JP4397382B2 - Toner for developing electrostatic image, and image forming method and apparatus using the same - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner resin, a master batch pigment, a toner, a developer, an image forming method, and an image forming apparatus.

  As the amount of work increases, image forming apparatuses such as copiers, facsimiles, and printers are used everywhere. An image forming method employing a typical electrophotographic method in this image forming apparatus is a charging process for uniformly charging the surface of a latent image carrier, and image-like exposure is performed on the charging process to dissipate the exposed charges. Exposure process to form an electric latent image (electrostatic charge image), development process to make the toner image visible by attaching a fine powder toner with electric charge to the latent image, transfer the obtained visible image to paper, etc. It consists of a transfer step for transferring to a material and a fixing step for fixing a visible image on a transfer member by heating or pressurization (usually using a heat roller).

  As a developer for developing the electrostatic image formed on the latent image carrier, a two-component developer composed of a carrier and a toner, and a one-component developer composed of only a toner without requiring a carrier ( Magnetic toner and non-magnetic toner) are known.

  The toner used in such an image forming method contains a binder resin and a colorant as main components and, if necessary, contains additives such as a charge control agent and an offset preventive agent. Various performances are required. For example, in the developing process, the toner and the binder resin for the toner are not affected by the surrounding environment such as temperature and humidity in order to attach the toner to the electric latent image, so that the copying machine, the printer, the printer, etc. The charge amount suitable for the image forming apparatus must be maintained. Further, in the fixing process by the heat roller fixing method, the non-offset property that does not adhere to the heat roller and the fixing property to paper or the like must be good. Furthermore, blocking resistance that prevents toner from blocking during storage in the image forming apparatus is also required.

  In addition, in a copying machine, a printer, a facsimile, or the like that employs an image forming method such as an electrophotographic method, an electrostatic recording method, or an electrostatic printing method, a heating roller heated to a temperature of about 100 to 230 ° C. is usually used. Used to fix the toner on paper or the like. In such a fixing process, the toner image is often fixed continuously on a large number of sheets of paper, and a very small amount of toner that does not affect the non-offset property is accumulated on the heating roller. The temperature of the heating roller rises due to continuous rotation and continuous supply of paper, etc., and the toner accumulated on the heating roller is heated, so that residual monomer and residual solvent remaining in the toner are volatilized. And generate odor.

  Such odors may be caused by binder resins and pigments in the toner, charge control agents, additives, raw materials such as masterbatch pigments mixed with resin and pigment, or residual monomers, low molecular weight components, residual solvents, etc. contained in the carrier. Volatile components, polar solvent-soluble components, various polar solvent-soluble components generated during toner production, etc., and for this reason, raw materials, residual monomers and residual solvents in toners, developers, volatile components, Reduction of polar solvent soluble components has been required.

  In response to these requirements, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 10-10882), it is judged by a method with poor objectivity such as whether or not an odor can be felt, or the amount of volatile components is determined. It was determined by the change in weight before and after drying and was not sufficiently separated from the moisture content. In Patent Document 2 (Japanese Patent Laid-Open No. 11-249334), the amount of residual monomer remaining in the toner is specified, but there is no particular idea as a method for detecting the monomer component, and it is detected by general gas chromatography or the like. The amount of the monomer component to be used is defined, and the amount of the polar solvent-soluble component which is a problem at this time has not been sufficiently considered.

  In addition, Patent Document 1 describes only a special suspension polymerized toner, describes only a detailed manufacturing method thereof, and does not have a general description. Further, the target is the amount of volatile components, not the polar solvent-soluble component for this purpose. Moreover, although patent document 2 has the following description, there was only general description and the effect of this objective was not fully exhibited. Furthermore, it controls all monomer components and is not a polar solvent-soluble component for this purpose. The polar solvent-soluble component includes dimer and trimer components other than the monomer, and there are many polar solvent-insoluble components such as a non-polar solvent such as hexane.

(Patent Document 2: Description of JP-A-11-249334)
As a method for reducing the residual monomer in the toner, a known method can be applied. For example, when the toner is produced by the production of a binder resin or a direct polymerization method, the method of adding an initiator and the reaction temperature are controlled. Thus, the residual monomer can be suppressed, or the residual monomer can be removed by distillation after the polymerization. In addition, when the toner is manufactured by a pulverization method, the raw material is removed under reduced pressure when the raw material is heated and kneaded by a kneader or the like. Residual monomer can be removed. In particular, when a toner is produced by a suspension polymerization method, it is possible to remove the toner particles when heat-drying.

  In addition, demands for reducing residual solvents, volatile components, and polar solvent soluble components are not only due to global environmental problems such as ecology, and human safety issues such as carcinogenicity and harmful substances, but also to toner quality issues. It is also desired to solve the problem. For example, the polar solvent-soluble component in the toner causes carrier spent, lowers the charge amount of the toner, and is one of the causes of image density reduction. It has become.

  On the other hand, as a binder resin, polystyrene, styrene are required in terms of properties required for toner, that is, transparency, insulation, water resistance, fluidity (as powder), mechanical strength, gloss, thermoplasticity, grindability, etc. -Acrylic copolymers, polyester resins, epoxy resins and the like are generally used, and among them, styrene resins are widely used because they are excellent in grindability, water resistance and fluidity.

  However, if the copy obtained with a styrene resin-containing toner is stored in a document holder made of a vinyl chloride resin sheet, the image surface of the copy is left in close contact with the vinyl chloride resin sheet. Therefore, the plasticizer contained in the sheet, that is, the vinyl chloride resin, is transferred and plasticized to the fixed toner image and welded to the sheet side. As a result, when the copy is separated from the sheet, a part or all of the toner image is copied from the copy. There was a drawback that the sheet was peeled off and the sheet was soiled. Such a defect is also seen in the polyester resin-containing toner.

  As measures for preventing the transition to the vinyl chloride resin sheet as described above, in Patent Document 3 (Japanese Patent Laid-Open No. 60-263951) and Patent Document 4 (Japanese Patent Laid-Open No. 61-24025), a styrene-based binder resin is used. Proposals have been made to blend an epoxy resin that is not plasticized with a plasticizer for a vinyl chloride resin into a resin or a polyester resin. However, when such a blend resin is used particularly for color toners, the incompatibility between different types of resins causes offset properties, fixed image curl, and glossiness (in the case of color toner images, poor images without gloss). Colorability, transparency, and color developability become problems. These problems cannot be solved by conventional epoxy resins or acetylated modified epoxy resins as proposed in Japanese Patent Application Laid-Open No. 61-235852.

  Therefore, it is conceivable to solve the above-mentioned problems by using an epoxy resin alone, but as a new problem, reactivity of the epoxy resin with amine occurs. Epoxy resins are generally used as curable resins having excellent mechanical strength and chemical resistance by reacting an epoxy group with a curing agent to form a crosslinked structure. Curing agents are roughly divided into amine-based and organic acid anhydride-based. Of course, epoxy resins used as toners are used as thermoplastic resins, but some dyes and pigments and charge control agents that are kneaded together with resins as toners are amine-based, and undergo crosslinking reaction during kneading. It may wake up and cannot be used as toner. In addition, the chemical activity of this epoxy group is considered to be biochemical, that is, toxic such as skin irritation, and its presence requires careful attention. In addition, since the epoxy group exhibits hydrophilicity, water absorption at a high temperature and high humidity is remarkable, which causes a decrease in charge, background contamination, poor cleaning, and the like. Furthermore, the charging stability in the epoxy resin is also a problem.

  Generally, a toner is composed of a binder resin, a colorant, a charge control agent, and the like. Various dyes and pigments are known as colorants, some of which have charge controllability, and some of which have two functions of a colorant and a charge control agent. The use of an epoxy resin as a binder resin to form a toner with the above-described composition is widely performed, but as a problem, there is dispersibility of dyes and pigments, charge control agents and the like.

  In general, kneading of a binder resin, a dye / pigment, a charge control agent and the like is generally performed by a hot roll mill, and it is necessary to uniformly disperse the dye / pigment, the charge control agent and the like in the binder resin. However, it is difficult to sufficiently disperse, and if the dye / pigment as a colorant is poorly dispersed, color development is poor and the coloring degree is lowered. Further, when the dispersion of the charge control agent or the like is poor, the charge distribution becomes non-uniform, which causes various defects such as charging failure, background smearing, scattering, insufficient ID, blurring, and cleaning failure.

  Patent Document 6 (Japanese Patent Laid-Open No. 61-219051) discloses a toner using an epoxy resin ester-modified with ε-caprolactone as a binder resin, but has improved PVC resistance, fluidity and the like. However, the modification amount was 15 to 90% by weight, and the softening point was too low and the gloss was too high.

  Patent Document 7 (Japanese Patent Application Laid-Open No. 52-86334) discloses a compound having a positive chargeability by reacting an aliphatic primary or secondary amine with a terminal epoxy group of a ready-made epoxy resin. As described above, there may be a case where the epoxy group and the amine cause a crosslinking reaction and cannot be used as a toner. In Patent Document 8 (Japanese Patent Laid-Open No. 52-156632), one or both of the terminal epoxy groups of the epoxy resin are reacted with alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride, or the like. However, when an epoxy group remains, problems such as reactivity with amine, toxicity, and hydrophilicity occur as described above. In addition, some of the reactants described above are hydrophilic, have an effect on charging, and have an effect on pulverizability when being made into toner, and are not necessarily all effective in the present invention.

