Toner, toner set, image transfer sheet, toner storage unit, image forming apparatus, and image forming method

Abstract

To provide a toner that is sufficiently fixed to a flexible recording medium such as cloth to which a conventional toner cannot be easily fixed.SOLUTION: A toner contains a polyester resin having a structure represented by the structure (A), and when a total amount of an organic component of the toner is defined as 100 wt%, contains THF insoluble organic matter in an amount of 26 wt% or more and less than 70 wt%. Structure (A): a structure having R1 having three or more bonding hands and R2s in the same number as the bonding hands, and bonding of each bonding hand of R1 with each R2 is represented by any one of following structural formulas 1)-3). 1) R1-NHCONH-R2. 2) R1-NHCOO-R2. 3) R1-OCONH-R2. (In the formulas, R1 represents an aromatic or aliphatic organic group derived from tri- or more-valent alcohol or derived from tri- or more-valent polyisocyanate, and R2 represents a group derived from polyester polyol.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a toner, a toner set, an image transfer sheet, a toner storage unit, an image forming apparatus, and an image forming method. [Background technology]

[0002] In the electrophotographic method, in which an electrostatic latent image is developed with a developer to form a visible image, an electrostatic latent image is formed on an electrostatic latent image carrier (also called a photoreceptor) containing a photoconductive material, the electrostatic latent image is developed with a developer containing toner to form a toner image, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed by applying heat and pressure to form a fixed image.

[0003] To form a full-color image by electrophotography, a toner set is generally used that combines a black toner with three process color toners (sometimes simply called process colors), that is, cyan, magenta, and yellow toners.

[0004] In recent years, as electrophotographic color image forming devices have come into widespread use, the uses of printed matter have expanded to a wide variety of applications. Particularly in the field of custom-made design consumer goods, there is an increasing need for electrophotographic printing on materials that cannot be printed (fixed) with conventional electrophotographic toners intended for printing on paper media. Specifically, there is an increasing need for printing on fabric media such as sports team uniforms, shoes, and bags.

[0005] Patent Document 1 discloses a thermal transfer print sheet obtained using a pulverized toner for thermal transfer print sheets that can adhere an image to a printing object by thermal melting on a white background without using an adhesive, and that does not damage the pulverizer. Summary of the Invention [Problem to be solved by the invention]

[0006] Toners used to form fixed images on cloth media are required to have characteristics not found in conventional toners for fixing to paper media, such as sufficient fixing to the uneven cloth fibers and a fixed toner layer with appropriate flexibility so that the toner layer can follow deformations in the cloth. However, a toner has not yet been found that has excellent fixing properties and flexibility on flexible recording media such as cloth, and that can conceal the color of the cloth.

[0007] The present invention aims to solve the above-mentioned problems in the prior art and to achieve the following object: That is, the present invention aims to provide a toner that can be sufficiently fixed to a flexible recording medium such as a cloth on which a conventional toner cannot be easily fixed. [Means for solving the problem]

[0008] One aspect of the present invention is a toner comprising a polyester resin having a structure represented by Structure (A), and containing 26 wt % or more and less than 70 wt % of THF-insoluble organic matter when the total amount of the organic components of the toner is taken as 100 wt %. Structure (A): A structure having R1 having three or more bonds and the same number of R2 as the number of bonds, in which the bonds of R1 and R2 are bonded to each other and are represented by any one of the following structural formulas 1) to 3). 1) R1-NHCONH-R2 2) R1-NHCOO-R2 3) R1-OCONH-R2 (In the above formula, R1 is an aromatic or aliphatic organic group derived from a trivalent or higher alcohol or a trivalent or higher polyisocyanate, R2 is a group derived from a polyester polyol, Represents.) Effect of the Invention

[0009] According to the present invention, it is possible to provide a toner that can be sufficiently fixed to a flexible recording medium such as a cloth, on which conventional toners cannot be easily fixed. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram showing an example of an image forming apparatus of the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing another example of the image forming apparatus of the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing another example of the image forming apparatus of the present invention. [Figure 4] FIG. 4 is a partially enlarged view of FIG. [Diagram 5] FIG. 5 is a schematic diagram showing an example of a process cartridge. [Figure 6] FIG. 6 is an image diagram for explaining the branched structure of a conventional polyester resin. [Figure 7] FIG. 7 is an image diagram for explaining the branched structure of the polyester resin defined in the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] (toner) The toner of the present invention contains a polyester resin, preferably further contains a crystalline polyester resin, and further contains other components such as a colorant, if necessary. The polyester resin contains a polyester resin having a structure represented by Structure (A) (hereinafter, also referred to as polyester resin A). Structure (A): A structure having R1 having three or more bonds and the same number of R2 as the number of bonds, in which the bonds of R1 and R2 are bonded to each other and are represented by any one of the following structural formulas 1) to 3). 1) R1-NHCONH-R2 2) R1-NHCOO-R2 3) R1-OCONH-R2 (In the above formula, R1 is an aromatic or aliphatic organic group derived from a trivalent or higher alcohol or a trivalent or higher polyisocyanate, R2 is a group derived from a polyester polyol, Represents.) That is, polyester resin A has a structure in which R2, which is a polyester or modified polyester portion, and R1, which corresponds to a branched structure, are bonded via a urethane or urea group.

[0012] In the toner of the present invention, the polyester resin has a branched structure in the molecular skeleton due to urethane or urea bonds, and the molecular chain has a three-dimensional network structure, so that it has rubber-like properties of deforming at low temperatures but not flowing. Therefore, even when printed on fabric, the toner has an excellent property of not easily cracking due to the expansion and contraction of the fabric or during washing and drying. In addition, the image durability is high due to its uniform three-dimensional structure. Even when the glass transition temperature of the polyester resin is very low, the toner can maintain its heat-resistant storage stability and high-temperature offset resistance.

[0013] Furthermore, if the network structure is non-uniform, the flow control of the resin is insufficient in the coarse network portion, resulting in deterioration of heat-resistant storage stability, and the deformability of the resin is insufficient in the dense network portion, resulting in a decrease in image strength. For example, when the portion forming the branch is an ester structure (i.e., when the portion R2 in the structural formula represented by the structure (A) defined in the present application has a branched structure), the branched structure is present non-uniformly as shown in the image diagram of Figure 6, and therefore the heat-resistant storage stability and image strength are not fully satisfactory. Figure 6 is a schematic diagram of the branched structure of a polyester resin obtained by a conventional synthesis method.

[0014] On the other hand, in the polyester resin A of the present invention, after R2, which is a polyester or modified polyester portion, is synthesized, it can be bonded to R1 via a urethane or urea group to form a network structure. Therefore, by narrowing the molecular weight distribution of the R2 portion, it is possible to make the network structure uniform. The state of the polyester resin A having a structure represented by the structure (A) defined in the present invention is shown in the image diagram of Figure 7. Figure 7 is a schematic diagram of the branched structure of the polyester resin obtained by the synthesis method of the present invention described below. Since the length of the linear polyester resin portion of the R2 portion is uniform, as shown in Figure 7, the branched structure of the polyester resin is uniform. In this way, by making the network structure of the polyester resin A uniform, it becomes possible to achieve both heat-resistant storage stability of the toner and image strength. Furthermore, since the branched structure portion of the polyester resin A has a urethane bond or urea bond with high cohesive energy, the polyester resin A behaves like a strong crosslinking point. Therefore, even if the polyester resin A has a coarser mesh structure, the resin has a strong effect of suppressing flow, making it possible to achieve both heat-resistant storage stability and image strength of the toner.

[0015] <Polyester resin A> The polyester resin A has a structure represented by Structure (A), in which R2, which is a polyester or modified polyester moiety, and R1, which corresponds to a branched structure, are bonded via a urethane or urea group. Since the polyester resin A has at least one of a urethane bond and a urea bond in the branched structure portion, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, and the rubber-like properties of the polyester resin A are enhanced, making it possible to produce a toner having excellent heat-resistant storage stability and cracking resistance. The polyester resin A contains, as a constituent component, a diol component, and more preferably contains, as a constituent component, a dicarboxylic acid component.

[0016] The polyester resin A is preferably an amorphous polyester resin.

[0017] The polyester resin A is not particularly limited as long as it is formed by bonding R2 corresponding to the polyester or modified polyester portion and R1 corresponding to the branched structure portion via a urethane or urea group, and can be appropriately selected depending on the purpose. The method for bonding R1 and R2 is not limited to the following three methods.

[0018] a) A method in which a diol component and a dicarboxylic acid component are subjected to an esterification reaction to produce a polyester polyol (R2) having hydroxyl groups at the terminals, and the resulting polyester polyol is reacted with a trivalent or higher polyisocyanate (R1). b) A method in which a diol component and a dicarboxylic acid component are subjected to an esterification reaction to produce a polyester polyol (R2) having hydroxyl groups at the terminals, the polyester polyol obtained is reacted with a divalent polyisocyanate to produce an isocyanate-modified polyester (R2), and the isocyanate-modified polyester obtained is reacted with a trivalent or higher alcohol (R1). c) A method in which a diol component and a dicarboxylic acid component are subjected to an esterification reaction to produce a polyester polyol (R2) having hydroxyl groups at the terminals, the resulting polyester polyol is reacted with a divalent polyisocyanate to produce an isocyanate-modified polyester (R2), and the resulting isocyanate-modified polyester is reacted with a trivalent or higher polyisocyanate (R1) in the presence of pure water. It is also possible to further react the hydroxyl groups remaining in the polyol obtained by any one of the above a) to c) with a divalent or higher polyisocyanate to form a polyester prepolymer, which can then be reacted with a curing agent in the toner production process. During the toner production process, a urethane or urea bond is generated by reaction with a curing agent, and the resulting bond behaves like a strong crosslinking point, thereby enhancing the rubber-like properties of the polyester resin A and further improving the heat resistance storage stability and high-temperature offset resistance. Therefore, it is more preferable that the R2 portion be a modified polyester resin modified with isocyanate.

[0019] In order to lower the Tg of the polyester resin A and to easily impart the property of deformation at low temperatures, the polyester resin A contains a diol component as a constituent component, and the diol component preferably contains an aliphatic diol having 3 to 12 carbon atoms, and more preferably contains an aliphatic diol having 4 to 12 carbon atoms.

[0020] The polyester resin A preferably contains the aliphatic diol having 3 to 12 carbon atoms in an amount of 50 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more.

[0021] Examples of the aliphatic diol having 3 to 12 carbon atoms include 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol.

[0022] In particular, it is more preferable that in the polyester resin A, the diol component is an aliphatic diol having 4 to 12 carbon atoms, the number of carbon atoms in the main chain of the diol component is an odd number, and the diol component has an alkyl group in the side chain. Examples of the aliphatic diol having 4 to 12 carbon atoms and an odd-numbered main chain and an alkyl group on the side chain include aliphatic diols represented by the following general formula (1). HO-(CR1R2)n-OH General formula (1) In the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents an odd number from 3 to 9. In the n repeating units, R1 may be the same or different. In the n repeating units, R2 may be the same or different.

[0023] In order to lower the Tg of the polyester resin A and easily impart the property of deformation at low temperatures, the polyester resin A preferably contains 50 mol % or more of an aliphatic diol having 3 to 12 carbon atoms in the total alcohol components.

