that an abundance ratio of the stereo-complex of the resins existing in the toner before fixing is made lower than an abundance ratio of the stereo-complex of the resins existing in a toner component on an image after fixing. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, an image forming method and an image forming apparatus using the toner. More specifically, the present invention relates to an electrostatic image developing toner, an image forming method, and an image forming apparatus used for a copying machine, a laser printer, and a plain paper fax machine using a direct or indirect electrophotographic developing system. Further, the present invention relates to a toner for developing an electrostatic image, an image forming method, and an image forming apparatus (developing apparatus) used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine and the like using a direct or indirect electrophotographic multicolor developing system. .

  Conventionally, as electrophotography, various methods are described in Patent Documents 1 to 3 and the like, but generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Then, the latent image is developed with toner, and the toner powder image is transferred onto paper or the like, if necessary, and then fixed by heating, pressurization or solvent vapor to obtain a copy image.

  The toner binder used in electrophotography, electrostatic recording, electrostatic printing, etc. can fix the toner even when the hot roll temperature is low (low temperature fixability), and the toner does not fuse to the hot roll even at a high hot roll temperature. Satisfying the contradictory performance (hot offset resistance). In recent years, from the viewpoint of energy saving, there has been a demand for further low-temperature fixability than before, and from the viewpoint of miniaturization of apparatuses such as copying machines, further resistance to hot offset has been demanded.

  Conventionally, styrene acrylic resins, polyesters, epoxy resins, and the like have been used as toner binders, but cross-linked polyesters are often used because of their excellent low-temperature fixability. As a method for improving the low-temperature fixability and hot offset resistance of polyester, a method of mixing two kinds of polyesters having different molecular weight distributions has been proposed (see Patent Documents 3 to 6). However, what is disclosed in these is a powder mixture of polyesters having different softening points, although the balance between low-temperature fixability and hot offset resistance is in an improving trend as compared with conventional polyesters. There is a problem in uniformity, and there is a problem that the pigment cannot be sufficiently dispersed when the toner is kneaded. When the difference between the softening points of the two kinds of polyesters is reduced, the pigment dispersibility is improved, but conversely, there is a problem that the low-temperature fixability and hot offset resistance are not sufficiently improved.

  On the other hand, with regard to binder resins that account for more than 70% of the constituent components of toner, most of the conventional materials are made from petroleum resources. Problems with the future depletion of petroleum resources, carbon dioxide due to large consumption of petroleum resources into the atmosphere There are concerns about the issue of global warming due to emissions. However, if toner binders can be synthesized from plants that grow by taking in carbon dioxide in the atmosphere, carbon dioxide can be circulated, and there is a possibility of simultaneously meeting the problems of suppressing global warming and depleting petroleum resources. Therefore, attention has been focused on polymers (biomass) made from plant resources.

  As a study of using a plant-derived resin as a toner binder, Patent Document 7 describes using polylactic acid as a binder resin. However, when polylactic acid is used as a toner as it is, it is compared with a polyester resin. Therefore, the ester group concentration is high, the thermal characteristics are very high, the action as a thermoplastic resin is low at the time of fixing, and the toner is very hard, so that it is not suitable for production due to lack of grindability. Patent Document 8 describes that a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a tri- or higher functional oxycarboxylic acid is used. Since the polyester resin is formed by the dehydration polycondensation reaction with the carboxylic acid group in the acid, the molecular weight is increased, the sharp melt property is impaired, and the low temperature fixability is lacking. Furthermore, in order to improve the thermal characteristics, in Patent Document 9, it is said that a polylactic acid-based biodegradable resin contains a terpene phenol copolymer as a low molecular weight component. However, no polylactic acid resin has been put to practical use for toner.

U.S. Pat. No. 2,297,691 Japanese Patent Publication No.49-23910 Japanese Patent Publication No.43-24748 JP-A-60-214368 JP 63-225244 A JP-A-4-313760 Japanese Patent No. 2909873 JP-A-9-274335 JP 2001-166537 A

Therefore, the present invention uses a plant-derived toner resin as a toner to reduce CO ₂ from the viewpoint of CO ₂ reduction due to global environmental problems, and to reduce power consumption in order to reduce CO ₂ consumption from the resin manufacturing stage and power consumption of the copying machine. Providing environment-friendly image forming method and toner by coexistence of low-temperature fixability and hot offset resistance, toner capable of forming a high-definition and high-definition image, developer having no image deterioration over a long period of time, and the toner It is an object of the present invention to provide an image forming apparatus using the above.