  In Patent Document 9 (Japanese Patent Application Laid-Open No. 1-267560), both terminal epoxy groups of an epoxy resin are reacted with a monovalent active hydrogen-containing compound and then esterified with monocarboxylic acids, their ester derivatives, or lactones. Although the reactivity, toxicity, and hydrophilicity of the epoxy resin have been solved, curling has not been improved much in fixing.

  Further, in general, a solvent such as xylene is often used during the synthesis of the epoxy resin or polyol resin (for example, Patent Document 10: JP-A-11-189646). However, these solvents or unreacted residual monomers such as bisphenol A are used. Etc. are present in the resin after the production, and the residual amount is large even in the toner using these resins.

  On the other hand, as a toner production method, as typified by Patent Document 11 (JP-A-1-304467), all the raw materials are mixed at once and heated, melted and dispersed by a kneader or the like to obtain a uniform composition. A method of producing a toner having a volume average particle size of about 6 to 10 μm by cooling, pulverizing, and classifying the product is generally adopted.

  In particular, a color toner used for forming a color image is generally constituted by dispersing various chromatic dyes or pigments in a binder resin. In this case, the performance required for the toner to be used is stricter than that for obtaining a black image. In other words, as a color toner, in addition to mechanical and electrical stability against external factors such as impact and humidity, appropriate color expression (coloring degree) and light transmission (transparency when used in an overhead projector (OHP)) Sex) is required.

  Examples of using a dye as a color toner colorant include those described in Patent Document 12 (Japanese Patent Laid-Open No. 57-130043) and Patent Document 13 (Japanese Patent Laid-Open No. 57-130044). However, when a dye is used as the colorant, the resulting image has excellent transparency and good color development, and a clear color image can be formed, but on the other hand, it is inferior in light resistance and left under direct light. In this case, there is a problem of discoloration or fading.

  In addition, examples of using a pigment as a colorant for a color toner include those described in Patent Document 14 (Japanese Patent Laid-Open No. 49-46951) and Patent Document 15 (Japanese Patent Laid-Open No. 52-17023). However, the light resistance of the pigment-based color toner is excellent, but the dispersibility of the pigment with respect to the binder resin is poor, so that there is a problem that the coloring degree (coloring property) and transparency are inferior.

  As methods for improving the dispersibility of the pigment with respect to the binder resin, there are descriptions in Patent Document 16 (Japanese Patent Laid-Open No. 62-280755), Patent Document 17 (Japanese Patent Laid-Open No. 2-66561), and the like. Dispersion of the pigment could not be obtained, and the current situation was that the coloring degree and transparency were inferior. The methods described in Patent Document 18 (Japanese Patent Laid-Open No. 9-101632), Patent Document 19 (Japanese Patent Laid-Open No. 4-39671), Patent Document 20 (Japanese Patent Laid-Open No. 4-230770) and the like improve the dispersion of the pigment. However, since any method uses a solvent, there are not a few residual solvents, which is a problem. In addition, the use of the solvent caused a problem that the amount of polar solvent-soluble components increased.

  On the other hand, non-contact heat fixing has advantages such as not deteriorating the resolution of the image during development, less likely to cause paper jamming, and effective for high-speed printing and simultaneous printing on both sides, compared to heat rollers, etc. This fixing method has a large energy dispersion ratio, poor thermal efficiency, and high power consumption. For this reason, the heat to be applied is larger than that of the heat roller, the heat influence on the toner is large, and there is a concern that the amount of volatile components or polar solvent-soluble components increases.

  Furthermore, in the energy-saving fixing system, in order to improve the thermal efficiency of the fixing roller, use a thin roller with a thin roller layer, low surface pressure fixing, or use a film or belt body to improve the fixing efficiency. Attempts have been made. To cope with these systems, there is a demand for toner that can be fixed at low temperature and low pressure and that does not cause offset. As a result, it is necessary to lower the average molecular weight or increase the amount of low molecular weight components so that the toner can be fixed at a low temperature, and inevitably low molecular weight volatile components and polar solvent soluble components are likely to increase. It became a trend and was a problem.

  Further, as an on-demand publishing system that prints a necessary number of necessary items when necessary, an electrophotographic laser printer as described above can be used. This on-demand publishing system has great merits such as reduction in printing cost, stock out of printed matter, and shortened delivery time. However, the amount of printing per day increases according to customer requirements. That is, one or a plurality of laser printers operate in a room with a limited volume and output printed matter all day. As a result, the amount of toner consumption has increased remarkably, and the conventional toner and developer containing a large amount of polar solvent-soluble components have been pointed out as having a risk of harming the health of operators.

Japanese Patent Laid-Open No. 10-10882 JP-A-11-249334 JP-A-60-263951 Japanese Patent Laid-Open No. 61-24025 JP 61-235852 A JP-A-61-219051 JP-A-52-86334 JP 52-156632 A JP-A-1-267560 JP 11-189646 A JP-A-1-304467 JP-A-57-130043 JP 57-130044 A JP 49-46951 A JP-A 52-17023 JP-A-62-280755 JP-A-2-66561 JP-A-9-101632 Japanese Patent Laid-Open No. 4-39671 JP-A-4-230770

The purpose of the present invention is to
1. There are few polar solvent soluble components that cause odors from toner and developer, excellent environmental charge stability as toner and developer, continuous image output, no image density reduction, fixability and non-offset Toner and developer with excellent balance of
2. Toner, developer, process cartridge, image forming method, and image forming apparatus, which have few polar solvent soluble components in the toner, are less harmful to the health of the operator, and are environmentally friendly,
3. Toner with less polar solvent soluble components, excellent color reproducibility, color clarity, color transparency, stable gloss,
4). Toner with less polar solvent soluble components in the toner, stable against amine compounds and biochemically stable,
5). Toner with less polar solvent soluble components in the toner, excellent environmental stability and storage stability,
6). Toner with good manufacturability that does not affect the health and safety of the operator due to sensitization, there are few polar solvent soluble components in the toner, no by-products from side reactions during production,
7). Toner that does not transfer the toner image to the sheet even when the polar image soluble component in the toner is small and the fixed image surface is closely attached to the vinyl chloride resin sheet,
8). It is an object of the present invention to provide a toner in which the polar solvent-soluble component in the toner is small and the fixed image is not substantially curled.

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors are soluble in a polar solvent (mixed solution of water and acetonitrile in a volume ratio of 5: 5) contained in toner, binder resin, masterbatch pigment, developer and the like. By reducing the amount, there is less odor, it does not affect the health and safety of the operator, it is clean, charging environment stability, excellent environmental preservation, less trouble such as image density reduction, and fixing It has been found that a toner, a binder resin, a master batch pigment, a developer, an image forming method, and an image forming apparatus that are excellent in balance with non-offset properties and excellent in color reproducibility and sharpness can be obtained.

  The mechanism is currently being elucidated, but the following were inferred from some analysis data. That is, the toner controls the charging characteristics using a base resin, a charge control agent, an external additive, etc. In the case of the two-component development method, the outermost surface of the toner and the outermost surface of the carrier (in the case of the one-component development method) , The developing sleeve surface, etc.) contributes the most to the chargeability. A component soluble in a polar solvent in the toner (for example, bisphenol A) adheres to the surface of the carrier during agitation charging, lowers the chargeability of the carrier, causes poor charging of the toner, and lowers the image density. Estimated.

Thus, according to the present invention, the following (1) to ( 29 ) are provided.

(1): An electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the binder resin contains at least a binder resin material before or during the synthesis of the binder resin. Water is added to the mixture to form a water mixture, and the water mixture is subjected to a bubbling treatment under reduced pressure to at least contain a polyol resin formed by reducing soluble components soluble in the mixture. Toner for charge image development.

(2) The electrostatic image developing toner according to (1), wherein volatile components are also reduced by the bubbling treatment.

(3) The electrostatic image developing toner according to ( 1) or ( 2), wherein the soluble component is soluble in the mixed solution.

(4): The soluble component is soluble in a mixed solution of water and acetonitrile in a volume ratio of 5: 5, and the content relative to 1 g of toner is 3 μg or more and 1000 μg or less. ) To (3) electrostatic image developing toner.

( 5 ): The electrostatic charge image developing toner according to any one of (1) to ( 4 ) above, wherein the weight concentration of bisphenol A as a binder resin of the toner is 1000 μg or less with respect to 1 g of the toner. .

( 6 ): The color toner having at least three colors, wherein the maximum value of the difference in weight concentration of the components soluble in the mixed solution between the color toners is 300 μg or less. Item 4. The toner for developing an electrostatic charge image according to any one of Items ( 5 ) to ( 5 ).

( 7 ): The toner according to any one of (1) to ( 6 ), wherein the toner has a melt viscosity at 140 ° C. of 120 mPa · s or less. Developing toner.

( 8 ): The toner according to any one of (1) to ( 7 ), wherein the toner has a softening point of 70 to 160 ° C. and a glass transition temperature (Tg) of 40 to 40. A toner for developing an electrostatic charge image, characterized by being at 70 ° C.

( 9 ): The toner according to any one of (1) to ( 8 ), wherein the toner has a number average molecular weight (Mn) of 2000 to 8000, and a weight average molecular weight / number average molecular weight (Mw). / Mn) is 1.5 to 20, and at least one peak molecular weight (Mp) is 3000 to 7000.

(10): the first (1) section, second (9) The toner according to any one of Items, the toner binder resin, a polyol having an epoxy resin part and a port polyoxyalkylene portion to at least the main chain An electrostatic image developing toner comprising at least a resin.

( 11 ): The toner according to any one of (1) to ( 10 ), wherein the binder resin of the toner has at least an epoxy resin part, a polyoxyalkylene part, and a polyester part in the main chain. A toner for developing an electrostatic charge image, comprising at least a polyol resin.