[0024] In order to lower the Tg of the polyester resin A and easily impart the property of deformation at low temperatures, it is preferable that the polyester resin A contains a dicarboxylic acid component as a constituent component, and that the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

[0025] The polyester resin A preferably contains 30 mol % or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

[0026] Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

[0027] -Diol component- The diol component is not particularly limited and can be appropriately selected depending on the purpose. For example, aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like. Examples of the diols include diols having an oxyalkylene group such as polypropylene glycol and polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide have been added; bisphenols such as bisphenol A, bisphenol F and bisphenol S; and alkylene oxide adducts of bisphenols such as bisphenols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide have been added. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred. These diols may be used alone or in combination of two or more.

[0028] -Dicarboxylic acid component- The dicarboxylic acid component is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, etc. In addition, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used. The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid. The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferred. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred. These dicarboxylic acids may be used alone or in combination of two or more.

[0029] -Trivalent or higher alcohols- The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the trihydric or higher alcohol include aliphatic trihydric or higher alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Examples of the trivalent or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolac, and cresol novolac. Examples of the alkylene oxide adducts of trivalent or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trivalent or higher polyphenols.

[0030] -Polyisocyanate- The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyisocyanate include diisocyanates and tri- or higher valent isocyanates. Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like. Examples of the tri- or higher hydric isocyanate include lysine triisocyanate, or a compound obtained by reacting a tri- or higher hydric alcohol with a diisocyanate, or a compound obtained by reacting a polyisocyanate to form an isocyanurate. Among these, it is more preferable to use a polyisocyanate having an isocyanurate skeleton, since it acts as a stronger crosslinking point and provides better heat resistance storage stability and high-temperature offset resistance.

[0031] The trivalent isocyanate component is preferably 0.2 mol% or more and 1.0 mol% or less of the resin components in the THF-insoluble organic matter of the toner. When a crosslinked structure is formed by a trivalent isocyanate component, the molecular chain cohesive force is increased by pseudo-crosslinking by urethane or urea bonds at the crosslinking points, so that the heat-resistant storage stability can be improved even with a low crosslinking density, and low-temperature fixability can be achieved at a high level. When the trivalent isocyanate component is less than 0.2 mol%, the formation of a branched structure becomes insufficient, and the network structure becomes non-uniform at the starting point, which may deteriorate the heat-resistant storage stability and filming resistance. When the trivalent isocyanate component is more than 1.0 mol%, the low-temperature fixability may be deteriorated by forming a dense crosslinked structure. The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate. The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatodiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, and 4,4'-diisocyanato-diphenyl ether. The aromatic aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the purpose. For example, α,α,α',α'-tetramethylxylylene diisocyanate is exemplified. The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate, tris(isocyanatocycloalkyl)isocyanurate, and the like. These polyisocyanates may be used alone or in combination of two or more kinds.

[0032] - Hardener - The curing agent is not particularly limited as long as it is a curing agent that can react with a polyester prepolymer (a reaction product of the polyester portion of R2 and the polyisocyanate, i.e., a reaction precursor to be reacted with a curing agent) to produce the polyester resin, and can be appropriately selected depending on the purpose. For example, an active hydrogen group-containing compound can be used.

[0033] --Compounds containing active hydrogen groups-- The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. These may be used alone or in combination of two or more.

[0034] The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, but amines are preferred because they are capable of forming a urea bond.

[0035] The amines are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, blocked amino groups of these, etc. These may be used alone or in combination of two or more. Among these, diamines and mixtures of diamines with small amounts of trivalent or higher amines are preferred.

[0036] The diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. The alicyclic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, and isophoronediamine. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethylenediamine, tetramethylenediamine, and hexamethylenediamine.

[0037] The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine. The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline. The amino mercaptan is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan. The amino acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino acid include aminopropionic acid and aminocaproic acid. The blocked amino group is not particularly limited and can be appropriately selected depending on the purpose. Examples of the blocked amino group include ketimine compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and oxazoline compounds.

[0038] The glass transition temperature of the polyester resin A is preferably from -60°C to 0°C, and more preferably from -40°C to -20°C. If the glass transition temperature is lower than -60°C, the flow of the toner at low temperatures cannot be suppressed, and the heat-resistant storage stability and filming resistance may deteriorate. If the glass transition temperature exceeds 0° C., the toner cannot be sufficiently deformed by the application of heat and pressure during fixing, and low-temperature fixing properties may be insufficient. In the polyester resin, it is preferable that R1 in the structure (A) has an isocyanurate skeleton represented by the following structural formula (I) from the viewpoints of heat-resistant storage stability and high-temperature offset resistance. [ka]

[0039] In addition, in the polyester resin A, the three-dimensional molecular network structure is suitable for achieving both low-temperature fixability, image gloss, heat-resistant storage stability, and offset resistance, although the detailed reason is not clear. Therefore, in the structure (A), it is more preferable that the number of bonds in R1 is 3.

[0040] In addition, in the polyester resin A, the organic group of R1 in the structure (A) is preferably composed of an organic group having a short carbon number, since this makes it easier to uniformize the network structure, and is preferably an aliphatic or aromatic organic group having 20 or less carbon atoms. The organic group of R1 may also contain an ester bond. Among these, the organic group for R1 is preferably an aliphatic compound or an aliphatic compound containing an ester bond, since the cohesive strength of the crosslinking points can be adjusted within an appropriate range and it is easy to achieve both high gloss and heat-resistant storage stability.

[0041] The weight average molecular weight of the polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 20,000 or more and 1,000,000 or less as measured by GPC (gel permeation chromatography). The weight average molecular weight of the polyester resin refers to the molecular weight of a reaction product obtained by reacting the reactive precursor with the curing agent. If the weight average molecular weight is less than 20,000, the toner tends to flow at low temperatures, and the heat-resistant storage stability may be poor. Furthermore, the viscosity of the toner when melted may decrease, which may result in poor high-temperature offset resistance.

[0042] The polyester resin in the present invention is sufficient if it contains polyester resin A having a structure represented by Structure (A). The polyester resin A having the structure represented by Structure (A) may be used alone, or another polyester resin (hereinafter also referred to as polyester resin B) may be used in combination with the polyester resin A having the structure represented by Structure (A).

[0043] (THF insoluble organic matter) When the total amount of organic components in the toner in the present invention is taken as 100 wt%, the amount of THF-insoluble organic matter is preferably 26 wt% or more and less than 70 wt%. This THF-insoluble organic matter is mainly derived from polyester resin A, and can be adjusted by the content of polyester resin A in the toner. If the amount of THF-insoluble organic matter is less than 26 wt%, the image strength is insufficient, and if the amount of THF-insoluble organic matter is more than 70 wt%, the fixed image is likely to adhere to the toner during drying in a dryer.

[0044] <Glass transition temperature (Tg1st)> The toner preferably has a glass transition temperature (Tg1st) at the first temperature rise in differential scanning calorimetry (DSC) of 20° C. or more and 40° C. or less. For conventional toners, when the Tg is about 50° C. or less, the toner is likely to aggregate due to temperature changes during transportation and storage in summer and tropical regions. As a result, the toner solidifies in the toner bottle and adheres to the developing machine. In addition, toner clogging in the toner bottle can cause poor replenishment, and toner adherence in the developing machine can cause image abnormalities. The toner of the present invention has a lower Tg than conventional toners. However, since the polyester resin A having the structure represented by Structure (A), which is a low Tg component in the toner, is non-linear, the toner of the present invention can maintain heat-resistant storage stability. In particular, when the polyester resin A having the structure represented by Structure (A) has a urethane bond or urea bond with high cohesive force, the effect of maintaining heat-resistant storage stability becomes more remarkable.

[0045] If the Tg1st is higher than the glass transition temperature of the toner of 40° C., the toner image is likely to crack when washed or stretched on a fabric. If the glass transition temperature of the toner is lower than 20° C., the images are likely to fuse together when dried in a dryer. A preferred embodiment of the present invention includes an embodiment in which the polyester resin contains two types of polyester resin, namely, polyester resin A having a structure represented by Structure (A) and polyester resin B, and the toner containing the polyester resin has a Tg1st of 20°C or more and 40°C or less.

[0046] <Volume average particle size> The volume average particle diameter of the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 μm to 18 μm, and more preferably 8 μm to 16 μm from the viewpoint of ensuring a sufficient amount of development.

[0047] (Compatibility between resins) In addition, it is preferable that no separate phases of the different polyester resins A and B can be confirmed in a vertical cross-sectional SEM image of the fixed image of the toner, that is, the polyester resins A and B are compatible with each other. If the resins are not compatible with each other, the distribution of image intensity becomes non-uniform, which leads to cracked interfaces in the image.

[0048] (Amorphous polyester resin B other than polyester resin A) The amorphous polyester resin B other than the polyester resin A used in the present invention is obtained by condensation polymerization of an alcohol and a carboxylic acid.

[0049] Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; etherified bisphenols such as 1,4-bis(hydroxymethyl)cyclohexane and bisphenol A; other dihydric alcohol monomers; and trihydric or higher polyhydric alcohol monomers. Among these, from the viewpoint of image strength, those which do not contain aromatic diols such as etherified bisphenols such as bisphenol A, and whose alcohol component is composed only of an aliphatic diol having 2 to 6 carbon atoms, are preferred. Furthermore, the aliphatic diol preferably contains at least a portion of ethylene glycol or 1,2-propylene glycol.

[0050] Examples of the carboxylic acid component include divalent organic acid monomers and trivalent or higher polyvalent carboxylic acid monomers. Examples of the divalent organic acid monomer include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid. Examples of the trivalent or higher polyvalent carboxylic acid monomer include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid.

[0051] The weight average molecular weight of the amorphous polyester resin B other than the polyester resin A is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of image strength, however, it is preferably 12,000 or more and 100,000 or less as measured by GPC (gel permeation chromatography).

[0052] <Crystalline polyester resin> In the toner of the present invention, in addition to the polyester resin A and the amorphous polyester resin B other than the polyester resin A, a crystalline polyester resin (hereinafter also referred to as crystalline polyester resin C) can also be used in combination. Crystalline polyester resin C has high crystallinity and exhibits a sharp melting property, which shows a rapid drop in viscosity near the fixing start temperature. By using crystalline polyester resin C having such a property together with polyester resin A and polyester resin B, a toner having both good fixing property to the substrate and image strength can be obtained.

[0053] The crystalline polyester resin C can be obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester. In the present invention, the crystalline polyester resin C refers to a resin obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester, as described above, and a modified polyester resin, for example, the polyester resin A, does not belong to the crystalline polyester resin.