As means for solving the above problems, the present invention has the following features.
(1) At least in the toner used in the image forming method fixed by heating, the stereocomplex existing ratio (before C) of the resin present in the toner before fixing and the resin present in the toner component on the image after fixing The stereo complex abundance ratio (after C) is
A toner for developing electrostatic charge, wherein C before <C after C.
(2) The toner uses at least two kinds of resins, and the first toner using one resin (A) and the second toner using the other resin (B) exist independently. The electrostatic charge developing toner of (1) above, wherein one resin (A) and the other resin (B) form a stereocomplex.
(3) The toner uses at least two kinds of resins, and includes first primary particles using one resin (A) and second primary particles using the other resin (B). (1) The electrostatic charge developing toner according to (1) above, comprising toner particles formed by aggregation, wherein one resin (A) and the other resin (B) form a stereocomplex.
(4) The electrostatic charge developing toner according to (3) above, wherein the toner is not subjected to a heating or heating step of 90 ° C. or higher between at least the aggregation and the fixing.
(5) The electrostatic charge according to any one of (1) to (4), wherein the two kinds of resins exist in a state where a stereocomplex is not formed in a toner state, and forms a stereocomplex after fixing. Development toner.
(6) The one resin (A) contains one or more right-handed helical polymer units (a) in the molecule, and the other resin (B) contains one or more left-handed helical polymers in the molecule. The electrostatic charge developing toner according to any one of (2) to (5) above, which contains a unit (b).
(7) The above (2), wherein the resins (A) and (B) are one or more resins selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, polyether resins and epoxy resins. ) To (6) toner for developing electrostatic charge.
(8) The electrostatic charge developing toner according to (6) or (7) above, wherein the monomer constituting the polymer units (a) and (b) comprises an optically active monomer (m).
(9) The optically active monomer (m) is α-alkyl (1 to 4 carbon atoms) -α-hydroxycarboxylic acid, α-hydrocarbyl (1 to 12 carbon atoms) -α-amino acid, α-hydrocarb. Bill (C1-8) methacrylate, cyclic ester having asymmetric carbon (C3-6), α-alkylethylene oxide (C6-9) and α-alkylethylene sulfide (C6-9) The electrostatic charge developing toner according to (8), wherein the toner is one or more selected from the group consisting of:
(10) The electrostatic charge development according to the above (8) or (9), wherein the optically active monomer (m) is L-lactic acid and D-lactic acid and / or L-lactide and D-lactide. Toner.
(11) The toner for developing an electrostatic charge is obtained by dissolving or dispersing a toner composition comprising at least a resin and a colorant in a polymerizable monomer, and emulsifying and dispersing the solution or dispersion in an aqueous medium. The electrostatic charge developing toner according to any one of the above (1) to (10), which is obtained by polymerizing the emulsified dispersion.
(12) The electrostatic charge developing toner is obtained by dispersing a toner composition comprising at least a resin and a colorant in an aqueous medium, aggregating the dispersion in an aqueous medium, and heating and aggregating the aggregate. The electrostatic charge developing toner according to the above (1) to (10), wherein the electrostatic charge developing toner dissolves or disperses a toner composition comprising at least a resin and a colorant in an organic solvent. The electrostatic charge developing toner according to any one of (1) to (10) above, which is obtained by emulsifying and dispersing the dissolved or dispersed material in an aqueous medium and removing the organic solvent.
(14) The toner for developing an electrostatic charge is obtained by dissolving or dispersing a toner composition comprising at least a resin and a colorant in an organic solvent, emulsifying and dispersing the solution or dispersion in an aqueous medium, and dissolving or dispersing the solution or dispersion. The toner for electrostatic charge development according to (1) to (10) above, which is obtained by subjecting a product to a polyaddition reaction and removing an organic solvent.
(15) The release agent contains at least one selected from the group consisting of carnauba wax, montan wax, candelilla wax, oxidized rice wax, Fischer-Tropsch wax, paraffin wax and polyolefin wax. (1) to (14) electrostatic charge developing toner.
(16) The electrostatic charge developing toner according to any one of (1) to (15) above, which contains a charge control agent.
(17) The electrostatic charge developing toner according to (1) to (16) above, wherein the toner has an average circularity of 0.94 or more.
(18) The volume average particle diameter of the toner is 3.0 to 8.0 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1.40. The electrostatic charge developing toner according to any one of (1) to (17) above, wherein the toner is in the range of
(19) For electrostatic charge development according to (1) to (18) above, wherein the shape factor SF-1 of the toner is in the range of 100 to 180 and the shape factor SF-2 is in the range of 100 to 180. toner.
(20) The shape of the toner is a spindle shape, and the spindle shape is defined by a major axis r ₁ , a minor axis r ₂ , and a thickness r ₃ (provided that r ₁ ≧ r ₂ ≧ r ₃ ). The ratio of the short axis r ₂ to the long axis r ₁ (r ₂ / r ₁ ) is in the range of 0.5 to 1.0, and the ratio of the thickness r ₃ to the short axis r ₂ (r ₃ / r ₍₂ ) is in the range of 0.7 to 1.0. (1) to (19) above.
(21) A developer for developing a two-component electrostatic charge image, comprising the toner for electrostatic charge development of (1) to (20) and a carrier.
(22) In the image forming method in which the toner is fixed on the fixing medium by at least heating, by using the electrostatic charge developing toner of (1) to (20) above, the presence of a stereocomplex of the resin present in the toner before fixing The ratio (before C) and the stereocomplex existing ratio (after C) of the resin present in the toner component on the image after fixing are as follows:
An image forming method, wherein C before <C after.
(23) An image forming apparatus in which a toner image on a transfer material is heated and melted by passing between a pair of opposed nips to fix the surface pressure (roller load) applied between the pair of opposed nips. An image forming apparatus having a fixing device that performs fixing at a contact area of 1.5 × 10 ⁵ Pa or less and using the toners of (1) to (20).
(24) The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. The image forming apparatus according to (23), wherein the image forming apparatus is a fixing device that heats and fixes a recording material on which an unfixed image is formed between pressure members.
(25) The image forming apparatus according to (23) or (24) above, wherein the photoconductor used for image formation is an amorphous silicon photoconductor.
(26) The image forming apparatus according to any one of (23) to (25), further comprising a developing unit provided with an electric field applying unit for applying an alternating electric field when developing the latent image on the photosensitive member.
(27) The image forming apparatus according to any one of (23) to (26), further comprising a charging device that performs charging by bringing a charging member into contact with the latent image carrier and applying a voltage to the charging member.
(28) A process cartridge that integrally supports at least one member selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit, and is detachable from an image forming apparatus main body. A process cartridge that is held and the toner is the toner of (1) to (20) above.

The toner of the present invention has the following effects.
1. Excellent heat melting characteristics and excellent low temperature fixability when used as toner for electrophotography, electrostatic recording, and electrostatic printing.
2. Excellent releasability from heat source when melted, improved hot offset resistance when used as toner for electrophotography, electrostatic recording and electrostatic printing, and widens the temperature range in which toner can be fixed on paper Can do.

  The image forming method of the present invention is an image forming method in which toner is fixed to a fixing medium at least by heating. In the image forming method of the present invention, before the stereocomplex ratio C of the resin present in the toner before fixing, After the stereocomplex abundance ratio C of the existing resin, it is characterized in that before C <after C.

The resin existing in the toner component by fixing forms a stereo complex, thereby improving the heat resistance and providing an image forming method excellent in hot offset resistance.
If the ratio of the stereo complex does not change before and after fixing, it is not possible to secure a fixing region that exhibits low temperature fixability and hot offset resistance.

Further, at least in the toner used in the image forming method fixed by heating,
The characteristic is that before the stereocomplex abundance ratio C of the resin present in the toner before fixing and after the stereocomplex abundance ratio C of the resin present in the toner component on the image after fixing is before C. To do.

  Specifically, the toner of the present invention includes a resin (A) having a right-handed helical polymer unit (a) and a resin (B) having a left-handed helical polymer unit (b) in the aggregate. When the aggregate of particles is used as a toner, it melts in contact with a heat source, so that (a) and (b) are mixed to form a stereo complex of (a) and (b). The pseudo-crosslinked structure formed by the stereocomplex formed at the time of melting increases the viscosity of the toner binder and improves the offset resistance of the electrophotographic toner. In addition, even if the initial melt is low viscosity, thickening due to stereocomplex formation occurs later in the melt, so that while maintaining the hot offset resistance, the molecular weight of the resin (A) and the resin (B) is reduced. It is possible to improve the low-temperature fixability.

  The toner of the present invention is an aggregate of resin particles comprising a resin (A) having at least one (a) in the molecule and / or a resin (B) having at least one (b) in the molecule. A toner comprising: One resin particle may contain (A) and (B) at the same time, or one resin particle may contain only one of (A) and (B). From the viewpoint of easy formation of a stereocomplex when the toner is melted, it is preferable that (A) and (B) are contained in the same resin particle. When (A) and (B) are contained in the same resin particle, they are composite resin particles comprising fine resin particles of (A) and (B), and (a) and (b) form a stereocomplex. It exists in a state that is not.

The number of (a) in (A) and the number of (b) in (B) are preferably 1 to 10, more preferably 2 to 6, respectively.
The weight ratio of (A) and (B) in the toner binder is preferably (A) :( B) = (20:80) to (80:20), more preferably (A) :( B) = ( 30:70) to (70:30), particularly preferably (A) :( B) = (40:60) to (60:40).

  Whether or not the stereocomplex of the present invention is formed is determined based on a diffraction peak by a wide-angle X-ray diffraction method, specifically, a diffraction peak that appears when a stereocomplex is formed (in the case of polylactic acid: flag angle (2θ) 11). .3 to 12.3 °, 20.1 to 21.1 °, around 23.3 to 24.3 °), or the calorific value (endothermic melting calorie) of the endothermic peak in differential scanning calorimetry (DSC), specifically Can be discriminated by the endothermic peak (around + 50 ° C. as compared with the single substance (A) or (B)) that appears when the stereo complex is formed.

  In the toner using at least two kinds of resins, the first toner using one resin (A) and the second toner using the other resin (B) exist independently and are mixed. Therefore, at the toner stage before fixing, one resin (A) and the other resin (B) are preferable because they do not form a stereo complex and are excellent in low-temperature fixability.