( 12 ): The toner according to any one of Items (1) to (11) , wherein the polyol resin terminal of the binder resin of the toner is inactive. Toner.

( 13 ): The toner according to any one of (1) to (12) , wherein at least (1) an epoxy resin and (2) a dihydric phenol are used as a binder resin of the toner. An alkylene oxide adduct or a glycidyl ether thereof, (3) a compound having one active hydrogen in the molecule that reacts with an epoxy group, and (4) a compound having two or more active hydrogens in the molecule that react with an epoxy group. An electrostatic charge image developing toner comprising at least a resin characterized by using a polyol resin obtained by reaction.

( 14 ): The toner according to any one of ( 10 ) to ( 13 ), wherein the epoxy resin constituting the polyol of the binder resin of the toner has at least two types having different number average molecular weights. A toner for developing an electrostatic charge image, which is the above bisphenol A type epoxy resin.

( 15 ): The toner according to item ( 14 ), wherein the epoxy resin constituting the polyol of the binder resin of the toner is at least two bisphenol A type epoxy resins having different number average molecular weights. A toner for developing an electrostatic charge image, wherein the low molecular weight component has a number average molecular weight of 360 to 2,000, and the high molecular weight component has a number average molecular weight of 3000 to 10,000.

( 16 ): The toner according to ( 15 ), wherein the epoxy resin constituting the polyol of the binder resin of the toner is at least two bisphenol A type epoxy resins having different number average molecular weights . A toner for developing an electrostatic charge image , wherein the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 wt% with respect to the polyol resin.

( 17 ): The toner according to any one of (13) to (16), wherein the glycidyl ether of an alkylene oxide adduct of a dihydric phenol constituting the polyol is an alkylene oxide of bisphenol A. A toner for developing an electrostatic charge image, characterized by using a diglycidyl ether as an adduct and a binder resin represented by the following general formula (1).

( 18 ): The toner according to any one of ( 13 ) to ( 17 ), wherein an alkylene oxide adduct of a dihydric phenol constituting the polyol or a glycidyl ether thereof is added to the polyol resin. A toner for developing an electrostatic charge image, comprising a binder resin contained in an amount of 10 to 40 wt%.

( 19 ): The toner according to any one of ( 10 ) to ( 18 ), wherein the binder resin has an epoxy equivalent of 20000 or more. .

( 20 ): A binder resin for an electrostatic charge image developing toner, wherein the binder resin is prepared by adding water to an organic solvent liquid containing at least a binder resin material before or during a binder resin synthesis reaction, None, A binder resin for an electrostatic charge image developing toner, comprising at least a polyol resin obtained by bubbling the water mixture under reduced pressure to reduce at least soluble components soluble in the mixture.
.

( 21 ): The electrostatic charge image developing toner according to ( 20 ), wherein the weight concentration of the component soluble in the mixed solution is 1000 μg or less with respect to 1 g of the resin. resin.

( 22 ): A method for producing a binder resin for an electrostatic charge developing toner containing at least a polyol resin, wherein water is added to an organic solvent liquid containing at least a binder resin material before or during a binder resin synthesis reaction and mixed with water. A method for producing a binder resin for an electrostatic charge developing toner, comprising a step of bubbling the water mixture under reduced pressure to reduce at least soluble components soluble in the mixture.

( 23 ): A masterbatch pigment in which a pigment is dispersed in a resin, wherein the toner resin and the pigment described in (20) or (21) are heated and kneaded. Masterbatch pigment for electrostatic image developing toner.

( 24 ): The master batch pigment according to ( 23 ), wherein the weight concentration of the component soluble in the mixed solution is 500 μg or less with respect to 1 g of the master batch pigment. Masterbatch pigment for developing toner.

( 25 ): The master back pigment according to any one of ( 23 ) or ( 24 ), wherein a dry powder pigment is used as the pigment, and the dry powder pigment and the binder resin are mixed. A masterbatch pigment for an electrostatic charge image developing toner, comprising a step of adding at least water to the mixture and heating and kneading the mixture to remove water during mixing.

( 26 ): An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to any one of (1) to ( 19 ) and a carrier.

( 27 ): The developer for developing an electrostatic charge image according to item ( 26 ), wherein the weight concentration of the component soluble in the mixed solution is 500 μg or less with respect to 1 g of the developer. Developer for developing electrostatic image.

( 28 ): The toner described in any one of (1) to ( 19 ) or the developer described in ( 26 ) or ( 27 ) is used. Image forming method.

( 29 ): A container filled with the toner according to any one of (1) to ( 19 ) or the developer according to ( 26 ) or ( 27 ). An image forming apparatus.

  By using the toner and developer for developing an electrostatic charge image in which the weight concentration of the soluble component of the polar solvent of the present invention is regulated, the environment-friendly safety is high and the toner spent is less likely to occur. By exhibiting storage stability and excellent environmental charge stability, stable images can be obtained even under various environments, and images that do not transfer to the PVC mat can be obtained. Further, when used for a color toner, it is possible to obtain a printed matter that exhibits appropriate gloss and color reproducibility and is substantially free from curling on the image surface.

  Hereinafter, the present invention will be described in more detail. As described above, the present invention seeks to obtain good quality toners, images and the like by reducing the amount of polar solvent soluble contained in the electrostatic image developing toner.

  The amount of the polar solvent-soluble component in the toner is controlled to 1000 μg or less, preferably 500 μg or less, more preferably 100 μg or less, more preferably 30 μg or less, and even more preferably 10 μg or less with respect to 1 g of the toner. It was found that it can be obtained.

  The amount of the polar solvent-soluble component in the toner is preferably 3 μg or more with respect to 1 g of the toner. In order to make the amount less than 3 μg with respect to 1 g of toner, a low molecular weight reactive group such as an alkylene oxide adduct of dihydric phenol or a glycidyl ether thereof is equivalent to a base polymer such as an epoxy resin or It is necessary to formulate and react less than that. As a result, there arises a problem that a reaction residue of the base polymer such as an epoxy group remains in the reaction. The chemical suitability of this epoxy group is considered to be biochemical, ie, toxic such as skin irritation, and its presence is not preferred. In addition, since the epoxy group exhibits hydrophilicity, water absorption at a high temperature and high humidity is remarkable, which causes a decrease in charge, background contamination, poor cleaning, and the like. Furthermore, a decrease in charging stability in the epoxy resin is also a problem. Further, it has been found that when the amount is less than 3 μg with respect to 1 g of toner, the interface between the polar solvent-soluble component and the binder resin is reduced, and the toner pulverization property is lowered. As a result, the toner yield decreases and the toner cost increases, which is not preferable. Further, the polar solvent-soluble component also affects the chargeability of the toner, and if the amount of this component is excessively reduced, the charge amount of the toner and the charge rising property are undesirably lowered.

  Furthermore, especially for the toner, the amount of bisphenol A relative to 1 g of the toner is controlled to be 1000 μg or less, preferably 500 μg or less, more preferably 100 μg or less, more preferably 30 μg or less, and even more preferably 10 μg or less. Thus, it is possible to obtain a toner that has less adverse effects on the human body and that is less likely to generate spent and has excellent charging stability.

  Further, the toner is a color toner for a multicolor image forming method, and the difference in the weight concentration of the polar solvent soluble component with respect to 1 g of each color toner is 300 μg or less, preferably 100 μg or less, more preferably 30 μg or less (ideally Is 0 μg), it is possible to obtain a toner for developing an electrostatic image having excellent charging environment stability with little variation in chargeability between colors. As a result, an image having excellent color reproducibility and sharpness after development and fixing can be obtained.

  Further, when the amount of the polar solvent soluble component decreases, the low molecular weight component decreases and the melt viscosity tends to increase. However, by controlling the melt viscosity at 140 ° C. of the toner to 120 mPas · sec or less, the viscosity of the toner Becomes sufficiently low, the toner image enters the fixing area, the toner surface melts, the gloss is increased, and the color can be sharpened. For example, in order to more precisely control the reaction state and the crosslinking state when producing the binder resin, the reaction temperature, time, type and amount of the catalyst are controlled, and the toner molecular chain does not break the toner kneading conditions. The above-mentioned sufficient melt viscosity can be obtained by kneading strongly to a certain degree or kneading for a long time at a high temperature.

  Further, when the amount of the polar solvent-soluble component is reduced, the thermal properties of the toner also change, but the softening point of the toner is 70 to 160 ° C., more preferably 90 to 120 ° C., and the glass transition temperature (Tg) is 40. By controlling the temperature to ˜70 ° C., more preferably 50 ° to 70 ° C., a toner having excellent fixability, color reproducibility, sharpness, and color transparency could be obtained.

  Further, the number average molecular weight (Mn) of the toner is controlled to 2000 to 8000, the weight average molecular weight / number average molecular weight (Mw / Mn) is 1.5 to 20, and at least one peak molecular weight (Mp) is controlled to 3000 to 7000. As a result, it was possible to obtain a toner that can be fixed at a low temperature and has excellent fixability, color reproducibility, sharpness, and color transparency.

  The toner binder resin contains at least a polyol resin, whereby environmental stability and stable fixing characteristics can be obtained. Further, the toner binder resin has at least an epoxy resin portion and a polyoxyalkylene portion in the main chain. By including at least a polyol resin, environmental stability, stable fixing characteristics, and prevention of transfer of the toner image to the sheet when in contact with the sheet of the copy-fixed image on the vinyl chloride resin can be achieved. When used in an image, it is effective in color reproducibility, stable gloss, curling prevention of copy-fixed images, and the like. Here, the epoxy resin part means an epoxy resin part that does not have an epoxy group itself and includes a modified group (such as a structure in which an epoxy ring is opened).