[0054] The presence or absence of crystallinity of the crystalline polyester resin C in the present invention can be confirmed by a crystal analysis X-ray diffraction device (for example, X'Pert Pro MRD Philips). The measurement method is described below. First, the target sample is ground in a mortar to prepare a powdered sample, and the powdered sample is evenly applied to a sample holder.Then, the sample holder is set in the diffraction device, and measurements are performed to obtain a diffraction spectrum. When the half-width of the peak having the greatest intensity among the peaks obtained in the range of 20°<2θ<25° among the obtained diffraction peaks is 2.0 or less, it is judged to have crystallinity. In contrast to crystalline polyester resins, polyester resins that do not show the above-mentioned state are called amorphous polyester resins in the present invention. The conditions for the X-ray diffraction measurements are as follows. [Measurement conditions] Tension kV: 45kV Current: 40mA MPSS Upper Gonio Scan mode: continuous Start angle: 3° End angle: 35° Angle Step: 0.02° Lucident beam optics Divergence slit: Div slit 1 / 2 Diffraction beam optics Anti scatter slit: As fixed 1 / 2 Receiving slit: Prog rec slit

[0055] -Polyhydric alcohol- The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyhydric alcohol include diols and trihydric or higher alcohols. Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferred, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferred. Examples of the saturated aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred because the crystalline polyester resin has high crystallinity and excellent sharp melting properties. Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. These may be used alone or in combination of two or more.

[0056] -Polycarboxylic acids- The polyvalent carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyvalent carboxylic acid include divalent carboxylic acids and trivalent or higher carboxylic acids. Examples of the divalent carboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2,6-dicarboxylic acid; and further include anhydrides of these acids and lower (carbon number: 1 to 3) alkyl esters of these acids. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, as well as anhydrides and lower (carbon number 1 to 3) alkyl esters thereof. The polycarboxylic acid may contain a dicarboxylic acid having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid. Furthermore, the polycarboxylic acid may contain a dicarboxylic acid having a double bond in addition to the saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid. These may be used alone or in combination of two or more.

[0057] The crystalline polyester resin C is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin C preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. This is preferable in that the resin has high crystallinity and excellent sharp melting properties, and can therefore exhibit excellent low-temperature fixability.

[0058] The molecular structure of the crystalline polyester resin C can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 Or 990±10cm -1 to the δ of olefin CH One example is a method for detecting a crystalline polyester resin that has absorption based on (out-of-plane bending vibration).

[0059] <Other ingredients> Examples of the other components include a release agent, a colorant, a charge control agent, an external additive, a flowability improver, a cleaning property improver, and a magnetic material.

[0060] -Release agent- The release agent that can be used in the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and partial oxides thereof, or aliphatic hydrocarbons such as fluorides and chlorides, animal oils such as beef tallow and fish oil, vegetable oils such as palm oil, soybean oil, rapeseed oil, rice bran wax, and carnauba wax, higher aliphatic alcohols and higher fatty acids such as montan wax, fatty acid amides, fatty acid bisamides, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, and zinc behenate, metal soaps, fatty acid esters, and polyvinylidene fluoride can be mentioned. These may be used alone or in combination of two or more. Of these, it is preferable to contain at least an ester wax such as a fatty acid ester.

[0061] When a maleic acid-modified polyolefin having a polypropylene block in the main chain is contained in a toner, if the content is high, the toner cannot be separated from the fixing roller (or fixing belt) during fixing, causing waste paper jams, but this problem can be suppressed by adding an ester wax as a release agent. Furthermore, maleic acid-modified polyolefin having a polypropylene block in the main chain can finely disperse the ester wax.

[0062] The content of the release agent in the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 to 8.0 mass %, more preferably 1.0 to 6.0 mass %. If the content is 0.1 mass % or more, the toner and the fixing roller (or fixing belt) are separated during fixing, and clogging of waste paper can be suppressed. Also, if the content is 8.0 mass % or less, the toner can be sufficiently fixed to the plastic film.

[0063] -Coloring agent- The colorant used in the toner of the present invention is not particularly limited, and any commonly used colorant can be appropriately selected and used. Depending on the color, a black toner, a cyan toner, a magenta toner, a yellow toner, a white toner, a green toner, a blue toner, etc. can be formed.

[0064] The colorant used in the black toner is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable to use carbon black alone or a mixture of carbon black as the main component and copper phthalocyanine or the like with the hue and brightness adjusted. The colorant used in the cyan toner is not particularly limited and can be appropriately selected depending on the purpose, but copper phthalocyanine, which is Cyan Pigment Blue 15:3, or a mixture of the above colorant and aluminum phthalocyanine is preferred. The colorant used in the magenta toner is not particularly limited and can be appropriately selected depending on the purpose, but Pigment Red 53:1, Pigment Red 81, Pigment Red 122, and Pigment Red 269 can be used alone or in combination. The colorant used in the yellow toner is not particularly limited and can be appropriately selected depending on the purpose, but Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, and Pigment Yellow 185 can be used alone or in combination. It is preferable to use Pigment Yellow 185 alone or in combination with Pigment Yellow 74 from the viewpoints of saturation and storage stability. The colorant used in the white toner is not particularly limited and can be appropriately selected depending on the purpose, and examples of the colorant that can be used include titanium dioxide that has been surface-treated with silicon, zirconia, aluminum, polyol, etc. Organic white pigments can also be used. The colorant used in the green toner is not particularly limited and can be appropriately selected depending on the purpose. For example, Pigment Green 7 can be used, but safety considerations must be taken into account. The colorant used in the blue toner is not particularly limited and can be appropriately selected depending on the purpose. Examples of the colorant include Pigment Blue 15:1 and Pigment Violet 23.

[0065] When the toner image formed by the toner of the present invention is used as a layer (underlayer) in contact with a peelable support or a flexible recording medium, an image using a conventional toner can be formed on the upper layer. In addition, since the toner of the present invention has rubber elasticity, the printed image is less likely to crack when pulled, bent, or washed. From this viewpoint and from the viewpoint of not impairing the color of the toner overlaid thereon, when a toner image formed by the toner of the present invention is used as a base layer, it is preferable that the toner is achromatic (white or colorless).

[0066] The colorant can also be used as a masterbatch composited with a resin. Examples of resins to be used in the preparation of the masterbatch or kneaded with the masterbatch include, in addition to the other polyester resins, styrene or its substituted polymers such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene 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, and styrene-α-chloromethyl methacrylate copolymer. styrene-based copolymers such as styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resins, epoxy polyol resins, polyurethanes, polyamides, polyvinyl butyral, polyacrylic acid resins, rosin, modified rosin, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. These may be used alone or in combination of two or more.

[0067] --Color toner-- When the toner image formed by the toner of the present invention is used as a layer (undercoat layer) in contact with a peelable support or a flexible recording medium, and an image is formed on the upper layer using a conventional toner, a color toner may be used as the conventional toner. The color toner contains a binder resin and the colorant, and can be a black toner, a cyan toner, a magenta toner, a yellow toner, a white toner, a green toner, a blue toner, or the like, depending on the color of the colorant.

[0068] The binder resin contained in the color toner is not particularly limited as long as the color toner exhibits good fixing property to the toner image formed by the toner of the present invention, and can be appropriately selected depending on the purpose.

[0069] -Charge control agent- The charge control agent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, metal salicylate, and metal salts of salicylic acid derivatives. Specific examples include the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, and the phenol condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, the boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. These charge control agents can be melt-kneaded together with the master batch and the resin and then dissolved and dispersed, or of course can be added when directly dissolving or dispersing in an organic solvent, or can be fixed on the toner surface after the toner particles are produced.

[0070] -External additives- In the toner of the present invention, inorganic fine particles and the like can be used as an external additive. The inorganic fine particles for external addition used in the present invention are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Among these, silica, alumina, and titanium oxide are preferred. In addition, inorganic fine particles may be surface-treated with hydrophobic treatment agent.Hydrophobic treatment agent is not particularly limited and can be appropriately selected according to purpose, for example, silane coupling agent, silylating agent, silane coupling agent having fluorinated alkyl group, organic titanate coupling agent, aluminum coupling agent, etc. are preferred surface treatment agents.Also, silicone oil can be used as hydrophobic treatment agent to obtain sufficient effect.

[0071] <Methods of calculating and analyzing various characteristics of toner and toner components> The SP value, Tg, acid value, hydroxyl value, molecular weight, and melting point of the polyester resin, the crystalline polyester resin, and the release agent may be measured for each of them. Alternatively, the SP value, Tg, molecular weight, melting point, and mass ratio of the constituent components may be calculated by separating the components from an actual toner by gel permeation chromatography (GPC) or the like and subjecting each separated component to the analytical method described below.

[0072] Separation of each component by GPC can be carried out, for example, by the following method. In GPC measurement using THF (tetrahydrofuran) as the mobile phase, the eluate is fractionated using a fraction collector or the like, and fractions corresponding to the desired molecular weight portion of the full integral of the elution curve are collected.

[0073] The combined eluate is concentrated and dried using an evaporator or the like, and the solid content is then dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, 1 H-NMR measurement is performed, and the ratio of constituent monomers of the resin in the eluted components is calculated from the integral ratio of each element.

[0074] As another method, the eluate is concentrated, hydrolyzed with sodium hydroxide or the like, and the decomposition products are qualitatively and quantitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the ratio of constituent monomers.

[0075] In addition, in the case where the toner manufacturing method forms toner base particles while generating a polyester resin by an elongation reaction and / or a crosslinking reaction between the non-linear reactive precursor and the curing agent, the polyester resin may be separated from the actual toner by GPC or the like to determine the Tg and the like of the polyester resin, or a polyester resin may be synthesized separately by an elongation reaction and / or a crosslinking reaction between the non-linear reactive precursor and the curing agent, and the Tg and the like of the synthesized polyester resin may be measured.

[0076] <<Means for separating toner components>> An example of a means for separating each component when analyzing the toner will be described in detail below. First, 1 g of toner is put into 100 mL of THF, and the mixture is stirred for 30 minutes at 25° C. to obtain a solution in which the soluble matter is dissolved. This is filtered through a membrane filter with an opening of 0.2 μm to obtain the THF-soluble portion of the toner. Next, this is dissolved in THF to prepare a sample for GPC measurement, and is injected into the GPC used for measuring the molecular weight of each of the above-mentioned resins. Meanwhile, a fraction collector is placed at the eluate outlet of the GPC to collect the eluate at predetermined counts, and the eluate is obtained at 5% area ratios from the start of elution (the rise of the curve) of the elution curve. Next, for each elution, 30 mg of the sample is dissolved in 1 mL of deuterated chloroform, and 0.05 vol. % of tetramethylsilane (TMS) is added as a standard substance. The solution is filled into a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by 128 accumulations at 23° C. to 25° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). The monomer composition and the constituent ratio of the polyester resin and the crystalline polyester resin contained in the toner can be determined from the peak integral ratio of the obtained spectrum.

[0077] For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is determined from the integral ratio of each peak. Peak assignments can be done, for example, Around 8.25 ppm: From the benzene ring of trimellitic acid (one hydrogen) Around 8.07ppm to 8.10ppm: From the benzene ring of terephthalic acid (4 hydrogen atoms) Around 7.1ppm to 7.25ppm: From the benzene ring of bisphenol A (4 hydrogen atoms) Around 6.8 ppm: From the benzene ring of bisphenol A (4 hydrogens) and from the double bond of fumaric acid (2 hydrogens) Around 5.2ppm to 5.4ppm: From methine of bisphenol A propylene oxide adduct (one hydrogen) Around 3.7ppm to 4.7ppm: Methylene-derived compounds of bisphenol A propylene oxide adducts (2 hydrogens) and methylene-derived compounds of bisphenol A ethylene oxide adducts (4 hydrogens) Around 1.6 ppm: From the methyl group of bisphenol A (6 hydrogen atoms) It can be said that:

[0078] From these results, for example, the extract recovered in a fraction in which polyester resin A having a structure represented by structure (A) accounts for 90% or more can be treated as polyester resin A having a structure represented by structure (A). Similarly, the extract recovered in the fraction in which polyester resin B accounts for 90% or more can be treated as polyester resin B. In addition, the extract recovered in the fraction in which the crystalline polyester resin C accounts for 90% or more can be treated as the crystalline polyester resin C.