  Further, in the toner using at least two kinds of resins, the first primary particles using one resin (A) and the second primary particles using the other resin (B) are aggregated and toner. By using particles, one resin (A) and the other resin (B) are always present at the time of fixing, so that a stereocomplex is quickly formed. Furthermore, it is preferable that the formation of a stereocomplex in toner formation can be minimized by not having a heating (heating) step of 90 ° C. or higher after aggregation (until it is used for fixing).

  The monomer constituting (a) and (b) is not particularly limited as long as it can form a helical polymer unit. However, since it is easy to introduce the helical polymer unit, it is composed of an optically active monomer (m). Is preferred. (M) includes not only monomers having asymmetric carbon but also monomers that generate asymmetric carbon by polymerization.

(A) and (b) can be produced separately by, for example, homopolymerizing (m) each having a specific optical rotation with a different sign. In order to form a stereo complex, It is preferably in the enantiomeric relationship. (A) and (b) may be a homopolymer of one type of optically active monomer (m), or two or more types of (m), or a combination of one or more types of (m) and other monomers. A polymer may be used, but in the case of a copolymer, since a helical polymer unit can be easily formed, a block copolymer containing one kind of (m) homopolymer portion is preferable. . The degree of polymerization of the homopolymer part (m) in the homopolymer and the block copolymer is preferably 10 to 100,000, more preferably 50 to 8000, from the viewpoint of easy formation of a stereocomplex.
Generally, it is known that a helical polymer is formed by homopolymerizing an optically active monomer having an optical purity of 100%. The structure of the helical polymer unit is confirmed by an X-ray crystal structure analyzer [manufactured by Rigaku Corporation]. , AFC7R, etc.] can be used to distinguish left-handed and right-handed.

  (M) includes α-alkyl (alkyl group having 1 to 4 carbon atoms) -α-hydroxycarboxylic acid, α-hydrocarbyl (hydrocarbyl group having 1 to 12 carbon atoms) -α-amino acid, α- Hydrocarbyl (hydrocarbyl group having 1 to 8 carbon atoms) methacrylate, cyclic ester having asymmetric carbon (total carbon number 3 to 6), α-alkylethylene oxide (total carbon number 6 to 9), α-alkyl Ethylene sulfide (total carbon number 6-9) etc. are mentioned.

  Examples of the alkyl group having 1 to 4 carbon atoms in the α-alkyl-α-hydroxycarboxylic acid include a methyl group, an ethyl group, and an isopropyl group, and specific examples thereof include L-lactic acid and D-lactic acid. The hydrocarbyl group having 1 to 12 carbon atoms in the α-hydrocarbyl-α-amino acid may be any of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group, such as a methyl group, an ethyl group, and a phenyl group. Group, benzyl group, α-methylbenzyl and the like, and specific examples include γ-benzylglutamic acid and γ-methylglutamic acid. Examples of the hydrocarbyl group in α-hydrocarbyl methacrylate include those described above, and specific examples include α-methylbenzyl methacrylate and methyl methacrylate. Specific examples of the cyclic ester having an asymmetric carbon include L-lactide, D-lactide, α-methyl-α-ethyl-β-propiolactone, and β- (1,1-dichloropropyl) -β-pro. Piolactone is mentioned. Examples of the alkyl group in α-alkylethylene oxide include those described above, and specific examples include t-butylethylene oxide. Examples of the alkyl group in the α-alkylethylene sulfide include those described above, and specific examples thereof include t-butylethylene sulfide.

  Of these, L-lactic acid, D-lactic acid, L-lactide, D-lactide, t-butylethylene oxide, t-butylethylene sulfide, α-methyl are preferable from the viewpoint of easy introduction of the helical polymer unit. -Α-ethyl-β-propiolactone, β- (1,1-dichloropropyl) -β-propiolactone, and combinations thereof, more preferably L-lactic acid and D-lactic acid, and / or L-lactide and D-lactide, particularly preferably L-lactide and D-lactide.

  As the polymerization reaction mode of the monomers constituting the right-handed helical polymer unit (a) and the left-handed helical polymer unit (b), any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. However, among these, from the viewpoint of easy stereoregular polymerization necessary for forming a helical polymer unit, a cyclic ester having an asymmetric carbon, α-alkylethylene oxide, α- Ring-opening polymerization of cyclic monomers such as alkylethylene sulfide and dehydration condensation of hydroxycarboxylic acid.

As a catalyst used for ring-opening polymerization and dehydration condensation, a known catalyst is used, and can be appropriately selected in consideration of reactivity and selectivity. For example, base catalysts include hydroxides of alkali metals (Li, Na, K, etc.), alcoholates of alkali metals (Li, Na, K, etc.), and alkylamines (monoalkylamines, dialkylamines, trialkylamines). Examples of acid catalysts include Lewis acid catalysts such as halides and alkoxides of metals (Al, Sb, B, Be, P, Fe, Zn, Ti, Zr, etc.), inorganic acids (HCl, HBr, H ₂ SO ₄ , HClO _{4, and the} like), and organic acids (acetic acid, oxalic acid, etc.), and two or more of them can be used in combination. The amount of the polymerization catalyst used is preferably 0.001 to 5% by weight based on the weight of all monomers to be reacted.

  The method of introducing (a) into the resin (A) and the method of introducing (b) into the resin (B) are not particularly limited, but constitute the helical polymer unit (a) or (b) in the resin. Examples thereof include a method of graft polymerization of monomers and a method of bonding the helical polymer unit (a) or (b) to a resin.

Specifically, as a method of graft polymerization to a resin, a polycondensation reaction to a functional group (hydroxyl group, carboxyl group, amino group, etc.) having active hydrogen in the resin, a ring-opening polymerization reaction, a vinyl polymerization in the resin And vinyl polymerization with a functional group. In addition, as a method of bonding the helical polymer unit to the resin, the functional group having active hydrogen (hydroxyl group, thiol group, carboxyl group, etc.) in the helical polymer unit and the functional group that reacts with the active hydrogen contained in the resin. Reaction with groups (isocyanate group, thioisocyanate group, epoxy group, etc.), and functional groups with active hydrogen in resin and functional groups with active hydrogen in helical polymer unit react with active hydrogen Examples include a method of bonding using a substance having two or more (isocyanate group, epoxy group, etc.).
The content of the helical polymer unit (a) or (b) contained in the resin (A) or (B) is preferably 10 to 99% by weight, more preferably 30 to 90%, from the viewpoint of easy formation of a stereocomplex. It is 97% by weight, particularly preferably 50 to 95% by weight.

  The resin (A) and the resin (B) may be thermoplastic resins or thermosetting resins. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyether resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin (A) and the resin (B), two or more of the above resins may be used in combination. Of these, vinyl resins, polyester resins, polyurethane resins, polyether resins, epoxy resins and combinations thereof are preferred from the viewpoint of good heat melting properties, and more preferably polyester resins, polyether resins and It is a combination of them.

Hereinafter, vinyl resin, polyester resin, polyurethane resin, polyether resin and epoxy resin, which are preferable resins, will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Carboxyl group-containing vinyl monomer and salts thereof:
C3-C20 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, etc. Carboxyl group-containing vinyl monomer.

(2) Vinyl hydrocarbons:
(2-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(2-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(2-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes, such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropanesulfonic acid, 2- ( T) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-C18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, Propylene, butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and Sulfate ester or sulfonic acid group-containing monomers represented by general formulas (3-1) to (3-3); and salts thereof.