  Further, when the polyol resin terminal of the toner binder resin is inactive, the toner can be made less environmentally stable and less harmful. The term “inert” as used herein means that there are no chemically reactive substituents at all, or even if they are present, they do not exist in a sufficient amount to adversely affect the quality characteristics of toners and resins, or harm human health. Means things. For example, it means that a highly reactive epoxy ring is opened and changed to an OH group to reduce the reactivity.

  The epoxy resin used in the present invention is preferably obtained by binding bisphenol such as bisphenol A or bisphenol F and epichlorohydrin. In order to obtain stable fixing characteristics and gloss, the epoxy resin is at least two types of bisphenol A type epoxy resins having different number average molecular weights. The low molecular weight component has a number average molecular weight of 360 to 2000, and has a high molecular weight component. The number average molecular weight is preferably 3000 to 10,000. Further, it is preferable that the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 wt%. When the amount of the low molecular weight component is too large or the molecular weight is lower than the molecular weight 360, there is a possibility that the gloss is too high or the storage stability is deteriorated. Further, when the amount of the high molecular weight component is too large or the molecular weight is higher than 10,000, the gloss may be insufficient or the fixing property may be deteriorated.

  Examples of the compound used in the present invention include the following as the alkylene oxide adduct of dihydric phenol. Examples include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The resulting adduct may be used after glycidylation with epichlorohydrin or β-methylepichlorohydrin.

  In particular, diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

  Moreover, it is preferable that 10-40 wt% of the alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained with respect to polyol resin. If the amount is too small, problems such as an increase in curl occur, and if n + m is 9 or more, or if the amount is too large, gloss may be excessively produced, and storage stability may be deteriorated.

  Examples of the compound having one active hydrogen in the molecule that reacts with the epoxy group used in the present invention include monohydric phenols, secondary amines, and carboxylic acids. Examples of monohydric phenols include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, and p-cumylphenol. Secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of carboxylic acids include propionic acid and caproic acid.

  In order to obtain a polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various raw material combinations are possible. For example, it can be obtained by reacting an epoxy resin having a glycidyl group at both ends and an alkylene oxide adduct of a dihydric phenol having both glycidyl groups with a dihalide, diisocyanate, diamine, dithiol, polyhydric phenol, or dicarboxylic acid. Among these, it is most preferable to react divalent phenol from the viewpoint of reaction stability. Moreover, it is also preferable to use polyhydric phenols and polyhydric carboxylic acids in combination with dihydric phenols as long as they do not gel. Here, the amount of polyphenols and polycarboxylic acids is 15% or less, preferably 10% or less, based on the total amount.

  Examples of the compound having two or more active hydrogens in the molecule that react with the epoxy group used in the present invention include dihydric phenols, polyhydric phenols, and polycarboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. Examples of the polyhydric phenols include orthocresol novolacs, phenol novolacs, tris (4-hydroxyphenyl) methane, and 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] benzene. Examples of the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.

  Further, by using a polyol resin having an epoxy resin part, a polyoxyalkylene part and a polyester part in the main chain in the resin used in the present invention, the viscoelasticity and hardness of the resin are changed particularly by the polyester component, so that the softer resin. It is more preferable because it is a physical property and curling of the image can be suppressed.

  Further, by controlling the epoxy equivalent of the binder resin to 10000 or more, preferably 30000 or more, more preferably 50000 or more, the thermal characteristics of the resin can be controlled, and a low-molecular epichlorohydrin that is a reaction residue, etc. Therefore, the toner can be made excellent in both safety and resin characteristics.

  In addition, in order to obtain a resin for use in a toner having a small amount of the polar solvent-soluble component, an organic solvent liquid containing at least a binder resin or a binder resin material before, during, or after a binder resin synthesis reaction is used. By adding water to form a water mixture and bubbling the water mixture under reduced pressure, a polar solvent can be effectively used by using a manufacturing process that reduces volatile components and soluble components soluble in the mixture. It has been found that dissolved components can be reduced. At that time, by controlling the residual water concentration in the binder resin to 1% or less, it is possible to obtain a toner with more excellent environmental stability.

  For raw materials such as toner charge control agents, external additives, pigments, carrier resins, charge control agents, etc., for example, by using higher purity raw materials, the polar solvent-soluble component weight concentration can be set to 1 g of toner. It is possible to make it 1000 μg or less. The purity can be confirmed, for example, by various analytical methods such as column chromatography, HPLC, GPC, and GC. Impurities from the production line and the like include frequent cleaning, overhaul, improvement of the efficiency of the exhaust duct system, etc. to keep the production line clean, exclusive use of the same kind of toner, operator training, and the like.

  In the master batch pigment in which the pigment is dispersed in the resin, the amount of the polar solvent-soluble component is preferably obtained by kneading the resin containing the low-polar component-soluble component and the pigment more preferably without using an organic solvent. The master batch pigment can be obtained with a small amount. More preferably, a dry powder pigment is used as the pigment, and when the dry powder pigment and the binder resin are mixed, at least water is added, and the mixture is heated and kneaded and then the water is removed, The dispersibility of the pigment is improved, and a master batch pigment having excellent color stability, transparency, and color reproducibility can be obtained.

  Furthermore, the weight concentration of the polar solvent-soluble component in the masterbatch pigment is 500 μg or less, more preferably 100 μg or less, and even more preferably 30 μg or less with respect to 1 g of the masterbatch pigment. The master batch pigment has a small amount of components soluble in a polar solvent and has excellent color stability and transparency.

  Further, by mixing and stirring a carrier with a small amount of residual polar solvent-soluble component with the above-mentioned toner, the weight concentration of the polar solvent-soluble component is 500 μg or less with respect to 1 g of developer, and for electrophotographic toner having excellent charging stability. A developer was obtained.

  Even when the image fixing method uses a non-contact heating fixing method in which the energy dispersion ratio to the surroundings is large and the power consumption is large, by using the toner and developer having a low polar solvent-soluble component, An image forming method and apparatus having excellent safety with little generation of polar solvent-soluble components due to heat during fixing were obtained.

  Furthermore, in a low-temperature fixing system using a thin roller, a low surface pressure fixing, or a film or belt body, it is necessary to reduce the average molecular weight in order to enable the toner to be fixed at a low temperature. This is a problem because the soluble component tends to increase, but by defining the amount of the polar solvent soluble component in the toner and developer, it is possible to form an image with excellent safety without sacrificing the thermal characteristics of the toner. A method and apparatus were obtained.

  Here, all known methods and materials for the toner and developer used in the present invention can be used. However, in the present invention, a device for setting the polar solvent-soluble component to the specified value of the present invention can be used. is necessary.

(Polar solvent component determination)
The weight concentration of the polar solvent-soluble component of the present invention can be determined by, for example, high performance liquid chromatography (HPLC) shown below. There is another method for obtaining by gas chromatography, but HPLC is preferred in terms of accuracy. A sample is dissolved in a solvent in which toner or resin is soluble (for example, tetrahydrofuran (THF), toluene, methyl ethyl ketone, dichloromethane, chloroform, etc.), and then a mixed solution of 50% water and 50% acetonitrile as a polar solvent in the solution. To form a precipitate to reduce polar solvent insoluble matter and extract polar solvent soluble matter. The extracted components are quantified using a standard sample after separation and qualification by HPLC.

Although a detailed example is shown below, it will not be limited to the following apparatuses and conditions as long as it is a technique which can analyze a polar solvent soluble content accurately.
1. Method: High performance liquid chromatography (HPLC)
2. Apparatus: Waters Alliance 2690, UV 2487 type detector Condition: Column Develosil ODS-Hg-3 (manufactured by Nomura Chemical Co., Ltd.) 4.6φ × 150 mm moving bed Water / acetonitrile = 65/35 flow rate 1.0 ml / min detection 228 nm injection volume 15 μl
4). Sample preparation ・ Weigh exactly 1 g of sample into a 100 ml Erlenmeyer flask.
-Add 30 ml of THF and dissolve.
-When completely dissolved, add 50 ml of methanol to form a precipitate.
Remove the solvent after filtering with 5A filter paper.
Make the volume constant with 5 ml of acetonitrile and 5 ml of distilled water.
-Filter the above solution with a filter to make an HPLC sample.
・ Prepare the standard samples in the same way.

(Polar solvent soluble component)
The polar solvent-soluble component defined in the present invention is the total amount of extraction components that can be dissolved in a mixed solution of 50% water and 50% acetonitrile in a volume ratio that is a polar solvent, and all substances that satisfy this condition are applicable. Specifically, resin unreacted residue, resin monomer component, impurities in colorant, impurities in charge control agent, impurities in external additive, impurities contained in production line during toner production, contained in master batch pigment Impurities or monomer components in the carrier overcoat layer, or as contaminants or intentionally in the production of resins, charge control agents, pigments, masterbatch pigments, external additives, or in the production of toners and developers Including various components.

(Melt viscosity)
The melt viscosity of the toner of the present invention was measured by a constant temperature method using an elevated flow tester (CFT-500) (manufactured by Shimadzu Corporation) under the conditions of a die pore diameter of 1 mm and a pressure of 20 kg / cm ² .

(Softening point)
The softening point of the toner of the present invention was measured using a softening point measuring device (FP90, manufactured by Mettler Co., Ltd.) at a heating rate of 1 ° C./min.