[0079] <<Analysis of THF-insoluble organic matter in toner>> The THF-insoluble organic matter of the toner can be extracted, for example, as follows. One part of toner is added to 40 parts of THF and refluxed for 6 hours, after which the insoluble components are precipitated using a centrifuge to separate the insoluble components from the supernatant. The insoluble components are dried at 40°C for 20 hours to obtain a THF-insoluble organic matter. The THF-insoluble organic matter corresponds to a nonlinear polyester resin. Therefore, the THF-insoluble organic matter contains multiple structural parts derived from trivalent isocyanate. The composition of the THF-insoluble organic matter can be analyzed by NMR measurement using a solution or solid, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurement, and the like. Conveniently, the analysis can be performed by pyrolysis and simultaneous methylation GC-MS method using a methylation reagent, for example, as follows. Device name: Shimadzu QP2010 Frontier Lab Py2020D Data analysis software: Shimadzu GCMSsolution Heating temperature: 280℃ Reaction pyrolysis temperature: 300℃ Column name: Ultra ALLOY-5 L=30m ID=0.25mm Film=0.25μm Constant temperature bath temperature: 50℃ (held for 1 minute) ~ 10℃ / min ~ 330℃ (held for 11 minutes) Carrier gas: 53.6kPa constant, He 1.0mL / min Injection mode: Split (1:100) Ionization method: EI method (70 eV) Measurement mode: Scan mode Library:NIST 20 MASS SPECTRAL

[0080] <<Melting point and glass transition temperature (Tg) measurement method>> The melting point and glass transition temperature (Tg) in the present invention can be measured, for example, by using a DSC system (differential scanning calorimeter) ("Q-200", manufactured by TA Instruments). Specifically, the melting point and glass transition temperature of a sample can be measured by the following procedure. First, about 5.0 mg of the target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, the sample is heated from -80°C to 150°C at a heating rate of 10°C / min (first heating). After that, the sample is cooled from 150°C to -80°C at a heating rate of 10°C / min, and further heated to 150°C at a heating rate of 10°C / min (second heating). During each of the first and second heating, a DSC curve is measured using a differential scanning calorimeter ("Q-200", manufactured by TA Instruments).

[0081] From the obtained DSC curves, the analysis program in the Q-200 system can be used to select the DSC curve at the first temperature rise and determine the glass transition temperature of the target sample at the first temperature rise. Similarly, the DSC curve at the second temperature rise can be selected and the glass transition temperature of the target sample at the second temperature rise can be determined.

[0082] From the obtained DSC curves, the analysis program in the Q-200 system can be used to select the DSC curve during the first heating and determine the endothermic peak top temperature during the first heating of the target sample as the melting point. Similarly, the DSC curve during the second heating can be selected and the endothermic peak top temperature during the second heating of the target sample as the melting point.

[0083] In this specification, when a toner is used as a target sample, the glass transition temperature during the first temperature increase is designated as Tg1st, and the glass transition temperature during the second temperature increase is designated as Tg2nd.

[0084] In this specification, the glass transition temperature and melting point of the polyester resin, the crystalline polyester resin, and other components such as the release agent are defined as the endothermic peak top temperature, Tg, during the second heating, unless otherwise specified, of each sample.

[0085] <<Method of measuring particle size distribution>> The volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, and the ratio thereof (D4 / Dn) can be measured using, for example, a Coulter Counter TA-II or a Coulter Multisizer II (both manufactured by Coulter Corporation). In the present invention, a Coulter Multisizer II was used. The measurement method is described below. First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 mL to 150 mL of the electrolyte solution. Here, the electrolyte solution is a 1 mass % NaCl aqueous solution prepared using first-class sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Then, 2 mg to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles or toner are measured using the measuring device with a 100 μm aperture as an aperture, and the volume distribution and number distribution are calculated. From the distribution thus obtained, the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner can be obtained. Thirteen channels are used: 2.00 μm or more but less than 2.52 μm; 2.52 μm or more but less than 3.17 μm; 3.17 μm or more but less than 4.00 μm; 4.00 μm or more but less than 5.04 μm; 5.04 μm or more but less than 6.35 μm; 6.35 μm or more but less than 8.00 μm; 8.00 μm or more but less than 10.08 μm; 10.08 μm or more but less than 12.70 μm; 12.70 μm or more but less than 16.00 μm; 16.00 μm or more but less than 20.20 μm; 20.20 μm or more but less than 25.40 μm; 25.40 μm or more but less than 32.00 μm; and 32.00 μm or more but less than 40.30 μm, and the target particles are 2.00 μm or more but less than 40.30 μm in diameter.

[0086] <<Molecular weight measurement>> The molecular weight of each of the components of the toner can be measured, for example, by the following method. Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-H 15cm triple column (Tosoh Corporation) Temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35mL / min Sample: 0.4 mL of 0.15% by mass sample injected Sample pretreatment: The toner is dissolved in tetrahydrofuran THF (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, and then filtered through a 0.2 μm filter, and the filtrate is used as the sample. 100 μL of the THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of a calibration curve prepared using several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for preparing a calibration curve, Shodex STANDARD Std. Nos. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, and S-0.580 manufactured by Showa Denko KK are used. The detector used is an RI (refractive index) detector.

[0087] <Toner manufacturing method> The toner manufacturing method is not particularly limited and can be appropriately selected depending on the purpose, but the toner contains the polyester resin, preferably further contains the crystalline polyester resin, and is preferably granulated by dispersing an oil phase containing the release agent, the colorant, etc., in an aqueous medium, as necessary. In particular, it is more preferable that the polyester resin contains two types of polyester resins, namely, polyester resin A having a structure represented by Structure (A) and another polyester resin B. The toner contains, as the polyester resin A, a polyester resin which is the polyester prepolymer (which is a reaction product of the polyester portion of the R2 and the polyisocyanate, i.e., a reaction precursor which is reacted with a curing agent), and the other polyester resin which does not have a urethane bond or a urea bond, and preferably contains the crystalline polyester resin, and further, as necessary, is more preferably granulated by dispersing an oil phase which contains the curing agent, the release agent, the colorant, etc., in an aqueous medium.

[0088] An example of the method for producing such a toner is a known dissolution suspension method. As an example of the method for producing the toner, a method for forming toner base particles while producing polyester resin A having a structure represented by Structure (A) by elongation reaction and / or crosslinking reaction between the polyester prepolymer and the curing agent is described below. In such a method, an aqueous medium is prepared, an oil phase containing toner materials is prepared, the toner materials are emulsified or dispersed, and the organic solvent is removed.

[0089] - Preparation of aqueous medium (aqueous phase) - The aqueous medium can be prepared, for example, by dispersing resin particles in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium.

[0090] The aqueous medium is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination of two or more. Among these, water is preferred.

[0091] The water-miscible solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, etc. The alcohol is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include methanol, isopropanol, ethylene glycol, etc. The lower ketone is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include acetone, methyl ethyl ketone, etc.

[0092] - Preparation of oil phase - The oil phase containing the toner materials can be prepared by dissolving or dispersing the toner materials, which include at least the polyester prepolymer, the other polyester resin, and the crystalline polyester resin, and further include the curing agent, the releasing agent, the colorant, and the like, as necessary, in an organic solvent.

[0093] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but an organic solvent having a boiling point of less than 150° C. is preferred in terms of ease of removal.

[0094] The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. These may be used alone or in combination of two or more.

[0095] Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc. are preferable, and ethyl acetate is more preferable.

[0096] -Emulsification or dispersion- The toner materials can be emulsified or dispersed by dispersing an oil phase containing the toner materials in the aqueous medium. When the toner materials are emulsified or dispersed, the curing agent and the polyester prepolymer undergo an elongation reaction and / or a crosslinking reaction to produce a polyester resin A having a structure represented by Structure (A).

[0097] The polyester resin A having the structure represented by the structure (A) can be produced, for example, by the following methods (1) to (3). (1) A method of producing a polyester resin A having a structure represented by Structure (A) by emulsifying or dispersing an oil phase containing the polyester prepolymer and the curing agent in an aqueous medium, and subjecting the curing agent and the polyester prepolymer to an elongation reaction and / or crosslinking reaction in the aqueous medium. (2) A method in which an oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium to which the curing agent has been added in advance, and the curing agent and the polyester prepolymer are subjected to an elongation reaction and / or a crosslinking reaction in the aqueous medium to produce a polyester resin A having a structure represented by Structure (A). (3) A method in which an oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent and the polyester prepolymer undergo an elongation reaction and / or a crosslinking reaction at the particle interface in the aqueous medium to produce a polyester resin A having a structure represented by Structure (A). In addition, when the curing agent and the polyester prepolymer are subjected to an elongation reaction and / or a crosslinking reaction from the particle interface, polyester resin A having a structure represented by Structure (A) is preferentially formed on the surface of the toner produced, and a concentration gradient of polyester resin A having a structure represented by Structure (A) can be provided in the toner.

[0098] The reaction conditions (reaction time, reaction temperature) for producing polyester resin A having a structure represented by Structure (A) are not particularly limited and can be appropriately selected depending on the combination of the curing agent and the polyester prepolymer. The reaction time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 minutes to 40 hours, and more preferably 2 hours to 24 hours. The reaction temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C to 150°C, and more preferably 40°C to 98°C. The method for stably forming a dispersion liquid containing the polyester prepolymer in the aqueous medium is not particularly limited and may be appropriately selected depending on the purpose. For example, there may be mentioned a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase, and the oil phase is dispersed by shear force. The dispersing machine for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. Examples of the dispersing machine include a low-speed shear type dispersing machine, a high-speed shear type dispersing machine, a friction type dispersing machine, a high-pressure jet type dispersing machine, and an ultrasonic dispersing machine. Among these, a high-speed shear type disperser is preferred because it is possible to control the particle size of the dispersion (oil droplets) to 2 μm to 20 μm. When the high-speed shear type dispersing machine is used, the conditions such as the rotation speed, dispersing time, and dispersing temperature can be appropriately selected depending on the purpose. The rotation speed is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1,000 rpm to 30,000 rpm, and more preferably 5,000 rpm to 20,000 rpm. The dispersion time is not particularly limited and can be appropriately selected depending on the purpose, but in the case of a batch method, it is preferably 0.1 to 5 minutes. The dispersion temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0° C. to 150° C. under pressure, and more preferably 40° C. to 98° C. In general, the higher the dispersion temperature, the easier the dispersion. The amount of the aqueous medium used when emulsifying or dispersing the toner materials is not particularly limited and can be appropriately selected depending on the purpose. However, the amount is preferably 50 parts by mass to 2,000 parts by mass, and more preferably 100 parts by mass to 1,000 parts by mass, relative to 100 parts by mass of the toner materials. If the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner materials may become poor, and toner base particles having the specified particle size may not be obtained. If the amount of the aqueous medium used is more than 2,000 parts by mass, the production cost may become high.