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (1), (3), and (4) include those exemplified as the neutralized salt of the carboxyl group. Preferred are alkali metal salts and amine salts, and more preferred are sodium salts and salts of tertiary monoamines having 3 to 20 carbon atoms.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N -Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc.

(6-2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (Meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl system Monomer: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc.

(6-4) Quaternary ammonium cationic group-containing vinyl monomers: tertiary such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized amine group-containing vinyl monomers (quaternized with quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomers: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomers:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (Two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, Tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide (hereinafter abbreviated as EO) ) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]

(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc.

(9-3) Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  Examples of the vinyl monomer copolymer include polymers obtained by copolymerizing any of the above monomers (1) to (10) at an arbitrary ratio. For example, styrene- (meth) acrylic acid ester- (meth). Acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid copolymer, styrene- (meth) Examples include acrylic acid copolymers, styrene- (meth) acrylic acid-divinylbenzene copolymers, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymers, and salts of these copolymers.

  As a method of introducing (a) or (b) into the vinyl resin, (i) at the time of polymerization of the vinyl monomer, the hydroxyl group-containing vinyl monomer (5), the epoxy group-containing vinyl monomer (7), etc. Then, after polymerizing a monomer containing a vinyl monomer having a functional group capable of reacting with the monomer (m) to synthesize a vinyl resin having a functional group capable of reacting with (m), the monomer containing (m) is reacted. (Ii) vinyl resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) And a functional group (isocyanate group, epoxy) which reacts with active hydrogen. A method in which binding with the substance [later polyisocyanates such as hexamethylene diisocyanate (15), etc.] with shea group) two or more thereof. Among these methods, the method (i) is preferable because the number of reaction steps is small.

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol having a valence of 3 to 8 or more (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and a valence of 3 to 6 or more. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The ratio of polyol and polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ˜¼, particularly preferably from 1 / 1.3 to ３.

  Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Alkylene oxides (hereinafter abbreviated as AO) [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1-30); bisphenols (bisphenols) A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (addition mole number 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol.

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid and 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].

Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol (12) having 3 to 8 or more valences include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside; AO adducts of trisphenols (such as trisphenol PA) 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers, etc.]; Etc.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

  Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid), etc.], alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

Examples of the tricarboxylic acid having a valence of 3 to 6 or more (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
As the dicarboxylic acid (13) or the polycarboxylic acid (14) having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

  As a method for introducing (a) or (b) into a polyester resin, (i) a monomer containing (m) is blocked from a hydroxyl group and / or a carboxyl group present as a terminal functional group of the polyester resin. (Ii) a polyester resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, etc.) and a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) (m) Or a block copolymer containing a homopolymerized portion of (m) and a substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen (polyethylenes described below such as hexamethylene diisocyanate) And the like, and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

  Polyurethane resins include polyisocyanate (15) and active hydrogen-containing compounds {water, polyol [including diol (11) [including diol (11a) having a functional group other than hydroxyl group], and 3 to 8 or more valences] Polyol (12)], polycarboxylic acid [dicarboxylic acid (13), and polycarboxylic acid (14) having 3 or more valences or more], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, active hydrogen A polyether polyol having a structure in which an alkylene oxide is added to a compound having an atom, a ring-opening polymer of a lactone having 6 to 12 carbon atoms, a polyamine (16), a polythiol (17), and a combination thereof, etc.} And a terminal isocyanate group formed by reacting (15) with an active hydrogen-containing compound. And polymers obtained by reacting an equivalent amount of primary and / or secondary monoamine (18) to isocyanate groups of the prepolymer, and amino group-containing polyurethane resins.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and minor amounts (eg 5-20%] )) With a trifunctional or higher functional polyamine]]: phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p -Isocyanatophenylsulfonyl isocyanate Such as theft and the like.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And aliphatic polyisocyanates.

Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to C18): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4-C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aromatics such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Reamines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, etc .; [2] aromatic polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), for example 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylene Diamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2, , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diame Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4 , 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substitution electron withdrawing Aromatic polyamines having groups (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro -1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro -1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) ) Sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3) -Methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [above [1] to [1] A part or all of —NH ₂ of the aromatic polyamine of [3] is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4 ′ -Di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamines: dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines ( Polyether polyamines such as low molecular weight polyamide polyamines obtained by condensation with alkylene diamines, polyalkylene polyamines, etc.) Hydrides of cyanoethylation products of polyols (polyalkylene glycol and the like).

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).

  As a method for introducing (a) or (b) into a urethane resin, (i) a block copolymer of a monomer containing (m) starting from a hydroxyl group and / or an isocyanate group present as a terminal functional group of the urethane resin (Ii) a urethane resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) (m ) Or a block copolymer containing a homopolymerized portion of (m) and a substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen [the above polymethylene such as hexamethylene diisocyanate And the like, and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

  Polyether resins include compounds having active hydrogen atoms (for example, diol (11), 3 to 8 or more polyol (12), dicarboxylic acid (13), 3 to 6 or more polycarboxylic acid. (14) primary and / or secondary monoamine (18) and the like) and compounds having a structure in which alkylene oxide is added, and mixtures thereof. Examples of the alkylene oxide added to the active hydrogen atom-containing compound include EO, PO, 1,2-, 1,3-, 1,4-, 2,3-butylene oxide, styrene oxide, and the like, and two or more kinds thereof. In combination (block and / or random addition). Among the polyether polyols, those having a polyoxypropylene chain and those having a polyoxypropylene chain and a polyoxyethylene chain (EO content of 25% by weight or less) are preferable. The polyether polyol is obtained by adding PO to the active hydrogen atom-containing compound; and PO and another alkylene oxide (hereinafter abbreviated as AO, preferably EO) in the order of 1) PO-AO. Added (chipd), 2) Added in the order of PO-AO-PO-AO (balanced), 3) Added in the order of AO-PO-AO, 4) Order of PO-AO-PO A block adduct such as those added in (5) (active secondary), etc .; 5) a random adduct in which PO and AO are mixed and added; and 6) those added in the order described in JP-A-57-209920, 7 ) Random / block adducts such as those added in the order described in JP-A-53-13700. These may be used in combination.

  As a method of introducing (a) or (b) into the polyether resin, (i) a method of block copolymerizing a monomer containing (m) starting from a hydroxyl group present as a terminal functional group of the polyether resin, (Ii) A polyether resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) (m) Or a block copolymer containing a homopolymer part of (m) and a substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen [the polymethylene such as hexamethylene diisocyanate] And the like, and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and active hydrogen group-containing compound (D) {water, polyol [the diol (11) and a trivalent or higher valent polyol (12)], dicarboxylic acid Acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17), etc.} polyaddition product, or polyepoxide (19) with dicarboxylic acid (13) or trivalent or higher polyvalent Examples include cured products of carboxylic acid (14) with acid anhydrides.

  The polyepoxide (19) is not particularly limited as long as it has two or more epoxy groups in the molecule. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the cross-linked structure becomes dense and the cured product has good physical properties such as water resistance, chemical resistance and mechanical strength. When the epoxy equivalent is 65 or more, synthesis is easy.

  Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like.

Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included.

  Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines.

  Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned.

  Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

  As a method of introducing (a) or (b) into an epoxy resin, (i) a monomer containing (m) starting from a functional group having an active hydrogen such as a hydroxyl group present in the epoxy resin is blocked. (Ii) an epoxy resin having a functional group having an active hydrogen such as a hydroxyl group and a polymer of (m) having a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) or ( m) a substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen and a block copolymer containing a homopolymerized moiety [the polyisocyanate (15) such as hexamethylene diisocyanate, etc.] And the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

The number average molecular weight (Mn), melting point, melting start temperature, Tg, SP value, hydroxyl value, and acid value of the resin (A) and the resin (B) can be appropriately adjusted within a preferable range depending on the use conditions when the toner is used. Good.
For example, Mn (measured by gel permeation chromatography) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (A) and (B) (measured by DSC, hereinafter the melting point is measured by DSC) is preferably 80 to 130 ° C, more preferably 85 to 120 ° C, particularly preferably 90 to 110 ° C. is there. 80 ° C. or higher is preferable from the viewpoint of heat-resistant storage stability, and 130 ° C. or lower is preferable from the viewpoint of low-temperature fixability.

  (A) and (B) melting start temperature (measured with a flow tester, hereinafter melting start temperature is measured with a flow tester) is preferably 80 to 130 ° C, more preferably 85 to 120 ° C, particularly preferably. 90-110 ° C. 80 ° C. or higher is preferable from the viewpoint of heat-resistant storage stability, and 130 ° C. or lower is preferable from the viewpoint of low-temperature fixability. Tg of (A) and (B) is preferably 30 to 80 ° C, more preferably 45 to 75 ° C, and particularly preferably 50 to 70 ° C. A Tg of 30 ° C. or higher is preferable from the viewpoint of heat-resistant storage stability, and a Tg of 80 ° C. or lower is preferable from the viewpoint of low-temperature fixability.

  The SP value of (A) and (B) is preferably 8 to 16, more preferably 9 to 14. The hydroxyl value of (A) and (B) is preferably 70 mgKOH / g or less, more preferably 5 to 50 mgKOH / g, and particularly preferably 10 to 45 mgKOH / g. A hydroxyl value of 70 mgKOH / g or less is preferable from the viewpoint of improving environmental stability and charge amount. The acid value of (A) and (B) is preferably 0 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g, particularly preferably 10 to 30 mgKOH / g, and most preferably 15 to 25 mgKOH / g. A smaller acid value improves environmental stability, but a more suitable acid value is preferable in terms of improving the rising of charging.

In the toner of the present invention, the first toner using one resin (A) and the second toner using the other resin (B) exist independently and are mixed. Well,
As the method, particles made of resin (A) alone or resin (B) alone are (i) coarsely pulverized (A) or (B) obtained by monomer polymerization, and finally a jet pulverizer or the like And (ii) (ii) the monomer obtained by polymerizing (A) or (B) is dissolved or dispersed in the polymerizable monomer, and the solution or dispersion (Ii-2) Dispersing in an aqueous medium, aggregating the dispersion in an aqueous medium, and heating the aggregate A method obtained by fusing, (ii-3) a method obtained by dissolving or dispersing in an organic solvent, emulsifying and dispersing the dissolved material or dispersion in an aqueous medium, and removing the organic solvent, (ii-4) organic Dissolve or disperse in a solvent, and dissolve or disperse the dissolved or disperse in an aqueous medium. And can be a dissolution or dispersion by a polyaddition reaction, a method obtained by removing the organic solvent or the like, may be used to select from commonly known methods used.

  The toner of the present invention is obtained by powder-mixing particles made of the resin (A) alone and particles made of the resin (B) alone, and can be mixed with ordinary mixing conditions and a mixing apparatus. The mixing conditions for mixing the powder are not particularly limited, but the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. Although it does not specifically limit as mixing time, Preferably it is 3 minutes or more, More preferably, it is 5 to 60 minutes. Although it does not specifically limit as a mixing apparatus, For example, a Henschel mixer, a Nauter mixer, a Banbury mixer, etc. are mentioned. A Henschel mixer is preferable. In the aggregate of resin particles obtained by powder mixing, unlike the case of melt mixing, the stereocomplexes (a) and (b) are not formed.

  The toner of the present invention may be composed of resin particles containing (A) and (B) at the same time. The first primary particles using one resin (A) and the other resin (B). In the case where the second primary particles using agglomerates into toner particles and one resin (A) and the other resin (B) are contained in the same resin particle, the above method (ii) ( The aqueous dispersion of A) and the aqueous dispersion of (B) are prepared separately, and after mixing, the organic solvent is removed to produce composite resin particles composed of fine resin particles of (A) and (B). The method is preferred. In the composite resin particles obtained as described above, (a) and (b) exist in a state where a stereo complex is not substantially formed before fixing. Here, the term “substantially” means that a stereocomplex is formed at the aggregation interface of the resins (A) and (B), but most of the resins (A) and (B) are scattered independently. It means that the state which does not form accounts for the majority.

  Furthermore, it is preferable not to have a heating (heating) step of 90 ° C. or higher after aggregation (until it is used for fixing), and more preferable to have a heating (heating) step of 80 ° C. or higher. Is not to. This is because the formation of a stereocomplex by melting due to sintering of the aggregation interface between the resins (A) and (B) can be minimized during aggregation, and the low-temperature fixability is excellent.

(Coloring agent)
As the colorant used in the toner of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium Mu yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG) ), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent Red 4R, Para Red, Faisere , Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacrid Red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Mara Kite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  The content of the toner binder in the toner is not particularly limited, but when a dye or pigment is used as the colorant, it is preferably 70 to 98% by weight, more preferably 74 to 96% by weight, based on the toner. When powder is used, it is preferably 20 to 85% by weight, more preferably 35 to 65% by weight, based on the toner.

(Release agent)
The toner of the present invention may contain various conventionally known release agents as necessary. The release agent works between the fixing roller and the toner interface, and is effective against high temperature offset without applying a release agent such as oil to the fixing roller, and has a low melting point of 50 to 120 ° C. A release agent having a melting point is preferable because it works more effectively as a release agent in the dispersion with the binder resin.

  Release agents include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax and candelilla wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, ozokerite and cercin, and Examples include petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, polyolefin waxes (polyethylene wax, polypropylene wax, etc.), long-chain hydrocarbons (paraffin wax, sazol wax, etc.), synthetic waxes such as esters, ketones, ethers and the like can be mentioned. It is done. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .

  The carnauba wax is a natural wax obtained from the leaves of carnauba palm, but a microcrystalline one is preferred, and those having an acid value of 5 or less are preferable because they can be uniformly dispersed in the binder resin. Further, a low acid value type from which free fatty acids are eliminated is more preferred. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. Oxidized rice wax is a natural wax obtained by refining crude wax produced in a dewaxing or wintering process when refining rice bran oil extracted from rice bran, and its acid value is 10-30. preferable. Synthetic ester wax is synthesized by ester reaction from monofunctional linear fatty acid and monofunctional linear alcohol.

These can be used alone or in combination, and in particular, at least one selected from the group consisting of carnauba wax, Fischer-Tropsch wax, paraffin wax, polyolefin wax, montan wax, candelilla wax and oxidized rice wax. It is preferable to contain a release agent from the viewpoint of achieving both low-temperature fixability and hot offset property.
When the release agent is contained, the content is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, particularly 0.5 to 10% by weight based on the toner. When the content of the release agent is in the range of 0.01 to 20% by weight, the hot offset resistance when the toner is used becomes better.