(Glass transition temperature (Tg))
The Tg of the toner of the present invention was measured under the following conditions using the following differential scanning calorimeter.
・ Differential scanning calorimeter: SEIKO1DSC100SEIKO1SSC5040 (Disk Station)
Measurement conditions: Temperature range: 25 to 150 ° C. Temperature increase rate: 10 ° C./min Sampling time: 0.5 sec Sample amount: 10 mg

(Molecular weight)
The number average molecular weight (Mn), weight average molecular weight (Mw), and Mp were measured by GPC (gel permeation chromatography) as follows. A sample solution is prepared by dissolving 80 mg of a sample in 10 ml of THF, filtered through a 5 μm filter, 100 μl of this sample solution is injected into the column, and the retention time is measured under the following conditions. Moreover, the retention time was measured using polystyrene having a known average molecular weight as a standard substance, and the number average molecular weight of the sample was determined in terms of polystyrene from a calibration curve prepared in advance.
Column: Guard column + GLR400M + GLR400M + GLR400 (all manufactured by Hitachi, Ltd.)
Column temperature: 40 ° C. Mobile phase (flow rate): THF (1 ml / min)
-Peak detection method: UV (254 nm)

(Epoxy equivalent)
The epoxy equivalent was determined by the indicator titration method shown in 4.2 of JIS K7236.

(Penetration)
The toner was weighed 10 g at a time, placed in a 20 cc glass container and left in a thermostatic bath set at 50 ° C. for 5 hours, and the penetration was measured with a penetration meter.

(Masterbatch pigment)
The masterbatch pigment of the present invention is more preferably a masterbatch pigment having excellent environmental charge stability by producing a low-polar solvent-soluble component amount of resin and pigment by heating and kneading without using an organic solvent. be able to. Furthermore, dispersibility can be further improved by using dry powder pigment and using water as a method of wetting with the resin. In addition, when the weight concentration of the polar solvent-soluble component is 500 μg or less, more preferably 300 μg or less, more preferably 100 μg, and even more preferably 30 μg or less with respect to 1 g of the masterbatch pigment, the environmental chargeability when used as a toner is improved. It will be better.

  Organic pigments that are generally used as colorants are hydrophobic, but in the manufacturing process, they are washed with water and dried, so if some force is applied, water is soaked into the pigment aggregate. It is possible. When a mixture of a pigment in which water is soaked into the aggregate and a resin is kneaded at a set temperature of 100 ° C. or higher with an open type kneader, the water inside the aggregate instantaneously reaches the boiling point and expands in volume. Therefore, a force is applied to break up the aggregate from the inside of the aggregate. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside. Furthermore, at this time, since the resin is heated to a temperature higher than the softening point, the viscosity is lowered and the aggregate is efficiently wetted. By being replaced by the effect, a master batch pigment in which the pigment is dispersed in a state close to primary particles can be obtained. Furthermore, in the process of evaporating water, the heat of vaporization accompanying water evaporation is taken away from the kneaded product, so the temperature of the kneaded product is kept at a relatively low temperature and high viscosity of 100 ° C. or less, so the shearing force is effective. In addition, it has the effect of being added to the pigment aggregate.

  As an open type kneader for producing a master batch pigment used in the present invention, in addition to the usual two rolls and three rolls, a method using a Banbury mixer as an open type, a continuous two roll kneader manufactured by Mitsui Mining Co., Ltd. Etc. can be used.

(Binder resin)
As the binder resin of the toner of the present invention, polymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like, and substituted products thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl Ketone copolymer, styrene Styrene copolymers such as tadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer: polymethyl methacrylate, poly Butyl 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, aliphatic or alicyclic Aromatic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

  More preferably, as described in the means for solving the problems, at least a polyol resin or at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain is included, so that environmental stability and stable fixing characteristics are achieved. It is possible to prevent the transfer of the toner image to the sheet when it is in close contact with the vinyl chloride resin surface of the copy-fixed image surface, especially when used for color toner, color reproducibility, stable gloss, copy-fixed image This is more preferable because it has an effect on curling prevention and the like.

  In order to obtain the resin of the present invention, water is added to an organic solvent liquid containing at least a binder resin or a binder resin material before, during, or after a binder resin synthesis reaction to form a water mixture, Bubbling treatment of the water mixture under the process includes a production process for reducing volatile components and soluble components soluble in the mixture, thereby more effectively dissolving polar solvent soluble components, residual solvents, unreacted Monomers, volatile components, water, etc. can be reduced, which is more desirable. In that case, it is more preferable that the residual water concentration in the resin is 1% or less, more preferably 0.5% or less, since the environmental chargeability when the toner is used is further improved.

(Coloring agent)
As the colorant of 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 yellow , Yellow iron oxide, ocher, yellow lead, titanium 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, Anslagen Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para red, fire red, parachlor ortho nitro Nilin Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scalate VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol 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, Thio Indigolet B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, black Munver Million, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC) ), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxazine Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof.

  Generally the usage-amount of a coloring agent is 0.1-50 weight part with respect to 100 weight part of binder resin. In order to control the amount of the polar solvent-soluble component in the toner, it is preferable that the amount of the polar solvent-soluble component in the pigment or in the impurities contained in the pigment is also small.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All 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 salts (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, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP 415 (manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP 2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEGVP 2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, Examples thereof include azo pigments and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

  Depending on the type of charge control agent, there are many polar solvent-soluble components in the main component or impurities, but the use of a charge control agent with few polar solvent-soluble components as a raw material is the amount of polar solvent-soluble components in the toner. It is more preferable to reduce the amount.

(External additive)
The toner of the present invention may contain an external additive as necessary. As the external additive, inorganic fine particles and hydrophobized inorganic fine particles can be used, and all of known ones can be used. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable external additives include hydrophobized silica, titania, and alumina fine particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21 (manufactured by Hoechst), and R972, R974, RX200, RY200, R202, R805, R812 (manufactured by Nippon Aerosil Co., Ltd.). is there. Further, as titania fine particles, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT -500B, MT-600B (manufactured by Teica).

  In particular, as hydrophobized titanium oxide fine particles, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T (manufactured by Fuji) Titanium Industry), MT-100S, MT-100T (above, manufactured by Teika), IT-S (made by Ishihara Sangyo), and the like.

  In order to obtain hydrophobized silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles must be treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can do. In addition, silicone oil-treated inorganic fine particles obtained by treating the silicone oil with heat if necessary to treat the inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino-modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.

  Examples of inorganic fine particles include silica, alumina, titanium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica And wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. Of these, silica and titanium dioxide are particularly preferred.

  The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged. The average particle diameter here is a number average particle diameter.

  The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics Co., Ltd. Since it is difficult to dissociate the secondary aggregation of the particles after the hydrophobization treatment, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

  Further, it is more preferable to use a charge control agent having a small amount of polar solvent-soluble components in the external additive in order to reduce the amount of polar solvent-soluble components in the toner. The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner.

(Career)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.

  When the carrier is coated with a resin, it is more preferable to reduce volatile components due to residual solvents and impurities in the coating resin by changing the coating conditions (drying temperature, drying time, atmosphere).

  Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins.

  Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(wax)
In order to impart releasability to the toner or developer, it is preferable to include a wax in the toner or developer. The wax has a melting point of 40 to 120 ° C., and preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point. The content of the wax is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight with respect to 100 parts by weight of the toner.

  Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. Particularly, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable.

  It is more preferable that a cleaning property improving agent for removing the transferred developer remaining on the photoreceptor or the primary transfer medium is contained in the toner or added to the toner surface, or contained in the developer or added to the surface. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, polystyrene 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 content of the cleaning property improving agent is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the toner.

(Magnetic material)
Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. When the magnetic toner is used, the toner particles may contain magnetic fine particles. Such magnetic materials include metals, alloys such as ferrite, magnetite and other irons, nickel, cobalt, etc., or compounds containing these elements, and those containing no ferromagnetic elements, but by applying an appropriate heat treatment. Examples include alloys that exhibit ferromagnetism, such as alloys such as manganese-copper-aluminum, manganese-copper-tin, and so-called Heusler alloys containing manganese and copper, chromium dioxide, and the like. It is preferable that the magnetic material is contained in a uniformly dispersed form in the form of fine powder having an average particle size of 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight, particularly preferably 20 to 50 parts by weight, with respect to 100 parts by weight of the obtained toner.

(Toner production method)
The toner manufacturing method of the present invention includes a step of mechanically mixing a developer component including at least a binder resin, a main charge control agent, and a pigment, a step of melt-kneading, a step of pulverizing, and a step of classifying. A method for producing toner having the above can be applied. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.

  The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and a subsequent classification step. It means fine particles or coarse particles other than the components that are produced as products having a desired particle size. It is preferable that such a by-product is mixed in the weight ratio of the other raw material 50 to the sub-product 50 from the other raw material 99 to the sub-product 1 in the mixing step and the melt-kneading step.

  The mixing step of mechanically mixing toner components including at least a binder resin, a main charge control agent and a pigment, and a by-product may be performed under normal conditions using a normal mixer using a rotating wing, and is not particularly limited. Absent.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used.

  It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chain of the binder resin. Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is lower than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed. When controlling the amount of volatile components and polar solvent soluble components in the toner, the melt kneading temperature, time, and atmosphere should be adjusted to the optimum conditions while monitoring the residual volatile component amounts and polar solvent soluble components. It is more preferable to set.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream or pulverizing with a narrow gap between a rotor and a stator that rotate mechanically is preferably used.

  After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner having a predetermined particle size, for example, an average particle size of 5 to 20 μm.