[0099] When the oil phase containing the toner materials is emulsified or dispersed, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets, forming a desired shape, and sharpening the particle size distribution. The dispersant is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymer-based protective colloids, etc. These may be used alone or in combination of two or more. Among these, surfactants are preferred. The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be used. The anionic surfactant is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include alkylbenzene sulfonate, α-olefin sulfonate, phosphate, etc. Among these, those having a fluoroalkyl group are preferred. A catalyst can be used in the elongation reaction and / or crosslinking reaction in producing polyester resin A having the structure represented by Structure (A). The catalyst is not particularly limited and can be appropriately selected depending on the purpose. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

[0100] -Removal of organic solvents- The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of gradually increasing the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion liquid in a dry atmosphere to remove the organic solvent in the oil droplets, and the like can be mentioned. When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and can further be classified, etc. The classification can be performed by removing fine particles in a liquid using a cyclone, decanter, centrifugal separation, etc., or the classification operation can be performed after drying. The obtained toner base particles may be mixed with particles of the external additive, the charge control agent, etc. At this time, by applying a mechanical impact force, it is possible to suppress the particles of the external additive, etc. from being detached from the surface of the toner base particles. The method of applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. Examples of the method include a method of applying an impact force to the mixture using a blade rotating at high speed, and a method of introducing the mixture into a high-speed air stream and accelerating it to cause particles to collide with each other or with an appropriate collision plate. The apparatus used in the above method is not particularly limited and can be appropriately selected depending on the purpose. Examples of the apparatus include Angmill (manufactured by Hosokawa Micron Corporation), an apparatus obtained by modifying an I-type mill (manufactured by Japan Pneumatic Mfg. Co., Ltd.) to reduce the grinding air pressure, a Hybridization System (manufactured by Nara Machinery Works, Ltd.), a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

[0101] (Developer) The developer of the present invention contains at least the toner, and optionally contains other components such as a carrier that are appropriately selected. For this reason, it is possible to stably form high-quality images with excellent transferability, charging property, etc. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer corresponding to the recent improvement in information processing speed, a two-component developer is preferable because of its improved life. When the developer is used as a one-component developer, even if the toner is balanced, there is little variation in the particle size of the toner, there is little filming of the toner on the developing roller, and there is little melting of the toner to components such as blades that thin the toner layer, and good and stable developability and images can be obtained even with long-term stirring in the developing device. When the developer is used as a two-component developer, the particle size of the toner changes little even when the toner is balanced over a long period of time, and good and stable developability and images can be obtained even when the toner is stirred for a long period of time in a developing device.

[0102] <Career> The carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having a core material and a resin layer covering the core material.

[0103] -Core material- The material of the core material is not particularly limited and can be appropriately selected according to the purpose. For example, manganese-strontium-based material of 50 emu / g to 90 emu / g, manganese-magnesium-based material of 50 emu / g to 90 emu / g, etc. can be mentioned. In order to ensure image density, it is preferable to use high magnetization materials such as iron powder of 100 emu / g or more, magnetite of 75 emu / g to 120 emu / g. In addition, it is preferable to use low magnetization materials such as copper-zinc-based materials of 30 emu / g to 80 emu / g, because it can reduce the impact of the developer in a standing state on the photoconductor and is advantageous for high image quality. These materials may be used alone or in combination of two or more.

[0104] The volume average particle diameter of the core material is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm. If the volume average particle diameter is less than 10 μm, the amount of fine powder in the carrier increases, the magnetization per particle decreases, and the carrier may scatter, while if it exceeds 150 μm, the specific surface area decreases, the toner may scatter, and in full color with many solid parts, the reproduction of the solid parts may be particularly poor.

[0105] When the toner is used in a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90 parts by mass to 98 parts by mass, more preferably 93 parts by mass to 97 parts by mass, relative to 100 parts by mass of the two-component developer.

[0106] The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

[0107] (Toner storage unit) The toner storage unit in the present invention refers to a unit having a function of storing toner and storing the toner. Examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge. The toner storage container refers to a container that stores toner. The developing device has a means for containing toner and developing the toner. The process cartridge is a cartridge which integrates at least an image carrier and a developing means, contains toner, and is detachably mountable to an image forming apparatus. The process cartridge may further include at least one selected from a charging means, an exposure means, and a cleaning means.

[0108] By mounting the toner storage unit of the present invention in an image forming apparatus and forming an image, it is possible to form an image taking advantage of the characteristics of the toner, such as no filming, excellent low-temperature fixing property, high-temperature offset resistance, high gloss, high color reproducibility, and heat-resistant storage stability. In the following, a developer container that contains a developer including a toner will be described in particular.

[0109] (Developer container) The developer storage container according to the present invention contains the developer of the present invention. The container is not particularly limited and can be appropriately selected from among known containers, and examples of the container include those having a container body and a cap. The size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, etc., and the inner surface is formed with spiral irregularities so that the developer content can be transferred to the outlet side by rotating, and it is particularly preferred that a part or all of the spiral irregularities have a bellows function. Furthermore, the material is not particularly limited, but it is preferred that the material has good dimensional accuracy, and examples of such materials include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin. The developer storage container is easy to store, transport, and the like, and has excellent handleability, and therefore can be detachably attached to a process cartridge, an image forming apparatus, and the like, which will be described later, and used for replenishing the developer.

[0110] (Image forming apparatus and image forming method) The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, an electrostatic latent image forming means, a developing means, a transferring means, and a fixing means, and further comprises other means as necessary. The image forming method according to the present invention includes at least an electrostatic latent image forming step, a developing step, a transferring step, and a fixing step, and may further include other steps as necessary. The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming means, the developing step can be suitably performed by the developing means, the transfer step can be suitably performed by the transfer means, the fixing step can be suitably performed by the fixing means, and the other steps can be suitably performed by the other means.

[0111] <Electrostatic latent image carrier> The material, structure, and size of the electrostatic latent image bearing member are not particularly limited and may be appropriately selected from known materials, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine, etc. Among these, amorphous silicon is preferred in terms of long life.

[0112] The amorphous silicon photoreceptor may be, for example, a photoreceptor having a photoconductive layer made of a-Si formed on the support by heating the support to 50° C. to 400° C., and forming the photoconductive layer on the support by a film forming method such as vacuum deposition, sputtering, ion plating, thermal CVD (chemical vapor deposition), photo CVD, plasma CVD, etc. Among these, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current, high frequency, or microwave glow discharge to form an a-Si deposition film on the support, is preferable.

[0113] The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably cylindrical. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and particularly preferably 10 mm to 30 mm.

[0114] <Electrostatic latent image forming means and electrostatic latent image forming process> The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and may be appropriately selected depending on the purpose. For example, the electrostatic latent image forming means may include a means having at least a charging member that charges the surface of the electrostatic latent image carrier, and an exposure member that exposes the surface of the electrostatic latent image carrier to light in an imagewise manner.

[0115] The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected depending on the purpose. For example, the electrostatic latent image forming step can be performed by charging the surface of the electrostatic latent image bearing member and then exposing it to light in an imagewise manner, using the electrostatic latent image forming means.

[0116] -Charging materials and charging- The charging member is not particularly limited and can be appropriately selected depending on the purpose. Examples of the charging member include a contact charger known per se having a conductive or semiconductive roller, brush, film, rubber blade, or the like, and a non-contact charger utilizing corona discharge such as a corotron or scorotron.

[0117] The charging can be carried out, for example, by applying a voltage to the surface of the electrostatic latent image bearing member using the charging member.

[0118] The shape of the charging member may be any shape, such as a roller, a magnetic brush, a fur brush, etc., and can be selected according to the specifications and shape of the image forming apparatus. The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which the amount of ozone generated from the charging member is reduced can be obtained.

[0119] -Exposure materials and exposure- The exposure member is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in the shape of an image to be formed, and can be appropriately selected depending on the purpose. Examples of the exposure member include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

[0120] The light source used in the exposure member is not particularly limited and can be appropriately selected depending on the purpose. Examples of the light source include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescence (EL), and other light-emitting materials.

[0121] In order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used.

[0122] The exposure can be carried out, for example, by exposing the surface of the electrostatic latent image bearing member imagewise using the exposure member.

[0123] In the present invention, a light back system may be adopted in which exposure is performed imagewise from the back side of the electrostatic latent image bearing member.

[0124] <Developing means and developing process> The developing means is not particularly limited as long as it is a means for developing the electrostatic latent image with a developer containing a toner to form a toner image, and can be appropriately selected depending on the purpose.

[0125] The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image with a developer containing a toner to form a toner image, and can be appropriately selected depending on the purpose. For example, the developing step can be performed by the developing means.

[0126] The developing means may be of a dry developing type or a wet developing type, and may be a single-color developing means or a multi-color developing means. The developing means is preferably a developing device having an agitator that frictionally agitates the toner to charge it, a magnetic field generating means fixed inside, and a developer carrier that can rotate and carries a developer containing the toner on its surface. In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction during this process and held in a standing state on the surface of a rotating magnet roller to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by electrical attraction. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier.

[0127] <Transfer means and transfer process> The transfer means is not particularly limited as long as it is a means for transferring the toner image onto a peelable support or a flexible recording medium having a surface roughness of 1 μm or more, and can be appropriately selected depending on the purpose. However, a preferred embodiment has a primary transfer means for transferring the toner image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto the peelable support or the flexible recording medium.

[0128] The transfer step is not particularly limited as long as it is a step of transferring the toner image onto a peelable support or a flexible recording medium having a surface roughness of 1 μm or more, and can be appropriately selected depending on the purpose. However, a preferred embodiment is one in which an intermediate transfer body is used, the toner image is primarily transferred onto the intermediate transfer body to form a composite transfer image, and then the composite transfer image is secondarily transferred onto the peelable support or the flexible recording medium, and this can be performed, for example, by the transfer means.

[0129] Here, when the image to be secondarily transferred onto the peeling support or the flexible recording medium is a color image composed of toners of multiple colors, the transfer means can be configured to sequentially overlay toners of each color on the intermediate transfer body to form an image on the intermediate transfer body, and the intermediate transfer means can be configured to secondarily transfer the image on the intermediate transfer body onto the peeling support or the flexible recording medium all at once.

[0130] The intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies depending on the purpose. For example, a transfer belt is preferably used.

[0131] The transfer means (the primary transfer means, the secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the photoreceptor onto the peeling support or the flexible recording medium. Examples of the transfer device include a corona transfer device that uses corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

[0132] <Fixing means and fixing process> The fixing means is not particularly limited as long as it is a means for fixing the toner image transferred onto the peeling support or the flexible recording medium, and may be appropriately selected depending on the purpose, but is preferably a known heating and pressing member. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.

[0133] The fixing step is not particularly limited as long as it is a step of fixing the toner image transferred onto the peeling support or the flexible recording medium, and can be appropriately selected according to the purpose, and for example, it may be performed for each color toner every time it is transferred onto the peeling support or the flexible recording medium, or it may be performed simultaneously for each color toner in a state where they are stacked. The fixing step can be performed, for example, by the fixing means.