(Charge control agent)
If necessary, the toner of the present invention can contain a charge control agent. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salt compounds, (fluorine Modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fees, other quaternary ammonium base-containing polymers, metal-containing azo dyes, sulfonic acid group-containing polymer, the carboxyl group-containing polymers, fluorine-containing polymers and halogen substituted aromatic ring-containing polymers. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The content of the charge control agent in the case of incorporating the charge control agent into the toner of the present invention is not particularly limited, but is preferably 0.00 on the basis of the total weight of the resins (A) and (B) and the charge control agent. 01 to 5%, more preferably 0.02 to 4%. The chargeability of the toner can be controlled moderately, and the decrease in developer fluidity and the decrease in image density due to an increase in electrostatic attraction with the developing roller can be prevented.

Further, the toner of the present invention may contain other resins than (A) and (B) as necessary. Although it does not specifically limit as other resin, In each said resin, resin etc. which do not contain helical polymer unit (a) and (b) are mentioned.
Other resin may be contained in the same resin particle as (A) and / or (B), or may exist as another resin particle.
Other resins preferably have the same ranges of Mn, melting point, melting start temperature, Tg, SP value, hydroxyl value and acid value as in (A) and (B).

The content of the other resin in the toner binder is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total weight of (A) and (B).
When the toner of the present invention contains the resin (A) and / or (B), a colorant, and / or a release agent, a charge control agent, or another resin, (A) and (B) and these components The mixing method is not particularly limited as long as the stereocomplex of (a) and (b) is not formed during mixing, but powder mixing may be performed in advance by the same method as described above, or at the time of toner formation You may mix. In addition, as a method for containing other resin in the same resin particles as (A) and / or (B), the same method as the method for producing the resin particles containing (A) and (B) at the same time. Is mentioned.

  The toner of the present invention may be mixed with additives such as a filler, an antistatic agent, a magnetic powder, an ultraviolet absorber, an antioxidant, an antiblocking agent, a heat stabilizer, and a flame retardant as necessary. .

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning improver for removing the developer after transfer remaining on the photosensitive member or the primary transfer medium include, for example, fatty acid metal salts such as zinc stearate, calcium stearate, and magnesium stearate, such as polymethyl methacrylate fine particles, polystyrene. Examples thereof include fine polymer particles produced by soap-free emulsion polymerization of fine particles and the like. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The average circularity of the toner is preferably in the range of 0.94 to 1.00. When the average circularity is less than 0.94 and the toner has a shape separated from the spherical shape, it is difficult to obtain a satisfactory transfer property or a high-quality image without dust. Such irregularly shaped particles have many points of contact with the smooth medium on the photoreceptor and the charge concentrates on the tip of the protrusion, so van der Waals force and mirror force are more than those with relatively spherical particles. Wearing power is high. For this reason, in the electrostatic transfer process, the spherical particles are selectively moved in the toner in which the amorphous particles and the spherical particles are mixed, and the character portion and the line portion image are lost. Further, the remaining toner has to be removed for the next development step, and there arises a problem that a cleaning device is necessary and the toner yield (the ratio of toner used for image formation) is low.

  The circularity of the toner is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow particle image analyzer (FPIA-2100; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.

  The toner has a volume average particle diameter (Dv) of 3.0 to 8.0 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.00 to 1.40. Preferably, the toner has a volume average particle size of 3.0 to 6.0 μm and a Dv / Dn of 1.00 to 1.15, so that any of heat resistant storage stability, low temperature fixability and hot offset resistance can be obtained. In particular, when used in a full-color copying machine, the glossiness of the image is excellent.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When used as a system developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
In addition, these phenomena are greatly related to the content of fine powder. Particularly, when the particle diameter of the toner exceeds 3%, the adhesion to the magnetic carrier and the stability of charging at a high level are hindered. Become.

  Conversely, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is performed. In many cases, the variation in the particle diameter of the toner increases. Further, when Dv / Dn exceeds 1.40, the resolving power decreases. When the volume average particle size is less than 3.0 μm, there is a concern about the influence on the human body due to the floating of the toner. When the volume average particle size exceeds 8.0 μm, the sharpness of the toner image on the photoreceptor is lowered and the resolving power is also lowered.

  The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter), laser diffraction / scattering LA-920 (manufactured by Horiba). . In the present invention, a Coulter counter TA-II type was used and connected to an interface (manufactured by Nikka Giken) and a PC9801 personal computer (manufactured by NEC) to output the number distribution and volume distribution.

The toner of the present invention is preferably a toner having a shape factor SF-1 in the range of 100 to 180 and SF-2 in the range of 100 to 180.
The shape factors SF-1 and SF-2 are represented by the following formulas (1) and (2).
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (2)

When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases. Further, when the value of SF-2 is 100, the unevenness does not exist on the toner surface, and as the SF-2 value increases, the unevenness of the toner surface becomes more prominent. FIG. 1A is a schematic diagram of a toner shape for explaining SF-1 and FIG. 1B is a diagram for explaining SF-2.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), introducing it into an image analyzer (LUSEX 3: manufactured by Nireco) and analyzing it. Calculated.

When the shape factors SF-1 and SF-2 are both close to 100 and the shape of the toner is close to a true sphere, the contact between the toner and the toner or the toner and the image carrier becomes a point contact. As a result, the fluidity becomes weaker, the fluidity becomes higher, and the adhesion between the toner and the image carrier becomes weaker, and the transfer rate becomes higher. The dot reproducibility is also improved. On the other hand, when the toner shape factors SF-1 and SF-2 are large to some extent, the margin for cleaning increases, and there is no problem such as defective cleaning. Therefore, it is preferable that the shape factors SF-1 and SF-2 are in the range of 100 to 180 as a range in which the image quality is not deteriorated from the balance between the two.
The toner of the present invention has a spindle shape and can be represented by the following shape rule.

FIG. 2 is a diagram schematically showing the shape of the toner of the present invention. In FIG. 2, when a spindle-shaped toner is defined by a major axis r ₁ , a minor axis r ₂ , and a thickness r ₃ (where r ₁ ≧ r ₂ ≧ r ₃ ), the toner of the present invention is a short toner. The ratio of the axis to the major axis (r ₂ / r ₁ ) (see FIG. 2B) is 0.5 to 1.0, and the ratio of the thickness to the minor axis (r ₃ / r ₂ ) (FIG. 2 ( c) is preferably in the range of 0.7 to 1.0. If the ratio of the minor axis to the major axis (r ₂ / r ₁ ) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, when the ratio of the thickness to the short axis (r ₃ / r ₂ ) is less than 0.7, it becomes close to a flat shape and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the short axis (r ₃ / r ₂ ) is 1.0, the rotating body has the long axis as the rotation axis, and the fluidity of the toner can be improved.
Note that r ₁ , r ₂ , and r ₃ were measured with a scanning electron microscope (SEM) while taking and observing photographs while changing the viewing angle.

The toner produced as described above can also be used as a one-component magnetic toner that does not use a magnetic carrier or a non-magnetic toner.
When used in a two-component developer, it may be used by mixing with a magnetic carrier, and the magnetic carrier is a ferrite containing a divalent metal such as iron, magnetite, Mn, Zn, Cu, A volume average particle size of 20 to 100 μm is preferred. If the average particle size is less than 20 μm, carrier adhesion is likely to occur on the photoreceptor during development, and if it exceeds 100 μm, the miscibility with the toner is low, the toner charge amount is insufficient, and charging failure during continuous use is likely to occur. . Further, Cu ferrite containing Zn is preferable because of high saturation magnetization, but can be appropriately selected according to the process of the image forming apparatus. The resin for coating the magnetic carrier is not particularly limited, and examples thereof include silicone resin, styrene-acrylic resin, fluorine-containing resin, and olefin resin. The manufacturing method may be that the coating resin is dissolved in a solvent, sprayed into the fluidized bed and coated on the core, or the resin particles are electrostatically attached to the core particles and then melted by heat to coat. You may do. The resin to be coated has a thickness of 0.05 to 10 μm, preferably 0.3 to 4 μm.