  In addition, when preparing the toner, in order to improve the flowability, storage stability, developability, and transferability of the developer, the hydrophobic silica fine powder listed above for the toner produced as described above, etc. Inorganic fine particles may be added and mixed. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.

  Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

(Non-contact fixing system)
In the present invention, the fixing system is more effective in the case of a non-contact heat fixing system such as oven fixing or flash fixing. In other words, even when using a non-contact heating and fixing method that consumes a large amount of energy to the surroundings and consumes a large amount of power, it is possible to use toner and developer with a small amount of volatile components and polar solvent soluble components. Thus, an image forming method and apparatus having a small amount of volatile components due to heat during fixing and excellent safety can be obtained. In the non-contact fixing method, the smoothness of the image surface is often insufficient. When fixing at a lower temperature is desired, it is still preferable to use a method of further improving the image gloss through a heating roller after fixing.

(Film fixing)
In the present invention, the fixing system includes a heating member that is fixedly installed, and a pressure member that presses and rotates against the heating member and presses the recording material against the heating member via a film material. The effect is exhibited in the case of a fixing method in which heat is fixed on the top. That is, in a low-temperature fixing system using a film or a belt body, it is necessary to lower the average molecular weight in order to enable toner to be fixed at a low temperature, which inevitably increases low molecular weight volatile components and polar solvent soluble components. This was a problem, but it was a problem. By defining the amount of volatile components and polar solvent-soluble components in the toner and developer, it is possible to form images with excellent safety without sacrificing the thermal properties of the toner. A method and apparatus were obtained.

  The fixing film material used in the present invention is not particularly limited, and a thin film having excellent heat resistance, releasability and durability and having a thickness of 100 μm or less, preferably 50 μm or less can be used. As the fixing film material, a single layer film or a composite layer film having the following materials can be used. As a single layer film, for example, polyester, tetrafluoroethylene polymer, polyimide, polyetherimide and at least ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene A heat-resistant resin such as a fluororesin such as a perfluoroalkyl vinyl ether copolymer, a tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, or the like can be used. Moreover, as a composite layer film, for example, there is one in which a release coat layer obtained by adding a conductive material to PTFE (tetrafluoroethylene polymer) at least on the image contact surface side is applied to a thickness of 5 to 15 μm.

  More specifically, the heating element fixedly installed on the gantry of the apparatus is preferably in a line shape with a low heat capacity, for example, 0.2 to 5.0 mm in thickness, more preferably 0.5. A resistor material is applied to 1.3 mm on an alumina substrate having a thickness of ˜3.5 mm, a width of 10 to 15 mm, and a longitudinal length of 240 mm, and energized from both ends. For example, the energization is performed by changing the pulse width according to the temperature / energy release amount controlled by the temperature sensor with a pulse waveform of DC100V with a period of 25 ms. The temperature T1 detected by the temperature sensor in the low heat capacity line-shaped heating element is such that the surface temperature T2 of the film material facing the resistance material is lower than T1. Here, T1 is preferably 140 to 200 ° C., and the temperature of T2 is preferably 0.5 to 10 ° C. lower than the temperature of T1. Further, the film material surface temperature T3 at the portion where the film material peels from the toner fixing surface is substantially equal to T2.

  The film material is transported without wrinkles or twists by the drive and tension of the drive roller and driven roller. The pressure roller has a rubber elastic layer having high releasability such as silicon rubber, and pressurizes and rotates with a heating body through a film material with a total pressure of 2 to 30 kg. FIG. 1 shows a schematic configuration of an embodiment of a fixing device used in the fixing method. In FIG. 1, reference numeral 4 denotes a fixedly installed heating body, which has an alumina substrate 5 coated with a resistance material and a temperature sensor 6. The temperature sensor 6 detects the temperature, and a control mechanism (not shown) Controls temperature and energy release. 2 is an endless belt-like film material, 1 is a driving roller for driving the film material 2, 3 is a driven roller, and 8 is a pressure roller for pressing the recording material to the heating body 4 via the film material 2. A guide plate 7 guides the recording material to the fixing device. The recording material (transfer paper such as paper) having a toner image moves in the direction of arrow K so that the toner image is in contact with the surface of the film material 2 and is sent to the fixing device. It is inserted and fixed.

(Low contact pressure fixing)
In the present invention, the fixing system is an image forming method for fixing by heating and melting by passing between two rollers, and the thickness of the fixing roller on the side in contact with the toner image supporting surface is 0.7 mm or less. Further, the effect is exhibited in the case of a method in which the surface pressure applied between the two rollers (roller load / contact area) is 1.5 × 10 ⁵ Pa or less. That is, in such a low surface pressure fixing system, it is necessary to lower the average molecular weight in order to enable toner to be fixed at low pressure, and inevitably low molecular weight volatile components and polar solvent soluble components tend to increase. However, by defining the amount of volatile components and polar solvent soluble components in the toner and developer, an image forming method having excellent safety without sacrificing the thermal characteristics of the toner, A device was obtained. FIG. 2 shows a schematic configuration of an embodiment of a fixing device used in the fixing method. In FIG. 2, 21 represents a fixing roller, and 22 represents a pressure roller. The fixing roller 21 has RTV, silicon rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), polytetrafluoroethylene (PFA) on the surface of a metal cylinder 23 made of a high thermal conductor such as aluminum, iron, stainless steel, or brass. An offset prevention layer 24 such as PTFE is coated. A heating lamp 25 is disposed inside the fixing roller 21. The metal cylinder 26 of the pressure roller 22 is often made of the same material as that of the fixing roller 21, and the surface thereof is covered with an offset prevention layer 27 such as PFA or PTFA. Although not necessarily required, a heating lamp 28 is disposed inside the pressure roller 22. Although the fixing roller and the pressure roller are not shown, they are pressed against and rotated by springs at both ends. The recording material S (transfer paper such as paper) of the toner image T is passed between the fixing roller 21 and the pressure roller 22 for fixing.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified. The obtained characteristics and evaluation results are shown in Table 1. In the examples, evaluation was performed as follows.

(Evaluation machine)
Images used in the evaluation were evaluated using any of the following evaluation machines A, B, C, D, E, and F.

(Evaluation machine A)
Full-color laser copy made by Ricoh Co., Ltd., in which the four-color developing unit develops two-component developer on each drum-shaped photoconductor, sequentially transfers it to an intermediate transfer member, and transfers all four colors onto transfer paper. Evaluation was performed using an evaluation machine A obtained by modifying the machine (IMAGIO COLOR 2800).

(Evaluation machine B)
Ricoh's full-color laser printer with a four-color development unit that develops a non-magnetic one-component developer on a belt photoconductor, sequentially transfers each color to an intermediate transfer member, and transfers all four colors onto a sheet of paper. Evaluation was performed using an evaluation machine B modified from (Ipsio 5000).

(Evaluation machine C)
Using an evaluation machine C, which is a modified tandem Fujitsu full-color LED printer (GL8300) that has a four-color non-magnetic one-component developing unit and a four-color photoconductor and sequentially transfers it to paper, etc. evaluated.

(Evaluation machine D)
Evaluation was performed with DCP32D manufactured by XEIKON, which is an electrophotographic full color on-demand machine including a non-contact fixing system, and an evaluation machine D. Image evaluation was performed with an oven fixing temperature of 140 ° C. and a printing speed of 15 sheets (A4) / min and 35 sheets (A4) / min.

(Evaluation machine E)
The fixing unit of the Ricoh copier MF200, as shown in FIG. 1, is subjected to press-and-rotation with a fixedly installed heating body facing the heating body after completion of the development process and the transfer process using a developer. The evaluation apparatus E was changed and modified to a fixing device including a fixing method in which a toner image is heated and fixed on the recording material by a pressure member that presses the recording material to the heating body through the material.

(Evaluation machine F)
As a low surface pressure fixing machine, an apparatus (evaluation machine D) in which a fixing unit of a copying machine MF-200 manufactured by Ricoh Co., which uses a polyfluoroethylene roller as a fixing roller, is modified. And set a copy test. It includes a fixing method in which the toner image formed on the transfer material is fixed by heating and melting by passing between two rollers, and the thickness of the fixing roller on the side in contact with the toner image support surface is 0.5 mm. In addition, a fixing machine having a surface pressure (roller load / contact area) applied between the two rollers of 1.2 × 10 ⁵ Pa was used (see FIG. 2).

(Evaluation item)
1) Amount of polar solvent soluble component The amount of a polar solvent soluble component in the toner is shown. In the case of 4-color toner, the maximum value is shown.

2) Image density After outputting a solid image on Ricoh 6000 paper, the image density was measured by X-Rite (X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

3) Spent After running 100,000 sheets of image chart with 7% image area in single color mode, evaluate spent component attached to developer or developing sleeve, and the amount of spent is small. A case where the amount of spent was slightly large was evaluated as Δ, and a case where the amount of spent was large was evaluated as x.

4) Heat-resistant storage Weigh 10g of each color toner, put them in a 20cc glass container, tap the glass bottle about 100 times, leave it in a thermostatic chamber set at 50 ° C for 24 hours, and then insert it with a penetration meter. The degree was measured. From the best, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

5) Transparency Fixed on an OHP sheet in a single color under the conditions of an image density of 1.0 mg / cm ² and a fixing temperature of 150 ° C., and measured with a continuous haze computer HGM-2DP type manufactured by Suga Test Instruments. The haze value was less than 15 as ◎, 15 or more and less than 25 as ◯, 25 or more and less than 35 as Δ, and 35 or more as x.

