JP6544052B2 - Toner, developer, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner, a developer, and an image forming apparatus.

  In recent years, toners are resistant to high-temperature and high-humidity during storage and transportation after manufacture, and reduction in particle size for high-quality output images, high-temperature offset resistance, low-temperature fixability for energy saving, and storage. Heat resistant storage stability is required. In particular, since the power consumption at the time of fixing occupies most of the power consumption in the image forming process, the improvement of the low temperature fixability is very important.

  Heretofore, toners produced by a kneading and pulverizing method have been used. The toner produced by the kneading and pulverizing method is difficult to be reduced in particle diameter, and the shape is irregular and the particle diameter distribution is broad, so that the quality of the output image is not sufficient, and the fixing energy is high There were problems such as. In addition, when a wax (release agent) is added to improve fixability, the toner produced by the kneading and pulverizing method has many waxes on the toner surface because it breaks at the wax interface during pulverization. Resulting in. Therefore, while the releasing effect is obtained, the toner adhesion (filming) to the carrier, the photosensitive member and the blade tends to occur, and there is a problem that the overall performance is not satisfactory.

Therefore, in order to overcome the above-mentioned problems of the kneading and pulverizing method, a method of producing a toner by a polymerization method has been proposed. The toner manufactured by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than the particle size distribution of the toner manufactured by the pulverization method, and further, the inclusion of the releasing agent is also possible. . As a method of producing a toner by a polymerization method, a method of producing a toner from a stretching reaction product of a urethane-modified polyester as a toner binder is disclosed for the purpose of improving low temperature fixability and improving high temperature offset resistance. (See, for example, Patent Document 1).
In addition, a method for producing a toner is disclosed which is excellent in powder flowability and transferability in the case of using a small particle size toner, and which is excellent in any of heat resistance storage stability, low temperature fixability and high temperature offset resistance. , Patent Documents 2 and 3).
In addition, a method for producing a toner having a ripening step is disclosed for producing a toner binder having a stable molecular weight distribution and achieving both low temperature fixability and high temperature offset resistance (see, for example, Patent Documents 4 and 5). .
However, these proposed techniques do not satisfy the high level of low temperature fixability required in recent years.

Therefore, in order to obtain a high level of low-temperature fixability, a toner is proposed which contains a resin containing a crystalline polyester resin and a releasing agent, and the resin and wax are incompatible with each other and have a sea-island phase separation structure. (See, for example, Patent Document 6).
Further, a toner containing a crystalline polyester resin, a releasing agent and a graft polymer has been proposed (see, for example, Patent Document 7).
Furthermore, in order to obtain a higher level of low temperature fixability, a toner is proposed which comprises an amorphous polyester obtained by the reaction of a reactive precursor having a branched structure with a very low glass transition temperature and a curing agent. (See, for example, Patent Document 8).

The proposed techniques described in Patent Documents 6 and 7 can achieve low-temperature fixing because the crystalline polyester resin melts more rapidly than the amorphous polyester resin. However, even if the crystalline polyester resin corresponding to the island in the sea-island phase separation structure melts, the amorphous polyester resin corresponding to most of the sea does not melt yet. In this case, since the fixing does not take place unless both the crystalline polyester resin and the amorphous polyester resin melt, the proposed techniques do not satisfy the high level of low-temperature fixability that has been increasing in recent years.
In addition, the proposed technology described in Patent Document 8 utilizes the property that a polyester resin with a very low glass transition temperature deforms at low temperature, and deforms in response to heating and pressure during fixing, and paper at a lower temperature And the like, which make it easy to adhere to recording media. In addition, since the reactive precursor is non-linear, it has a branched structure in its molecular skeleton and the molecular chain has a three-dimensional network structure, so it deforms at a low temperature but does not flow. It has the nature. Therefore, it is possible to maintain the heat resistant storage stability of the toner and the high temperature offset resistance.
However, according to this technique, a three-dimensional network structure is obtained by ester reaction of a diol, a dicarboxylic acid, a polyhydric alcohol, or an acid, and a polyhydric alcohol or an acid having a branched structure is nonuniformly present. Therefore, there are portions with loose mesh structures and dense portions, and the loose portions cause deterioration of the heat resistant storage stability, and the dense portions cause deterioration of low-temperature fixability, image gloss, image density and color reproducibility.
Further, the part forming a branch is an ester structure, and as a crosslink point of the resin, the cohesion is weak, so if it does not have a dense network structure, it is difficult to maintain the heat resistant storage property. Low temperature fixability and image gloss can not be obtained. It does not satisfy the high level of low temperature fixability and image quality that have been increasing in recent years.
Therefore, at present, there is a need for toners that do not have filming, and have excellent low-temperature fixability, high-temperature offset resistance, high gloss, high color reproducibility, excellent charging characteristics, and heat-resistant storage stability.