An image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 3 is a schematic diagram showing the configuration of an embodiment of the image forming apparatus according to the present invention. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.

  The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided. Above the tandem image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoconductor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.

  A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22.

The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

The developing device 4 of the image forming unit 18 uses a developer containing the above toner. In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the toner charge amount distribution can be narrowed, and the developability can be improved.
In addition, the photosensitive member 40 and the developing device are integrally supported, and the process cartridge can be formed to be detachable from the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit.

The operation of the image forming apparatus is as follows.
First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and reflects by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15, 16 is rotated by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan monochrome images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and the image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after image transfer, and is prepared for re-image formation by the tandem image forming apparatus 20.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. Hereinafter, “parts” means “parts by weight” unless otherwise specified.

<Example 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries, Ltd.), 1000 parts of L-lactide and 1 part of tin octylate were charged, and after nitrogen substitution Polymerization was conducted at 160 ° C. for 6 hours to obtain [Resin 1]. [Resin 2] was obtained in the same manner except that L-lactide was changed to D-lactide. As a result of X-ray crystal structure analysis (manufactured by Rigaku Corporation, using AFC7R, the same applies below), it was found that [Resin 1] contained a left-handed helical structure and [Resin 2] contained a right-handed helical structure. .
[Resin 1] 100 parts, Colorant [carbon black MA-100, manufactured by Mitsubishi Chemical Corporation] 2 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 2 parts Was melt-mixed by a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain [Resin Particles 1] having a particle size (Dv) of about 9 μm. The same operation was performed except that [Resin 1] was changed to [Resin 2] to obtain [Resin particles 2]. 100 parts of [Resin Particle 1] and 100 parts of [Resin Particle 2] were mixed with powder using a Henschel mixer (30 ° C., 60 minutes) to obtain a toner (P1) comprising the toner binder of the present invention.

<Example 2>
In a beaker, 100 parts of [Resin 1] and 40 parts of ethyl acetate were mixed, 500 parts of water and 3 parts of sodium dodecylnaphthalene sulfonate were added, and then a TK homomixer (made by Tokushu Kika) was used. An aqueous dispersion 1 was obtained by mixing at 12,000 rpm for 1 minute at 25 ° C. [Aqueous dispersion 2] was obtained in the same manner except that [Resin 1] was changed to [Resin 2].
100 parts of [Aqueous Dispersion 1], 100 parts of [Aqueous Dispersion 2], 4 parts of a colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Corporation], and a mold release agent [Biscol 550P (softening point 150) ° C); Sanyo Chemical Industries Co., Ltd.] [Aqueous Dispersion 3] consisting of 4 parts and 50 parts of water was mixed, and TK homomixer (manufactured by Tokushu Kika) was used. The mixture was stirred for minutes to obtain [Aqueous dispersion 4]. After stirring [Aqueous Dispersion 4] at 50 ° C. for 3 hours, the process of centrifuging, adding 100 parts of water and solid-liquid separation is repeated three times, and the toner of the present invention having a particle size (Dv) of about 5 μm Toner (P2) comprising a binder was obtained.

<Comparative Example 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries), 1000 parts of racemic-lactide and 1 part of tin octylate were added, and after nitrogen substitution And polymerized at 160 ° C. for 6 hours to obtain [Resin 3]. As a result of X-ray crystal structure analysis, it was found that [Resin 3] has a random structure and does not contain a helical structure.
[Resin 3] 100 parts, Colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Corporation] 4 parts, and Mold Release Agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 The parts were melt-mixed with a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain a toner (CP1) made of a comparative toner binder having a particle size (Dv) of about 9 μm.

<Comparative example 2>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries, Ltd.), 333 parts of racemic-lactide and 1 part of tin octylate were added, and after nitrogen substitution And polymerized at 160 ° C. for 6 hours to obtain [Resin 4]. [Resin 5] was obtained in the same manner except that 333 parts of racemic-lactide was changed to 1666 parts of racemic-lactide. As a result of X-ray crystal structure analysis, it was found that [Resin 4] and [Resin 5] had a random structure and did not contain a helical structure.
[Resin 4] 50 parts, [Resin 5] 50 parts, Colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Co., Ltd.] 4 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries [Made by Co., Ltd.] was melt-mixed with a twin-screw kneader [Ikegai PCM-30]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] The toner (CP2) made of a comparative toner binder having a particle size (Dv) of about 9 μm was obtained.

The physical properties of the toners (P1), (P2), (CP1) and (CP2) obtained as described above were confirmed and their performance was evaluated. The results are shown in Table 1.
Measurement of physical properties and performance evaluation were performed as follows.

(1) Number average molecular weight measurement The THF soluble content of the resin alone was measured by gel permeation chromatography (GPC).
The conditions for molecular weight measurement by GPC are as follows.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: Two TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 25 ° C
Sample solution: 0.25 wt% tetrahydrofuran (THF) solution Injection amount: 200 μl
Detection apparatus: Refractive index detector The molecular weight calibration curve was prepared using standard polystyrene.

(2) Stereocomplex abundance ratio The formation and abundance ratio of the stereocomplex in the present invention was determined by using “DSC-60” manufactured by Shimadzu Corporation. The toner before fixing (before C) was the toner alone, and the toner after fixing ( After C), a transparent film (Toray Lumirror 50-T60 cut to A4 size) was printed on a solid state image on a copying machine, and then about 5.0 mg each of the toner was scraped and collected from the film. Place the sample in a sample container, place the sample on the holder unit, and heat from 20 ° C. to 250 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere to determine the area of the endothermic peak that appears when a stereo complex is formed. Each was before C and after C.
If the toner stereo complex is not formed before fixing and is formed by fixing, the value before C is zero. If a new peak appears approximately 50 ° C. above the toner before fixing and a slight amount of stereocomplex formation occurs before fixing, it can be compared by (omitted) a change in the formation ratio of the stereocomplex.

(3) Melting characteristics The melting start temperature of the toner was measured with a flow tester (measuring device: constant-heavy extrusion type capillary rheometer flow tester CFT-500D (manufactured by Shimadzu Corporation), measurement conditions: plunger 1 cm2, die diameter 1 mm, load 20 KgF, preheating temperature 50 to 80 ° C., preheating time 300 sec, temperature rising time 6 ° C./min). The lowering start temperature of the plunger was taken as the melting start temperature.

(4) Minimum fixing temperature (MFT) and hot offset generation temperature (HOT)
A non-fixed image developed with a commercial copier [AR5030, manufactured by Sharp Corporation] using the above toner is modified with a fixing unit of a commercial full-color copier [LBP-2160, manufactured by Canon Inc.] to adjust the heat roller temperature. Fixing is performed at a process speed of 80 mm / sec using a variable fixing machine. The heat roller temperature at which the residual ratio of the image density after rubbing the fixed image with the cloth pad becomes 70% or more is defined as the minimum fixing temperature (MFT). Further, the temperature at which hot offset starts to occur by visual determination is defined as hot offset generation temperature (HOT).