6) Color vividness and color reproducibility Color vividness and color reproducibility were determined by visually evaluating an image output on 6000 paper manufactured by Ricoh Co., Ltd. and using a specified limit sample. A: Vivid colors are visible to anyone, and there is also color reproducibility. ○: The color is vivid and reproducible to the extent that the difference cannot be seen without approaching. Δ: The minimum vividness and reproducibility of the color that can withstand visual perception as a printed matter. X: Vividness and reproducibility of colors that are not very practical for products.

7) Gloss Using the gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.), the light output angle and the light receiving angle are adjusted to 60 ° for the image output to 6000 paper manufactured by Ricoh, and S, S / 10 The changeover SW was adjusted to S and measured after zero adjustment and standard setting using a standard plate. Since the glossiness is good, ◎: 20 or more, ◯: 10 or more and less than 20, Δ: 5 or more and less than 10 and x: less than 5.

8) Curling property of image paper After outputting an image on 6000 paper manufactured by Ricoh, the curling property of the output image paper was evaluated. Especially good ones without curling were marked with 良好, good ones with good, and curled ones not preferred with x.

9) Environmental charging stability In an environment of temperature 40 ° C and humidity 90%, a part of the developer was sampled every 1000 sheets while running 30,000 image charts of 7% image area in monochrome mode. The charge amount was measured by the blow-off method to evaluate the charging stability. Compared with the initial charge amount, the decrease or increase of the charge amount is within 10%, ◯ is within 20%, Δ is within 40%, and x is more than that.

10) Fixability The minimum fixing temperature and the maximum fixing temperature of the toner are sufficiently within the fixing temperature range, no hot offset or cold offset occurs, and paper jams and other transport problems do not easily occur. It was evaluated as a level that can be satisfied by anyone with very few troubles, ○: a level that can be satisfied to a certain extent, Δ: a level that is barely established as a product, and ×: a level that is not established as a product at all.

11) Vinyl chloride sheet resistance After outputting an image on 6000 paper manufactured by Ricoh Co., Ltd., a storage experiment was conducted in which the sheet was placed in close contact with the vinyl chloride sheet and allowed to stand at room temperature for 180 hours to evaluate the transfer of the PVC sheet to the image. When the image paper is separated from the sheet, the toner image is partially or completely peeled off and the sheet is also stained.

Example 1
(Epoxy polyol resin 1)
In a separable flask equipped with a stirrer, a thermometer, an N2 inlet, and a cooling tube, 378.4 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360), a high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 2700) 86.0 g, diglycidylated product of bisphenol A type propylene oxide adduct [n + m: about 2.1 in the above general formula (1)] 191.0 g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, xylene 200 g was added. The temperature was raised to 70 to 100 ° C. under N ₂ atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., water was added under reduced pressure, and water and xylene were volatilized by bubbling water and xylene. And the polar solvent-soluble component is removed and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours, Mn: 3800, Mw / Mn: 3.9, Mp: 5000, softening point 109 ° C., Tg 58 ° C., 1000 g of a polyol resin having an epoxy equivalent of 30,000 or more was obtained (hereinafter referred to as epoxy polyol resin 1). The reaction conditions were controlled so that no monomer component remained in the polymerization reaction. The polyoxyalkylene part of the main chain was confirmed by NMR. In addition, the polar solvent soluble component weight concentration of resin was 55 micrograms with respect to 1 g of resin.

(Manufacture of toner)
[Black Toner]
1000 parts of water Water containing phthalocyanine green cake (solid content 30%) 200 parts Carbon black (MA60 manufactured by Mitsubishi Chemical Corporation) 540 parts Epoxy polyol resin 1 1200 parts The above raw materials are mixed in a Henschel mixer, and water is added to the pigment aggregate. A mixture soaked with water was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment. continue,
Epoxy polyol resin 1 100 parts Master batch pigment 8 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts The above materials were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, an impingement plate type pulverizer using a jet mill (I-type mill: manufactured by Nippon Pneumatic Industry Co., Ltd.) and a wind classifier using a swirling flow (DS classifier: manufactured by Nippon Pneumatic Industry Co., Ltd.) are used. Of black colored particles were obtained. Further, 0.5 wt% of hydrophobic silica (H2000, Clariant Japan) was added, mixed with a Henschel mixer, passed through a sieve having an aperture of 50 μm, and aggregates were removed to obtain black toner 1. Here, the melt viscosity at 140 ° C. of the toner was 96 mPas · sec.

[Yellow Toner]
600 parts of water
Pigment Yellow 17 hydrous cake (solid content 50%) 1200 parts Epoxy polyol resin 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment. continue,
Epoxy polyol resin 1 100 parts Master batch 8 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts The above materials were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the black colored particle production example, and yellow colored particles having a volume average particle diameter of 8.5 μm were obtained. Further, 0.5 wt% of hydrophobic silica (H2000, Clariant Japan) was added, mixed with a Henschel mixer, passed through a sieve having an opening of 50 μm, and aggregates were removed to obtain yellow toner 1. Here, the melt viscosity at 140 ° C. of the toner was 98 mPas · sec.

[Magenta toner]
600 parts of water
Pigment Red 57 hydrous cake (solid content 50%) 1200 parts Epoxy polyol resin 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment.
Epoxy polyol resin 1 100 parts Master batch 8 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts The above materials were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the black colored particle production example, and magenta colored particles having a volume average diameter of 8.5 μm were obtained. Further, 0.5 wt% of hydrophobic silica (H2000, Clariant Japan) was added, mixed with a Henschel mixer, passed through a sieve having an opening of 50 μm, and aggregates were removed to obtain magenta toner 1. Here, the melt viscosity at 140 ° C. of the toner was 17 mPas · sec.

[Cyan toner]
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) 1200 parts Epoxy polyol resin 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment. continue,
Epoxy polyol resin 1 100 parts Master batch 8 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts The above materials were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the black colored particle production example, and cyan colored particles having a volume average particle diameter of 8.5 μm were obtained. Further, 0.5 wt% of hydrophobic silica (H2000, Clariant Japan) was added, mixed with a Henschel mixer, passed through a sieve with an opening of 50 μm, and aggregates were removed to obtain cyan toner 1. Here, the melt viscosity at 140 ° C. of the toner was 34 mPas · sec.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin with an average thickness of 0.3 μm is used, and the container rolls 5 parts of each color toner with respect to 100 parts of the carrier. Then, the developer was prepared by uniformly mixing and charging using a tumbler mixer of the type stirred. A carrier having a low volatile component amount was produced by changing the coating conditions (volatilization temperature, time, atmosphere) of the coating resin. In Example 1, the weight concentration of the polar solvent-soluble component was 370 μg with respect to 1 g of the developer.

(Examples 2 to 22)
In Example 1, a toner and a developer were prepared and evaluated in the same manner except that a resin synthesized and produced in the same manner based on the raw materials, addition amounts, and physical properties shown in Table 2 was used.

(Example 23)
In Example 1, it evaluated similarly except having changed into the phthalate ester of the bisphenol A type propylene oxide adduct instead of the diglycidylation product of the bisphenol A type propylene oxide adduct. , Mn: 3100, Mw / Mn: 6.1, Mp: 5000, softening point 112 ° C., Tg 58 ° C., and epoxy resin 1000 g having an epoxy equivalent of 30000 or more were obtained. The reaction conditions were controlled so that no monomer component remained in the polymerization reaction. The polyoxyalkylene part of the main chain was confirmed by NMR. The polyester component was confirmed by infrared spectroscopy. The weight concentration of the polar solvent soluble component of the resin was 53 μg with respect to 1 g of the resin.

(Example 24)
Evaluation was made in the same manner as in Example 1 except that the production conditions of the toner were changed so that the weight concentration of bisphenol A was 868 μg with respect to 1 g of the toner.

(Example 25)
In Example 1, the evaluation was made in the same manner except that the production conditions of the toner were changed so that the weight concentration of bisphenol A was 356 μg with respect to 1 g of the toner.

(Example 26)
Evaluation was made in the same manner as in Example 1 except that the production conditions of the toner were changed so that the weight concentration of bisphenol A was 88 μg with respect to 1 g of the toner.

(Example 27)
In Example 1, the evaluation was performed in the same manner except that the toner production conditions were changed so that the weight concentration of bisphenol A was 9 μg with respect to 1 g of the toner.

(Example 28)
In Example 1, the amount of the volatile component of each color pigment and the production of the toner so that the difference in the polar solvent soluble component concentration of 1 g of each color of the black toner, cyan toner, magenta toner, and yellow toner is 14 μg. Evaluation was performed in the same manner except that the conditions were adjusted.

(Example 29)
In Example 1, the same procedure was applied except that the toner kneading conditions were changed so that the melt viscosity of the black toner at 140 ° C. was 121 mPas · sec, and the melt viscosity of the yellow toner at 140 ° C. was 122 mPas · sec. And evaluated.

(Example 30)
In Example 1, the toner was evaluated in the same manner except that the toner kneading conditions were changed so that the softening point of the toner was 113 ° C. and the glass transition temperature (Tg) was 61 ° C.

(Example 31)
In Example 1, the number average molecular weight (Mn) of the toner is 3750, the weight average molecular weight / number average molecular weight (Mw / Mn) is 4.0, and at least one peak molecular weight (Mp) is 5000. Thus, the evaluation was made in the same manner except that the toner kneading conditions were changed.

(Example 32)
In Example 1, acetone was evaluated in the same manner except that the synthesis conditions of the resin were changed so that the epoxy equivalent of the binder resin was 9000 or more during the production of the master batch pigment.