  Therefore, an object of the present invention is to provide a toner which does not have filming, and has excellent low temperature fixability, high temperature offset resistance, high gloss, high color reproducibility, excellent charging characteristics and heat resistant storage stability.

The means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing at least a polyester resin, and the polyester resin has a structure represented by any one of the following structural formulas 1) to 3).
1) R1- (NHCONH-R2-X-R3) n-
2) R1- (NHCOO-R2-X-R3) n-
3) R1- (OCONH-R2-X-R3) n-
(In the above formula, n = 3
R1: aromatic or aliphatic organic group,
R2: a polyester derived from at least one of a polycarboxylic acid and a polyol, and a group derived from any resin of a modified polyester in which the polyester is isocyanate-modified
X: urea bond or urethane bond,
R3 represents a group derived from a compound represented by the following general formula (I).
[In the above general formula (I), T ₁ , T ₂ , T ₃ , T ₄ and T ₅ each independently represent a hydrogen atom or an isocyanate group, at least one of which is an isocyanate group, U ₁ , U ₂ , U ₃ , U ₄ and U ₅ each represent either a hydrogen atom or an isocyanate group, and at least one is an isocyanate group. ])

  According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, high-temperature offset resistance, high gloss, high color reproducibility, excellent charging characteristics, and heat resistant storage stability.

FIG. 1 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 2 is a schematic block diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is an image view for explaining the branched structure of a conventional polyester resin. FIG. 4 is an image view for explaining the branched structure of the polyester resin defined in the present invention.

(toner)
The toner of the present invention at least 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 has a structure represented by any one of the following structural formulas 1) to 3).
1) R1- (NHCONH-R2-X-R3) n-
2) R1- (NHCOO-R2-X-R3) n-
3) R1- (OCONH-R2-X-R3) n-
(In the above formula, n = 3
R1: aromatic or aliphatic organic group,
R2: a polyester derived from at least one of a polycarboxylic acid and a polyol, and a group derived from any resin of a modified polyester in which the polyester is isocyanate-modified
X: urea bond or urethane bond,
R3 represents a group derived from a compound represented by the following general formula (I).
[In the above general formula (I), T ₁ , T ₂ , T ₃ , T ₄ and T ₅ each independently represent a hydrogen atom or an isocyanate group, at least one of which is an isocyanate group, U ₁ , U ₂ , U ₃ , U ₄ and U ₅ each represent either a hydrogen atom or an isocyanate group, and at least one is an isocyanate group. ])
That is, the polyester resin has a structure in which R2 which is a polyester or modified polyester portion and R1 corresponding to a branched structure are bonded by a urethane or urea group, and further has a structure in which R2 and R3 are bonded.

In order to improve low-temperature fixability, a method of lowering the glass transition temperature or a method of decreasing the molecular weight may be considered so as to melt the polyester resin (for example, an amorphous polyester resin) with the crystalline polyester resin. However, when the melt viscosity is lowered simply by lowering the glass transition temperature of the polyester resin or decreasing the molecular weight, it is easily imagined that the heat resistant storage stability of the toner and the high temperature offset property at the time of fixing deteriorate. Ru.
On the other hand, in the toner of the present invention, the polyester resin has a branched structure in the molecular skeleton by urethane or urea bond, and the molecular chain becomes a three-dimensional network structure, so it deforms at low temperature. , Has a rubber-like property that does not flow. Therefore, even when the glass transition temperature of the polyester resin is extremely lowered, it is possible to maintain the heat resistant storage stability and the high temperature offset resistance of the toner.
In addition, if the mesh structure is not uniform, the heat resistance storage stability is deteriorated because the flow control of the resin is insufficient at the coarse mesh portion, and the resin deformability is insufficient at the dense mesh portion. As a result, the low temperature fixability and the image gloss decrease.
For example, in the polyester resin described in Japanese Patent No. 5408210 (corresponding to the above-mentioned Patent Document 8) described in the above-mentioned background art, when the part forming a branch has an ester structure (that is, the above-mentioned In the structural formulas represented by any one of 1) to 3), when the portion of R2 has a branched structure, as shown in the image view of FIG. The glossiness is not sufficiently satisfactory. FIG. 3 is a schematic view of a branched structure of a polyester resin obtained by a conventional synthesis method.
As described above, in the conventional polyester resin, the low temperature fixability and the image glossiness are good, while the heat resistant storage stability and the high temperature offset resistance are also good, and all these items give a well-balanced result. It is not easy.