  The toner of the present invention is extremely useful as a toner for use in toners used for electrophotography, electrostatic recording, electrostatic printing, and the like because of excellent heat melting characteristics and hot offset resistance.

It is the figure which represented typically the shape of the toner in order to demonstrate shape factor SF-1 and shape factor SF-2. It is a figure which shows typically the shape of the toner which concerns on this invention. 1 is a schematic configuration diagram showing an embodiment of an image forming apparatus using a toner according to the present invention.

Explanation of symbols

4 Developing device 10 Intermediate transfer belt 14, 15, 16 Support roller 18 Image forming means 20 Tandem image forming device 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 28 Reversing device 32 Contact glass 33 First Traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photosensitive body (latent image carrier)
43 Paper bank 44 Paper feed cassette 45 Separation roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separation roller 53 Manual feed path 55 Switching claw 56 Paper discharge roller 57 Paper output tray 62 Primary transfer means 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (28)

At least in the toner used in the image forming method fixed by heating, the stereocomplex abundance ratio of the resin present in the toner before fixing (before C) and the stereocomplex of the resin present in the toner component on the image after fixing The abundance ratio (after C) is
A toner for developing electrostatic charge, wherein C before <C after C.   The toner uses at least two kinds of resins, and the first toner using one resin (A) and the second toner using the other resin (B) exist independently and are mixed. The electrostatic charge developing toner according to claim 1, wherein one resin (A) and the other resin (B) form a stereocomplex.   The toner uses at least two kinds of resins, and agglomerates first primary particles using one resin (A) and second primary particles using the other resin (B). 2. The electrostatic charge developing toner according to claim 1, wherein the toner (1) and the other resin (B) form a stereocomplex.   4. The toner for electrostatic charge development according to claim 3, wherein the toner is not subjected to a heating or heating step of 90 [deg.] C. or more between at least the aggregation and the fixing. 5. The electrostatic charge development according to claim 1, wherein the two kinds of resins exist in a state where a stereo complex is not formed in a toner state, and form a stereo complex after fixing. Toner.   The one resin (A) contains one or more right-handed helical polymer units (a) in the molecule, and the other resin (B) contains one or more left-handed helical polymer units (b) in the molecule. 6) The toner for electrostatic charge development according to any one of claims 2 to 5, further comprising:   The resins (A) and (B) are one or more resins selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, polyether resins, and epoxy resins. The electrostatic charge developing toner according to any one of the above.   The electrostatic charge developing toner according to claim 6 or 7, wherein the monomer constituting the polymer units (a) and (b) comprises an optically active monomer (m).   The optically active monomer (m) is an α-alkyl (carbon number 1 to 4) -α-hydroxycarboxylic acid, α-hydrocarbyl (carbon number 1 to 12) -α-amino acid, α-hydrocarbyl (carbon). Number 1-8) A group consisting of methacrylate, cyclic ester having asymmetric carbon (3 to 6 carbon atoms), α-alkylethylene oxide (6 to 9 carbon atoms) and α-alkylethylene sulfide (6 to 9 carbon atoms). The electrostatic charge developing toner according to claim 8, wherein the toner is one or more selected from the above.   10. The electrostatic charge developing toner according to claim 8, wherein the optically active monomer (m) is L-lactic acid and D-lactic acid, and / or L-lactide and D-lactide.   The electrostatic charge developing toner is obtained by dissolving or dispersing a toner composition comprising at least a resin and a colorant in a polymerizable monomer, and emulsifying and dispersing the solution or dispersion in an aqueous medium. The electrostatic charge developing toner according to claim 1, which is obtained by polymerizing a liquid.   The electrostatic charge developing toner is obtained by dispersing a toner composition comprising at least a resin and a colorant in an aqueous medium, aggregating the dispersion in an aqueous medium, and heating and aggregating the aggregate. The toner for electrostatic charge development according to any one of claims 1 to 10.   The electrostatic charge developing toner is obtained by dissolving or dispersing a toner composition comprising at least a resin and a colorant in an organic solvent, emulsifying and dispersing the dissolved or dispersed material in an aqueous medium, and removing the organic solvent. The toner for electrostatic charge development according to any one of claims 1 to 10.   In the electrostatic charge developing toner, a toner composition comprising at least a resin and a colorant is dissolved or dispersed in an organic solvent, the dissolved or dispersed material is emulsified and dispersed in an aqueous medium, and the dissolved or dispersed material is overlapped. 11. The electrostatic charge developing toner according to claim 1, wherein the toner is obtained by addition reaction and removal of the organic solvent.   The release agent contains at least one selected from the group consisting of carnauba wax, montan wax, candelilla wax, oxidized rice wax, Fischer-Tropsch wax, paraffin wax and polyolefin wax. 14. The electrostatic charge developing toner according to any one of items 14.   The electrostatic charge developing toner according to claim 1, further comprising a charge control agent.   The electrostatic charge developing toner according to claim 1, wherein the toner has an average circularity of 0.94 or more.   The volume average particle diameter of the toner is 3.0 to 8.0 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40. 18. The electrostatic charge developing toner according to claim 1, wherein the toner is an electrostatic charge developing toner.   The toner for electrostatic charge development according to any one of claims 1 to 18, wherein the toner has a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180. . The shape of the toner is a spindle shape, and the spindle shape is defined by a major axis r ₁ , a minor axis r ₂ , and a thickness r ₃ (where r ₁ ≧ r ₂ ≧ r ₃ ), and the minor axis. The ratio (r ₂ / r ₁ ) between r ₂ and major axis r ₁ is in the range of 0.5 to 1.0, and the ratio (r ₃ / r ₂ ) between thickness r ₃ and minor axis r ₂ is The electrostatic charge developing toner according to claim 1, wherein the toner is in a range of 0.7 to 1.0.   A developer for developing a two-component electrostatic charge image, comprising the toner for electrostatic charge development according to any one of claims 1 to 20 and a carrier. In an image forming method for fixing a toner to a fixing medium by heating at least, a stereocomplex abundance ratio of a resin present in the toner before fixing by using the electrostatic charge developing toner according to claim 1. (Before C) and the stereocomplex abundance ratio (after C) of the resin present in the toner component on the image after fixing,
An image forming method, wherein C before <C after. An image forming apparatus in which a toner image on a transfer material is heated and melted by passing between a pair of opposed nips to fix the surface pressure (roller load / contact area) applied between the pair of opposed nips. 21. An image forming apparatus comprising: a fixing device that performs fixing at 1.5 × 10 ⁵ Pa or less, and using the toner according to claim 1.   The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member 24. The image forming apparatus according to claim 23, wherein the image forming apparatus is a fixing device that heats and fixes a recording material on which an unfixed image is formed.   25. The image forming apparatus according to claim 23, wherein the photoconductor used for image formation is an amorphous silicon photoconductor.   26. The image forming apparatus according to claim 23, further comprising a developing unit provided with an electric field applying unit for applying an alternating electric field when developing the latent image on the photosensitive member.   27. The image forming apparatus according to claim 23, further comprising a charging device that performs charging by bringing a charging member into contact with the latent image carrier and applying a voltage to the charging member.   A process cartridge that integrally supports at least one unit selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit, and is detachable from the image forming apparatus main body, the developing unit holding toner, 21. A process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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