[0134] The heating temperature in the heating and pressing member is usually preferably 80°C to 200°C.

[0135] In the present invention, depending on the purpose, for example, a known optical fixing device may be used together with or instead of the fixing means.

[0136] The surface pressure in the fixing step is not particularly limited and can be appropriately selected depending on the purpose. 2 ~80N / cm 2 It is preferable that:

[0137] <Other means and other steps> Examples of the other means include a cleaning means, a discharging means, a recycling means, and a control means. Examples of the other steps include a cleaning step, a static elimination step, a recycling step, and a control step.

[0138] -Cleaning means and cleaning process- The cleaning means is not particularly limited as long as it is capable of removing the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose. Examples of the cleaning means include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

[0139] The cleaning step is not particularly limited as long as it is a step that can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose. For example, the cleaning step can be performed by the cleaning unit.

[0140] -Static charge removal means and static charge removal process- The charge removing means is not particularly limited as long as it is a means for removing electricity by applying a charge removing bias to the photoconductor, and may be appropriately selected depending on the purpose. For example, a charge removing lamp may be used.

[0141] The charge removing step is not particularly limited as long as it is a step of removing electricity by applying a charge removing bias to the photoconductor, and may be appropriately selected depending on the purpose. For example, the charge removing step may be performed by the charge removing unit.

[0142] -Recycling methods and processes- The recycling means is not particularly limited as long as it is a means for recycling the toner removed in the cleaning step back to the developing device, and may be appropriately selected depending on the purpose. For example, a known transport means may be used.

[0143] The recycling process is not particularly limited as long as it is a process for recycling the toner removed by the cleaning process back into the developing device, and can be appropriately selected depending on the purpose. For example, the recycling process can be performed by the recycling means.

[0144] -Control means and control process- The control means is not particularly limited as long as it is a means capable of controlling the movement of each of the means, and can be appropriately selected depending on the purpose. For example, devices such as a sequencer and a computer can be mentioned.

[0145] The control step is not particularly limited as long as it is a step that can control the movement of each step, and can be appropriately selected depending on the purpose. For example, it can be performed by the control means.

[0146] Next, one embodiment of a method for forming an image on a peeling support by the image forming apparatus of the present invention and obtaining an image transfer sheet will be described with reference to Fig. 1. The image forming apparatus 100A shown in Fig. 1 includes a photoconductor drum 10 (hereinafter sometimes referred to as "photoconductor 10") as the electrostatic latent image carrier, a charging roller 20 as the charging means, an exposure device 30 as the exposure means, a developing device 40 as the developing means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

[0147] The intermediate transfer body 50 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 51 arranged inside and stretching it. Some of the three rollers 51 also function as transfer bias rollers capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer body 50. Also, a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) the developed image (toner image) to the peeling support 95 is arranged facing the intermediate transfer body 50 near the intermediate transfer body 50. A corona charger 58 for applying a charge to the toner image on the intermediate transfer body 50 is arranged around the intermediate transfer body 50 between the contact portion between the photoconductor 10 and the intermediate transfer body 50 and the contact portion between the intermediate transfer body 50 and the peeling support 95 in the rotation direction of the intermediate transfer body 50.

[0148] The developing device 40 is composed of a developing belt 41 as the developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the developing belt 41. The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt that is rotatably stretched around a plurality of belt rollers, and a part of the developer container 45K is in contact with the electrostatic latent image carrier 10.

[0149] In the image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 uniformly charges the photoconductor drum 10. The exposure device 30 exposes the photoconductor drum 10 imagewise to light to form an electrostatic latent image. The electrostatic latent image formed on the photoconductor drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer body 50 by a voltage applied from the roller 51, and is further transferred (secondary transfer) onto the peeling support 95. As a result, a transfer image is formed on the peeling support 95, and an image transfer sheet is obtained. The remaining toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the static elimination lamp 70.

[0150] Another example of the image forming apparatus of the present invention is shown in Fig. 2. The image forming apparatus 100B has the same configuration as the image forming apparatus 100A shown in Fig. 1, except that the developing belt 41 is not provided and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged directly opposite each other around the photoconductor drum 10.

[0151] Another example of the image forming apparatus of the present invention is shown in Fig. 3. The image forming apparatus shown in Fig. 3 includes a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

[0152] An endless belt-like intermediate transfer body 50 is provided in the center of the copying machine main body 150. The intermediate transfer body 50 is stretched around support rollers 14, 15, and 16, and can rotate clockwise in FIG. 3. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is provided near the support roller 15. A tandem type developing device 120 is provided on the intermediate transfer body 50 stretched around the support rollers 14 and 15 along the conveying direction of the intermediate transfer body 50, in which four image forming means 18 for yellow, cyan, magenta, and black are arranged in a row facing each other. An exposure device 21, which is the exposure member, is provided near the tandem type developing device 120. A secondary transfer device 22 is provided on the side of the intermediate transfer body 50 opposite the side on which the tandem type developing device 120 is provided. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper transported on the secondary transfer belt 24 and the intermediate transfer body 50 can come into contact with each other. A fixing device 25, which is the fixing means, is disposed near the secondary transfer device 22. The fixing device 25 includes a fixing belt 26, which is an endless belt, and a pressure roller 27 disposed so as to be pressed against the fixing belt 26.

[0153] In the tandem image forming apparatus, a sheet reversing device 28 is disposed near the secondary transfer device 22 and the fixing device 25 for reversing the transfer paper so that images can be formed on both sides of the transfer paper.

[0154] Next, a description will be given of the formation of a full-color image (color copy) using the tandem type developing device 120. That is, first, an original is set on the original table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and an original is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.

[0155] When a start switch (not shown) is pressed, the scanner 300 is driven after the original is transported and moved onto the contact glass 32 when an original is set on the automatic original transport device 400, or immediately when an original is set on the contact glass 32. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from a light source is irradiated by the first traveling body 33, and the reflected light from the original surface is reflected by a mirror in the second traveling body 34, and is received by the reading sensor 36 through the imaging lens 35 to read the color original (color image), which is converted into image information of black, yellow, magenta, and cyan.

[0156] Then, the image information for black, yellow, magenta, and cyan is transmitted to the image forming means 18 (image forming means for black, image forming means for yellow, image forming means for magenta, and image forming means for cyan) in the tandem developing device 120. Then, in each image forming means, a toner image for black, yellow, magenta, and cyan is formed. That is, as shown in FIG. 4, each image forming means 18 (image forming means for black, image forming means for yellow, image forming means for magenta, and image forming means for cyan) in the tandem developing device 120 includes an electrostatic latent image carrier 10 (electrostatic latent image carrier for black 10K, electrostatic latent image carrier for yellow 10Y, electrostatic latent image carrier for magenta 10M, and electrostatic latent image carrier for cyan 10C), a charging device 160 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and a charging device 160 which charges the electrostatic latent image carrier 10 based on each color image information. The image forming apparatus includes an exposure device that exposes the electrostatic latent image carrier to light (L in FIG. 4) in the form of an image corresponding to each color image to form an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, a developing device 61 that is the developing means that develops the electrostatic latent image with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer body 50, a cleaning device 63, and a static eliminator 64. Each image forming means 18 is capable of forming a single color image (black image, yellow image, magenta image, and cyan image) based on image information of the respective color. The black image formed on the black electrostatic latent image carrier 10K, the yellow image formed on the yellow electrostatic latent image carrier 10Y, the magenta image formed on the magenta electrostatic latent image carrier 10M, and the cyan image formed on the cyan electrostatic latent image carrier 10C are sequentially transferred (primary transfer) onto the intermediate transfer body 50 which is rotated by the support rollers 14, 15, and 16. Then, the black image, the yellow image, the magenta image, and the cyan image formed on the cyan electrostatic latent image carrier 10C are superimposed on the intermediate transfer body 50 to form a composite color image (color transfer image).

[0157] On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed a sheet (peel support) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145 and sent to the paper feed path 146, then conveyed by the conveyance roller 147 and guided to the paper feed path 148 in the copying machine main body 150, where they are stopped by striking against the registration roller 49. Alternatively, the paper feed roller 142 is rotated to feed a sheet (recording paper) on the manual feed tray 54, and the sheets are separated one by one by the separation roller 52 and placed in the manual feed path 53, where they are also stopped by striking against the registration roller 49. The registration roller 49 is generally used while being grounded, but may be used with a bias applied to remove paper dust from the sheets. Then, the registration roller 49 is rotated in time with the composite color image (color transfer image) composited on the intermediate transfer body 50, a sheet (peel-off support) is sent between the intermediate transfer body 50 and the secondary transfer device 22, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (peel-off support) by the secondary transfer device 22. In this way, a color image is transferred and formed on the sheet (peel-off support). Note that residual toner on the intermediate transfer body 50 after the image transfer is cleaned by the intermediate transfer body cleaning device 17.

[0158] The sheet (peel-off support) on which the color image has been transferred and formed is transported by the secondary transfer device 22 and sent to the fixing device 25, where the composite color image (color transfer image) is fixed onto the sheet (peel-off support) by heat and pressure. Thereafter, the sheet (peel-off support) is switched by a switching claw 55, discharged by discharge rollers 56, and stacked on a paper output tray 57. Alternatively, the sheet (peel-off support) is switched by a switching claw 55, inverted by a sheet inverting device 28, and guided to the transfer position again, an image is also recorded on the back side, and then discharged by discharge rollers 56 and stacked on a paper output tray 57. In this manner, an image transfer sheet is obtained.

[0159] (Process cartridge) The process cartridge according to the present invention is molded so as to be detachably mountable to various image forming apparatuses, and has at least an electrostatic latent image carrier for carrying an electrostatic latent image, and a developing means for developing the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge of the present invention may further have other means as necessary.

[0160] The developing means includes at least a developer container for containing the developer of the present invention, and a developer carrier for carrying and transporting the developer contained in the developer container. The developing means may further include a regulating member for regulating the thickness of the developer carried.

[0161] 5 shows an example of a process cartridge according to the present invention. The process cartridge 110 has the photosensitive drum 10, a corona charger 52, a developing device 40, a transfer roller 80 and a cleaning device 90. EXAMPLES

[0162] Examples of the present invention will be described below, but the present invention is not limited to the following examples. "Parts" refers to "parts by mass" unless otherwise specified. "%" refers to "% by mass" unless otherwise specified.

[0163] The measured values ​​in the following examples were measured by the methods described in the present specification. The Tg and molecular weight of the polyester resin A having the structure represented by Structure (A), the other polyester resins, the crystalline polyester resin, etc. were measured from each resin obtained in the production examples.

[0164] (Production Example 1) <Synthesis of ketimines> In a reaction vessel equipped with a stirring bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50° C. for 5 hours to obtain [Ketimine Compound 1]. The amine value of [Ketimine Compound 1] was 418.