However, since the polyester resin of the present invention can be combined with R1 with a urethane or urea group to form a network structure after synthesis of R2 which is a polyester or a modified polyester moiety, for example, as an example of the production method, 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 having the structural formula represented by any one of the above 1) to 3) defined in the present invention is shown as an image diagram of FIG. FIG. 4 is a schematic view of the branched structure of the polyester resin obtained by the synthesis method described below. Since the lengths of the linear polyester resin portion of the R2 portion are uniform, as shown in FIG. 4, the branched structure of the polyester resin is uniformed.
Thus, by making the network structure of the polyester resin uniform, it is possible to achieve both the heat resistant storage stability of the toner, the low temperature fixability, the image gloss, and the high temperature offset resistance.
Furthermore, since the polyester resin has a urethane structure or a urea bond with high cohesive energy, the polyester resin behaves like a strong crosslinking point, and therefore, even when the mesh structure is coarser, the resin flow is suppressed. Thus, the heat resistant storage stability of the toner, the low temperature fixability, the image gloss, and the high temperature offset resistance can be simultaneously achieved.

  In the polyester resin, a group derived from the compound represented by the above general formula (I) represented by R3 is bonded via R2 and X, and the R3 portion is contained. It is possible to provide a toner capable of achieving a high level of low-temperature fixability and heat-resistant storage stability, while having a proper and high charge level, with little variation of the charge amount in the developing device, and a long life. .

<Polyester resin>
The polyester resin has a structure represented by any one of the structural formulas 1) to 3), and R2 which is a polyester or modified polyester portion is bonded to R1 corresponding to a branched structure by a urethane or urea group. The R2 moiety is further linked to the R3 moiety via X.
Since the polyester resin 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 rubbery properties of the polyester resin are strong. Thus, a toner excellent in heat resistant storage stability and high temperature offset resistance can be produced.
The polyester resin contains a diol component as a component, and more preferably contains a dicarboxylic acid component as a component.
The polyester resin is preferably an amorphous polyester resin.
The polyester resin is obtained by combining R2 corresponding to a polyester resin or a modified polyester resin portion with R1 corresponding to a branched structure portion by a urethane or urea group, and the surface is represented by R2 and the general formula (I). There is no particular limitation as long as it is a group in which a group derived from the compound to be derived is bonded to R3 by a urethane or urea group, and can be appropriately selected depending on the purpose.

<< R1 part, R2 part >>
The method of combining R 1 and R 2 is not limited to the following, but there are, for example, the following three methods.

a) A method of esterifying a diol component and a dicarboxylic acid component to prepare a polyester polyol (R2) having a terminal hydroxyl group, and reacting the obtained polyester polyol with a trivalent or higher polyisocyanate (R1).
b) The diol component and the dicarboxylic acid component are ester-reacted to prepare a polyester polyol (R2) having a terminal hydroxyl group, and the obtained polyester polyol is reacted with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2) A method of producing and reacting the obtained isocyanate-modified polyester with a trivalent or higher alcohol (R1).
c) The diol component and the dicarboxylic acid component are ester-reacted to prepare a polyester polyol (R2) having a terminal hydroxyl group, and the obtained polyester polyol is reacted with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2) A method of producing and reacting the obtained isocyanate-modified polyester with a trivalent or higher polyisocyanate (R1) in the presence of pure water.
It is also possible to react the hydroxyl group remaining in the polyol obtained by any of the above a) to c) with a polyisocyanate having a valence of 2 or more to form a polyester prepolymer, and react with a curing agent in the toner preparation process. .

In order to lower the Tg of the polyester resin and to easily impart the property of deformation at low temperature, the polyester resin contains a diol component as a component, and the diol component is an aliphatic diol having 3 to 12 carbon atoms. It is preferable to contain the aliphatic diol having 4 to 12 carbon atoms.
The polyester resin preferably contains 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more of the aliphatic diol having 3 to 12 carbon atoms.