(Example 33)
In Example 1, at the time of producing the master batch pigment, water, a water-containing cake pigment, and a resin were mixed, kneaded at 150 ° C. for 30 minutes, 1000 parts of xylene were added, and further kneaded for 1 hour. Evaluation was performed in the same manner as in Example 1 except that a master batch pigment was produced by pulverization with a pulverizer and two passes with a three-roll mill. The weight concentration of the polar solvent-soluble component of the masterbatch pigment was 483 μg with respect to 1 g of the toner.

(Example 34)
In Example 1, it evaluated similarly except having changed the water | moisture-content volatilization conditions so that the water | moisture-content density | concentration of this binder resin might be 1.2%.

(Example 35)
In Example 1, the same procedure as in Example 1 was used, except that a dry powder pigment was used as the pigment and the weight ratio of the pigment (solid content), resin, and water was the same as in Example 1 when the masterbatch pigment was produced. evaluated. The weight concentration of the polar solvent-soluble component of the master batch pigment was 18 μg with respect to 1 g of the toner.

(Example 36)
In Example 1, the resin was changed to a polyester resin (acid value: 3, hydroxyl value: 25, Mn: 45000, Mw / Mn: 4.0, Tg: 60 ° C.), and the polar solvent soluble component in the toner Evaluation was performed in the same manner as in Example 1 except that the amount was reduced.

(Example 37)
In Example 1, it evaluated similarly except having used the evaluation machine B.

(Example 38)
In Example 1, it evaluated similarly except having used the evaluation machine C.

(Example 39)
In Example 1, it evaluated similarly except having used the evaluation machine D.

(Example 40)
In Example 1, it evaluated similarly except having used the evaluation machine E. FIG.

(Example 41)
In Example 1, it evaluated similarly except having used the evaluation machine F. FIG.

(Comparative Example 1)
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the toner production conditions, particularly the kneading and pulverization conditions were changed so that the weight concentration of the polar solvent-soluble component was 1240 μg with respect to 1 g of the toner.

(Comparative Example 2)
In Example 1, the resin was changed to a polyester resin (acid value: 4, Mn: 45000, Mw / Mn: 4.0, Tg: 61 ° C., softening point: 106 ° C.), and the weight concentration of the polar solvent-soluble component The toner was evaluated in the same manner as in Example 1 except that the toner production conditions, particularly the kneading and pulverization conditions were changed to 1130 μg per 1 g of toner.

1 is a schematic configuration diagram illustrating an example of a fixing device used in an image forming method of the present invention. 1 is a schematic configuration diagram illustrating an example of a fixing device used in an electrophotographic image forming method of the present invention.

Explanation of symbols

(In Fig. 1)
DESCRIPTION OF SYMBOLS 1 Drive roller 2 Fixing film material 3 Tension roller 4 Heating body 5 Alumina substrate 6 Temperature sensor 7 Paper feed guide 8 Pressure roller (in FIG. 2)
21 Fixing roller 22 Pressure roller 23 Metal cylinder (fixing roller)
24 Offset prevention layer (fixing roller)
25 Heating lamp (fixing roller)
26 Metal cylinder (pressure roller)
27 Offset prevention layer (Pressure roller)
28 Heating lamp (pressure roller)
T toner image S recording material

Claims (29)

An electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the binder resin is prepared by adding water to an organic solvent liquid containing a binder resin material at least before or during a synthesis reaction of the binder resin. And at least a polyol resin formed by bubbling the water mixture under reduced pressure to reduce soluble components soluble in the mixture. toner. 2. The electrostatic image developing toner according to claim 1, wherein volatile components are also reduced by the bubbling treatment. Wherein the soluble component according to claim 1 or 2 toner according to, characterized in that soluble in the mixed solution. The static component according to any one of claims 1 to 3, wherein the soluble component is soluble in a mixed solution of water and acetonitrile in a volume ratio of 5: 5, and the content relative to 1 g of toner is 3 µg or more and 1000 µg or less. Toner for charge image development. The toner according to claim 1, wherein the weight concentration of bisphenol A in the binder resin of the toner is less than 1000μg the toner 1g. A color toner comprising at least three colors, any one of claims 1 to 5, wherein the maximum value of the difference between the weight concentrations of soluble components in the mixed solution between respective color toner is 300μg or less 1 The toner for developing an electrostatic charge image according to 1. A toner according to any one of claims 1 to 6, the toner for developing electrostatic images, wherein the melt viscosity at 140 ° C. of the toner is less than 120mPas · sec. The toner according to any one of claims 1 to 7 , wherein the toner has a softening point of 70 to 160 ° C and a glass transition temperature (Tg) of 40 to 70 ° C. Toner for charge image development. A toner according to any one of claims 1-8, a number average molecular weight of the toner (Mn) is 2,000 to 8,000, a weight average molecular weight / number average molecular weight (Mw / Mn) in 1.5 to 20 An electrostatic charge image developing toner, wherein at least one peak molecular weight (Mp) is 3000 to 7000. A toner according to any one of claims 1-9, electrostatic the toner binder resin, wherein at least comprises a polyol resin having at least an epoxy resin part and Po polyoxyalkylene unit in the main chain Toner for charge image development. The toner according to any one of claims 1 to 10 , wherein the binder resin of the toner includes at least a polyol resin having an epoxy resin portion, a polyoxyalkylene portion, and a polyester portion in the main chain. Toner for developing electrostatic image. The toner for developing an electrostatic charge image according to any one of claims 1 to 11 , wherein a terminal of the polyol resin of the binder resin of the toner is inactive. A toner according to any one of claims 1 to 12, as a binder resin of the toner, and at least (1) an epoxy resin, and (2) a bivalent alkylene oxide adduct or a glycidyl ether of phenol, ( 3) Use of a polyol resin obtained by reacting a compound having one active hydrogen reacting with an epoxy group in the molecule and (4) a compound having two or more active hydrogen reacting with an epoxy group in the molecule. A toner for developing electrostatic images, comprising at least a resin as described above. 14. The toner according to claim 10 , wherein the epoxy resin constituting the polyol of the binder resin of the toner is at least two or more bisphenol A type epoxy resins having different number average molecular weights. A toner for developing an electrostatic charge image. 15. The toner according to claim 14 , wherein the epoxy resin constituting the polyol of the binder resin of the toner is at least two or more bisphenol A type epoxy resins having different number average molecular weights, and the number average of low molecular weight components. A toner for developing an electrostatic charge image, having a molecular weight of 360 to 2,000 and a high molecular weight component having a number average molecular weight of 3,000 to 10,000. 16. The toner according to claim 15 , wherein the epoxy resin constituting the polyol of the binder resin of the toner is at least two or more bisphenol A type epoxy resins having different number average molecular weights , and the low molecular weight component is a polyol resin. The toner for developing an electrostatic charge image is characterized by being 20 to 50 wt% and a high molecular weight component of 5 to 40 wt%. The toner according to any one of claims 13 to 16, wherein the glycidyl ether of an alkylene oxide adduct of dihydric phenol constituting the polyol is a diglycidyl ether of an alkylene oxide adduct of bisphenol A, and A toner for developing an electrostatic charge image, wherein a binder resin represented by the formula (1) is used.

18. The toner according to claim 13 , wherein a binder resin containing 10 to 40 wt% of a dihydric phenol alkylene oxide adduct or a glycidyl ether thereof constituting a polyol is used. An electrostatic charge image developing toner. The toner according to claim 10 , wherein the binder resin has an epoxy equivalent of 20000 or more.
A binder resin for an electrostatic charge image developing toner, wherein the binder resin is made into a water mixture by adding water to an organic solvent solution containing at least the binder resin material before or during the binder resin synthesis reaction, and under reduced pressure. A binder resin for an electrostatic charge image developing toner, comprising at least a polyol resin obtained by bubbling the water mixture to reduce at least soluble components soluble in the mixture. 21. The resin for electrostatic image developing toner according to claim 20 , wherein the weight concentration of the component soluble in the mixed solution is 1000 μg or less with respect to 1 g of the resin. A method for producing a binder resin for an electrostatic charge developing toner containing at least a polyol resin, wherein water is added to an organic solvent solution containing at least a binder resin material before or during the binder resin synthesis reaction to form a water mixture, A method for producing a binder resin for an electrostatic charge developing toner, comprising a step of bubbling the water mixture under reduced pressure to reduce at least soluble components soluble in the mixture. A masterbatch pigment in which a pigment is dispersed in a resin, which is produced by heating and kneading the toner resin and the pigment according to any one of claims 20 and 21 . Masterbatch pigment. 24. The masterbatch pigment for an electrostatic charge image developing toner according to claim 23 , wherein the weight concentration of the component soluble in the mixed solution is 500 μg or less with respect to 1 g of the masterbatch pigment. The master back pigment according to any one of claims 23 and 24 , wherein a dry powder pigment is used as the pigment, and at least water is added when the dry powder pigment and the binder resin are mixed, and the mixture is heated. A masterbatch pigment for an electrostatic charge image developing toner, comprising a step of kneading and removing water during mixing. Electrostatic image developer which comprises a toner according, and a carrier to any one of claims 1 to 19. 27. The developer for developing an electrostatic charge image according to claim 26 , wherein a weight concentration of a component soluble in the mixed solution is 500 μg or less with respect to 1 g of the developer. . An image forming method using the toner according to any one of claims 1 to 19 or the developer according to claim 26 or 27 . An image forming apparatus loaded with the toner according to any one of claims 1 to 19 or a container filled with the developer according to claim 26 or 27 .

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