[0165] (Manufacturing example A-1) <Synthesis of Polyester Resin A-1> -Synthesis of prepolymer A-1- Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, terephthalic acid, adipic acid, and titanium tetraisopropoxide (1,000 ppm relative to the resin component) were added so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 1.2, the diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 50 mol% terephthalic acid and 50 mol% adipic acid. Thereafter, the temperature was raised to 200°C over about 4 hours, and then to 230°C over 2 hours, and the reaction was continued until no water was discharged. Thereafter, the mixture was further reacted for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain an intermediate polyester A'-1. The resulting intermediate polyester A'-1 had a Tg of -40°C, an Mw of 15,000 and an Mw / Mn of 2.0. Next, intermediate polyester A'-1 and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 1.5, diluted with ethyl acetate to give a 50% ethyl acetate solution, and then reacted at 100°C for 5 hours to obtain intermediate polyester A-1 solution. The resulting intermediate polyester A-1 had a Tg of -35°C, an Mw of 20,000 and an Mw / Mn of 2.2. Next, intermediate polyester A-1 and lysine triisocyanate (RTI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate group of RTI / isocyanate group of intermediate polyester) of 0.2, and diluted with ethyl acetate to give a 50% ethyl acetate solution. Pure water was then added dropwise in an amount to give a molar ratio of 0.5 relative to the amount of isocyanate present in the reaction system, and the mixture was allowed to react at 100°C for 5 hours to obtain a prepolymer A-1 solution.

[0166] -Synthesis of polyester resin A-1- The obtained prepolymer A-1 was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amine amount of [ketimine compound 1] was equimolar to the amount of isocyanate in prepolymer A-1. After stirring at 45°C for 10 hours, the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain amorphous polyester resin A-1. The polyester resin A-1 has a structure corresponding to structural formula 1) of Structure (A).

[0167] (Manufacturing example A-2) <Synthesis of Polyester Resin A-2> -Synthesis of prepolymer A-2- Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, terephthalic acid, adipic acid, and titanium tetraisopropoxide (1,000 ppm relative to the resin component) were added so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 1.18, the diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 40 mol% terephthalic acid and 60 mol% adipic acid. Thereafter, the temperature was raised to 200°C over about 4 hours, and then to 230°C over 2 hours, and the reaction was continued until no water was discharged. Thereafter, the mixture was further reacted for 6 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain an intermediate polyester A'-2. The resulting intermediate polyester A'-2 had a Tg of -53°C, an Mw of 15,000 and an Mw / Mn of 2.0. Next, intermediate polyester A'-2 and isocyanurate triisocyanate derived from hexamethylene diisocyanate (Burnock DN-901S manufactured by DIC Corporation) were added in a molar ratio (isocyanate group of DN-901S / hydroxyl group of intermediate polyester) of 0.4 into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and after diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100°C for 5 hours to obtain intermediate polyester A-2 solution. The Tg of the obtained intermediate polyester A-2 was -43°C, Mw was 24,000, and Mw / Mn was 2.4. Next, the intermediate polyester A-2 solution and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) of 1.5, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain a prepolymer A-2 solution.

[0168] -Synthesis of polyester resin A-2- The obtained prepolymer A-2 was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amine amount of [ketimine compound 1] was equimolar to the amount of isocyanate in prepolymer A-2. After stirring at 45°C for 10 hours, the prepolymer elongation product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain amorphous polyester resin A-2. The polyester resin A-2 has a structure corresponding to structural formula 2) of Structure (A).

[0169] (Manufacturing example A-3) <Synthesis of polyester resin A-3> -Synthesis of prepolymer A-3- Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, terephthalic acid, adipic acid, and titanium tetraisopropoxide (1,000 ppm relative to the resin component) were added so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 1.2, the diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 50 mol% terephthalic acid and 50 mol% adipic acid. Thereafter, the temperature was raised to 200°C over about 4 hours, and then to 230°C over 2 hours, and the reaction was continued until no water was discharged. Thereafter, the mixture was further reacted for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain intermediate polyester A-3. The resulting intermediate polyester A-3 had a Tg of -40°C, an Mw of 15,000 and an Mw / Mn of 2.0. Next, intermediate polyester A-3 and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 1.5, diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain an intermediate polyester A-3 solution. Next, the intermediate polyester solution A-3 and trimethylolpropane (TMP) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of intermediate polyester A-3 / hydroxyl groups of TMP) of 5.0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain prepolymer A-3.

[0170] -Synthesis of polyester resin A-3- The obtained prepolymer A-3 was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amine amount of [ketimine compound 1] was equimolar to the amount of isocyanate in prepolymer A-3. After stirring at 45°C for 10 hours, the prepolymer elongation product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain amorphous polyester resin A-3. The polyester resin A-3 has a structure corresponding to structural formula 3) of Structure (A).

[0171] (Manufacturing example A-4) <Synthesis of Polyester Resin A-4> -Synthesis of prepolymer A-4- Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, terephthalic acid, adipic acid, and titanium tetraisopropoxide (1,000 ppm relative to the resin component) were added so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 1.2, the diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 50 mol% terephthalic acid and 50 mol% adipic acid. Thereafter, the temperature was raised to 200°C over about 4 hours, and then to 230°C over 2 hours, and the reaction was continued until no water was discharged. Thereafter, the mixture was further reacted for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain an intermediate polyester A'-4. The resulting intermediate polyester A'-4 had a Tg of -40°C, an Mw of 15,000 and an Mw / Mn of 2.0. Next, intermediate polyester A'-4 and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 0.2, diluted with ethyl acetate to give a 50% ethyl acetate solution, and then reacted at 100°C for 5 hours to obtain intermediate polyester A-4 solution. The resulting intermediate polyester A-4 had a Tg of -34°C, an Mw of 17,000 and an Mw / Mn of 2.2. Next, the intermediate polyester A-4 solution and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) of 1.5, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain a prepolymer A-4 solution.

[0172] -Synthesis of polyester resin A-4- The obtained prepolymer A-4 was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amine amount of [ketimine compound 1] was equimolar to the amount of isocyanate in prepolymer A-4. After stirring at 45°C for 10 hours, the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain amorphous polyester resin A-4. Note that polyester resin A-4 does not correspond to any of structural formulas 1) to 3) of structure (A).

[0173] (Manufacturing example B-1) <Synthesis of Polyester Resin B-1> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, 1,2-propylene glycol, terephthalic acid, adipic acid, and adipic acid were charged in a molar ratio of 120 / 98 / 2, and the mixture was heated under a nitrogen atmosphere. Then, 0.05 g of dibutyltin oxide was added and the mixture was reacted while maintaining the temperature at 200° C. to obtain polyester resin B-1. Resin B-1 had a Tg of 60° C. and a Mw of 12,000.

[0174] (Manufacturing example C-1) <Synthesis of crystalline polyester resin C-1> Into a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a heat exchanger, dodecanedioic acid and 1,6-hexanediol were charged so that the molar ratio of hydroxyl group to carboxyl group, OH / COOH, was 0.9. Together with titanium tetraisopropoxide (500 ppm based on the resin component), the mixture was reacted at 180 °C for 10 hours, then the temperature was raised to 200 °C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin C-1.

[0175] (Example 1) <Preparation of Masterbatch (MB)> 1,200 parts of water, 500 parts of an organic white pigment (Hakkol OWP, manufactured by Showa Chemical Industry Co., Ltd.), and 500 parts of the polyester resin B-1 were added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded at 150 °C for 30 minutes using two rolls, then rolled and cooled and pulverized with a pelletizer to obtain [Masterbatch 1].

[0176] <Preparation of WAX Dispersion> Into a container equipped with a stirrer and a thermometer, 50 parts of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., hydrocarbon wax, melting point 75 °C, SP value 8.8) as a mold release agent 1 and 450 parts of ethyl acetate were charged. The temperature was raised to 80 °C with stirring and held at 80 °C for 5 hours, then cooled to 30 °C in 1 hour. Using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.), dispersion was carried out under the conditions of a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80 vol% filling of zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [WAX Dispersion 1].

[0177] <Preparation of Crystalline Polyester Resin Dispersion> 50 parts of crystalline polyester resin C-1 and 450 parts of ethyl acetate were placed in a vessel equipped with a stirring rod and a thermometer, heated to 80°C with stirring, and held at 80°C for 5 hours. After that, the mixture was cooled to 30°C over 1 hour. Dispersion was carried out using a bead mill (Ultra Visco Mill, manufactured by Imex) at a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume filled with 0.5 mm diameter zirconia beads, and 3 passes to obtain [crystalline polyester resin dispersion 1].

[0178] <Preparation of oil phase> 500 parts of [WAX dispersion 1], 800 parts of [Prepolymer A-1], 500 parts of [Crystalline polyester resin dispersion 1], 450 parts of [Polyester resin B-1], 100 parts of [Master batch 1], and 2 parts of [Ketimine compound 1] as a curing agent were placed in a container and mixed at 5,000 rpm for 60 minutes with a TK Homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain [Oil phase 1].

[0179] <Synthesis of organic fine particle emulsion (fine particle dispersion)> In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, resulting in a white emulsion. The mixture was heated to a temperature of 75°C and reacted for 5 hours. Furthermore, 30 parts of 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75°C for 5 hours to obtain an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-sodium salt of methacrylic acid ethylene oxide adduct sulfate) [fine particle dispersion 1]. The volume average particle diameter of [Fine Particle Dispersion 1] was measured with an LA-920 (manufactured by HORIBA Corp.) and was found to be 0.14 μm. A part of [Fine Particle Dispersion 1] was dried to isolate the resin content.

[0180] <Preparation of aqueous phase> 990 parts of water, 83 parts of [fine particle dispersion], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid, which was designated as [aqueous phase 1].

[0181] <Emulsification / solvent removal> To the vessel containing the [oil phase 1], 1,200 parts of [water phase 1] was added and mixed for 20 minutes at 13,000 rpm using a TK homomixer to obtain [emulsified slurry 1]. [Emulsified slurry 1] was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30°C for 8 hours, and then aged at 45°C for 4 hours to obtain [Dispersed slurry 1].

[0182] <Washing and drying> 100 parts of [Dispersion Slurry 1] is filtered under reduced pressure to obtain a filter cake, (1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. (2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (at 12,000 rpm for 30 minutes), and then filtered under reduced pressure. (3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (4) 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. The above operations (1) to (4) were repeated twice to obtain a filter cake. The filtered cake was dried in a circulating air dryer at 45° C. for 48 hours, and sieved through a 75 μm mesh to obtain toner base particles 1.

[0183] <External Addition Treatment> 100 parts by mass of toner base particles 1 were mixed with 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 parts by mass of titanium oxide having an average particle size of 20 nm, and 0.8 parts of hydrophobic silica fine powder having an average particle size of 15 nm in a Henschel mixer to obtain [Toner 1].

[0184] Example 2 [Toner base particles 2] were obtained in the same manner as in Example 1, except that prepolymer A-1 in Example 1 was replaced with prepolymer A-2, and [toner 2] was obtained using the [toner base particles 2].

[0185] Example 3 [Toner base particles 3] were obtained in the same manner as in Example 1, except that prepolymer A-1 in Example 1 was replaced with prepolymer A-3, and [Toner 3] was obtained using the [Toner base particles 3].

[0186] Example 4 In Example 2, except that the composition ratio of polyester resin A and polyester resin B was changed as shown in Table 1, [toner base particle 5] was obtained in the same manner as in Example 1, and [toner 5] was obtained using the [toner base particle 5].

[0187] Example 5 In Example 2, except that the composition ratio of polyester resin A and polyester resin B was changed as shown in Table 1, [toner base particles 6] was obtained in the same manner as in Example 1, and [toner 6] was obtained using the [toner base particles 6].

[0188] Comparative Example 1 [Toner base particles 4] were obtained in the same manner as in Example 1, except that prepolymer A-1 in Example 1 was replaced with prepolymer A-4, and [Toner 4] was obtained using the [Toner base particles 4].

[0189] Comparative Example 2 In Example 2, except that the composition ratio of polyester resin A and polyester resin B was changed as shown in Table 1, [toner base particle 7] was obtained in the same manner as in Example 1, and [toner 7] was obtained using the [toner base particle 7].

[0190] Comparative Example 3 In Example 2, except that the composition ratio of polyester resin A and polyester resin B was changed as shown in Table 1, [toner base particle 8] was obtained in the same manner as in Example 1, and [toner 8] was obtained using the [toner base particle 8].

[0191] <Preparation of carrier> 100 parts by mass of silicone resin (organo straight silicone), 5 parts by mass of γ-(2-aminoethyl)aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added to 100 parts by mass of toluene, and dispersed for 20 minutes with a homomixer to prepare a resin layer coating liquid. Using a fluidized bed type coating device, the resin layer coating liquid was applied to the surface of 1,000 parts by mass of spherical magnetite with an average particle size of 50 μm to prepare a carrier.

[0192] <Preparation of developer> 5 parts by weight of the toner of each of the Examples and Comparative Examples and 95 parts by weight of the carrier were mixed in a ball mill to prepare a developer.

[0193] <Creating evaluation images> (1) The developer using the toner of each of the examples and comparative examples was set at the fifth station of a RICOH Pro C7200S (manufactured by Ricoh Co., Ltd.), and the toner adhesion amount was 1.0 mg / cm 2 The development and transfer conditions were adjusted by a process controller so that the toner solid image was output in the image layer formation area on a release paper (product name: WoW Light 8.0, manufactured by Piotec Corporation). (2) The toner image transferred to the release paper was then fixed. (3) Place a 100% polyester cloth over the toner image on the release paper and iron it at 160°C with a load of 600g / cm 2The toner image was thermally transferred onto the cloth fabric for 10 seconds to produce an evaluation image.

[0194] In each of the examples and comparative examples, the following evaluations of various properties were carried out.

[0195] <Analysis of THF-insoluble organic matter> One part of toner was added to 40 parts of THF and refluxed for 6 hours. Then, the insoluble components were sedimented by a centrifuge to separate the insoluble components from the supernatant. The insoluble components were dried at 40 °C for 20 hours to obtain THF-insoluble organic matter. The content rate of the THF-insoluble organic matter was determined from this weight.

[0196] <Analysis of compatibility> The cross-section of the toner particles of each toner was confirmed by observing the reflected electron image with a scanning electron microscope (SEM). The presence of the sea part and the island part (incompatible domain) could be confirmed by the color difference between the polyester and the urethane. In order to create contrast and facilitate the discrimination between the island part and the sea part, ruthenium tetroxide staining (substance name: ruthenium tetroxide, manufactured by TAAB) was carried out as necessary. For the crushed product of the melt-kneaded mixture of each toner component stained with ruthenium, SEM images of the particle cross-section at approximately half the position of each particle diameter were taken under the following conditions, and the presence or absence of the sea-island structure was confirmed. The procedure is as follows. Each toner particle was embedded in an epoxy resin, and observation was carried out under the following conditions using a scanning electron microscope (manufactured by Hitachi, Ltd., SU8230). At this time, since the non-stained part is observed as a dark part, it can be distinguished from the stained part (bright part). ·Acceleration voltage: 5 kv ·Emission current: 10 μA ·Probe current: Norm ·Condenser lens 1: 5.0 ·W.D.: 8.0 mm ·Observation mode: SE ·Magnification: ×2,000 or ×5,000 [Evaluation criteria] ○: There is no sea-island structure ×: There is a sea-island structure

[0197] <Method for evaluating heat resistance storage stability> The toner was left for 24 hours in a high-temperature, high-humidity chamber at a temperature of 55° C. and a humidity of 50%. After leaving the toner, the degree of toner blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] ◎: No toner clumps are visible ○: There are a few small clumps of toner that crumble when lightly poked. △: There are clumps of toner that crumble when lightly poked. ×: There are toner lumps that are too hard to crumble even when lightly poked.

[0198] <How to evaluate washability> The evaluation images obtained using each developer were subjected to a wash resistance test according to the test method of JIS0844:2011 and evaluated according to the following criteria. [Evaluation Criteria] ◎: JIS0844 discoloration grayscale rank 5, and no deterioration of image even after 10 washes ○: JIS0844 discoloration grayscale rank 5, and after 10 washes, some of the image cracks △: JIS0844 discoloration grayscale rank 4~3 ×: JIS0844 discoloration grayscale rank 2~1

[0199] <Method for evaluating fixation to flexible media> An adhesive tape having a predetermined adhesive strength was applied to the surface of the evaluation image obtained using each developer, and then the adhesive tape was peeled off to evaluate the remaining condition of the evaluation image. [Evaluation Criteria] ◎: No toner is transferred to the tape at all ○: Some toner transfers to the tape but is not noticeable, no change in image is noticeable △: Some of the toner has been transferred to the tape, and upon closer inspection the image is faded. ×: Too much toner has been transferred to the tape and the image is faded.

[0200] <Method for evaluating dryer durability> The evaluation images obtained using each developer were wetted with water, dried for 90 minutes at 60° C. using a dryer (Armis, small household clothes dryer Moco2 ASD-2.5TP), and evaluated according to the following criteria. [Evaluation Criteria] ◎: No image degradation ○: Slight roughness is observed on some parts of the image surface. △: Slight cracks in parts of the image ×: Cracks appear all over the image

[0201] The evaluation results of each of the examples and comparative examples are shown in Table 1.

[0202] [Table 1] In Table 1, the polyester resin A-4 contained in Comparative Example 1 does not correspond to any of the structural formulas 1) to 3) of the structure (A), and is therefore indicated with "X."

[0203] The aspects of the embodiment of the present invention are as follows, for example. <1> The toner contains a polyester resin having a structure represented by Structure (A), and is characterized in that it contains 26 wt% or more and less than 70 wt% of THF-insoluble organic matter when the total amount of the organic components of the toner is taken as 100 wt%. Structure (A): A structure having R1 having three or more bonds and the same number of R2 as the number of bonds, in which the bonds of R1 and R2 are bonded to each other and are represented by any one of the following structural formulas 1) to 3). 1) R1-NHCONH-R2 2) R1-NHCOO-R2 3) R1-OCONH-R2 (In the above formula, R1 is an aromatic or aliphatic organic group derived from a trivalent or higher alcohol or a trivalent or higher polyisocyanate, R2 is a group derived from a polyester polyol, Represents.) <2> The toner contains a polyester resin that does not contain bisphenol A. <1> The toner is as described above. <3> The weight average molecular weight Mw of the polyester resin not containing bisphenol A is 12,000 or more. <2> The toner is as described above. <4> The toner has a glass transition temperature of 20° C. to 40° C. <1> from <3> The toner according to any one of claims 1 to 5, <5> The toner is achromatic. <1> from <4> The toner according to any one of claims 1 to 5, <6> The toner contains two or more resins including a polyester resin having a structure represented by Structure (A), and the polyester resin having a structure represented by Structure (A) is in a compatible state with other resins. <1> from <5> The toner according to any one of claims 1 to 5, <7> a color toner including a binder resin and a colorant; <1> from <6> and a toner according to any one of the above. <8> A peeling support, and on the peeling support, <1> from <6> 2. An image transfer sheet having an image formed by the toner according to claim 1. <9> <1> from <6> A toner storage unit comprising the toner according to any one of claims 1 to 5. <10> an electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; <1> from <6> a developing means for developing a toner image with a developer containing the toner according to any one of claims 1 to 5 to form a toner image, a transfer means for transferring the toner image onto a peelable support or a flexible recording medium having a surface roughness of 1 μm or more, and a fixing means for fixing the toner image transferred onto the peelable support or the flexible recording medium. <11> An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; <1> from <6> a transfer step of transferring the toner image onto a peelable support or onto a flexible recording medium having a surface roughness of 1 μm or more; and a fixing step of fixing the toner image transferred onto the peelable support or onto the flexible recording medium. <12> forming the toner image as a layer in contact with the peelable support or the flexible recording medium; <11> 2. The image forming method according to claim 1 . <13> The flexible recording medium is a fabric containing fibers. <11> from <12> 13. The image forming method according to claim 12, wherein [Explanation of symbols]

[0204] 10 Electrostatic latent image carrier 18 Image forming means 95 Peeling support 100A Image forming device 100B Image forming device [Prior art documents] [Patent documents]

[0205] [Patent Document 1] Patent No. 5510517

Claims

1. A toner comprising a polyester resin having a structure represented by Structure (A), and containing 26 wt % or more but less than 70 wt % of THF-insoluble organic matter when the total amount of organic components of the toner is taken as 100 wt %. Structure (A): A structure having R1 having three or more bonds and the same number of R2 as the number of bonds, in which a bond between each bond of R1 and each R2 is represented by any one of the following structural formulas 1) to 3). 1) R1-NHCONH-R2 2) R1-NHCOO-R2 3) R1-OCONH-R2 (In the above formula, R1 is an aromatic or aliphatic organic group derived from a trivalent or higher alcohol or a trivalent or higher polyisocyanate, R2 is a group derived from a polyester polyol, Represents.)

2. 2. The toner according to claim 1, wherein the toner contains a polyester resin that does not contain bisphenol A.

3. 3. The toner according to claim 2, wherein the weight average molecular weight Mw of the polyester resin not containing bisphenol A is 12,000 or more.

4. 2. The toner according to claim 1, wherein the toner has a glass transition temperature of 20° C. to 40° C.

5. 2. The toner of claim 1, wherein the toner is achromatic.

6. 2. The toner according to claim 1, wherein the toner contains two or more resins including a polyester resin having a structure represented by Structure (A), and the polyester resin having a structure represented by Structure (A) is in a state of being compatible with other resins.

7. A toner set comprising: a color toner containing a binder resin and a colorant; and the toner according to claim 1 .

8. A peeling support; 7. An image transfer sheet comprising an image formed of the toner according to claim 1 on said peelable support.

9. A toner storage unit, comprising the toner according to claim 1 .

10. An electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; a developing means for developing the electrostatic latent image with a developer containing the toner according to any one of claims 1 to 6 to form a toner image; a transfer means for transferring the toner image onto a peelable support or onto a flexible recording medium having a surface roughness of 1 μm or more; a fixing unit for fixing the toner image transferred onto the peeling support or the flexible recording medium.

11. an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image with a developer containing the toner according to any one of claims 1 to 6 to form a toner image; a transfer step of transferring the toner image onto a peelable support or onto a flexible recording medium having a surface roughness of 1 μm or more; a fixing step of fixing the toner image transferred onto the peeling support or the flexible recording medium.

12. The image forming method according to claim 11, wherein the toner image is formed as a layer in contact with the peelable support or the flexible recording medium.

13. The image forming method according to claim 11, wherein the flexible recording medium is a cloth containing fibers.

Images