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, and 3-methyl. 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
In particular, in the polyester resin, the diol component is an aliphatic diol having 4 to 12 carbon atoms, and the carbon number of the portion to be the main chain of the diol component is an odd number, and the diol component is an alkyl group It is more preferable that it has one of the side chains.
As an aliphatic diol which carbon number of the part used as a principal chain is odd-numbered, and has a C4-12 carbon atom which has an alkyl group in a side chain, the aliphatic diol represented by following General formula (1) is mentioned, for example.
HO-(CR ¹ R ² ) _n -OH ... General formula (1)
However, in said general formula (1), R < ¹ > and R < ² > respectively independently represent a hydrogen atom and a C1-C3 alkyl group. n represents an odd number of 3 to 9. In n repeating units, R ¹ may be identical to or different from each other. In addition, in n repeating units, R ² may be identical to or different from each other.
Further, in order to lower the Tg of the polyester resin and to easily impart the property of deformation at low temperature, the polyester resin contains 50 mol% or more of aliphatic diols having 3 to 12 carbon atoms in all alcohol components. Is preferred.

In order to lower the Tg of the polyester resin and to easily impart the property of deforming at a low temperature, the polyester resin contains a dicarboxylic acid component as a component, and the dicarboxylic acid component has a fat having 4 to 12 carbon atoms. It is preferred to contain a family dicarboxylic acid.
The polyester resin preferably contains 30 mol% or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
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.

-Diol component-
There is no restriction | limiting in particular as said diol component, According to the objective, it can select suitably, For example, 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, 1, Aliphatic diols such as 12-dodecanediol; diols having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A etc Alicyclic diols; adducts of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide with alicyclic diols; bisphenols such as bisphenol A, bisphenol F, bisphenol S; bisphenols with ethylene oxide, propylene oxide, butylene And alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as oxides. Among these, aliphatic diols having 4 to 12 carbon atoms are preferable.
These diols may be used alone or in combination of two or more.

-Dicarboxylic acid component-
There is no restriction | limiting in particular as said dicarboxylic acid component, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned. Moreover, these anhydrides may be used, a lower (C1-C3) alkylesterified thing may be used, and a halide may be used.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, fumaric acid and the like.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, A C8-C20 aromatic dicarboxylic acid is preferable.
There is no restriction | limiting in particular as said C8-C20 aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferable.
These dicarboxylic acids may be used alone or in combination of two or more.

Alcohol of -3 or more
There is no restriction | limiting in particular as said trivalent or more alcohol, According to the objective, it can select suitably, For example, trivalent or more aliphatic alcohol, trivalent or more polyphenols, and alkylene of trivalent or more polyphenols Oxide adducts and the like can be mentioned.
Examples of the trivalent or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolac, cresol novolac and the like.
Examples of the alkylene oxide adduct of the trivalent or higher polyphenols include, for example, those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to a trivalent or higher polyphenols.

-Polyisocyanate-
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate, etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking them with a phenol derivative, oxime, caprolactam or the like.
Examples of the trivalent or higher isocyanate include those obtained by reacting lysine triisocyanate or trivalent or higher alcohol with diisocyanate.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate and decamethylene. Diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc. may be mentioned.
There is no restriction | limiting in particular as said alicyclic diisocyanate, According to the objective, it can select suitably, For example, isophorone diisocyanate, a cyclohexyl methane diisocyanate, etc. are mentioned.
There is no restriction | limiting in particular as said aromatic diisocyanate, According to the objective, it can select suitably, For example, tolylene diisocyanate, 1, 5- naphthlene diisocyanate, 4, 4'- diisocyanato diphenyl, 4, 4 ' Examples include '-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenylether and the like.
There is no restriction | limiting in particular as said aromatic aliphatic diisocyanate, According to the objective, it can select suitably, For example, alpha, alpha, alpha ', alpha'- tetramethyl xylylene diisocyanate etc. are mentioned.
There is no restriction | limiting in particular as said isocyanurate, According to the objective, it can select suitably, For example, tris (isocyanato alkyl) isocyanurate, tris (isocyanato cycloalkyl) isocyanurate etc. are mentioned.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
As the curing agent, a curing agent capable of reacting with a polyester prepolymer (a reaction product of the polyester resin portion of R2 and the polyisocyanate, that is, a reaction precursor to be reacted with the curing agent) to produce the polyester resin If it is, there is no restriction | limiting in particular, According to the objective, it can select suitably, For example, an active hydrogen group containing compound etc. are mentioned.
--Active hydrogen group containing compound--
There is no restriction | limiting in particular as an active hydrogen group in the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, 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.
There is no restriction | limiting in particular as said active hydrogen group containing compound, Although it can select suitably according to the objective, Amines are preferable at the point which can form a urea bond.
There is no restriction | limiting in particular as said amines, According to the objective, it can select suitably, For example, what blocked the amino group, such as diamine, trivalent or more amine, amino alcohol, amino mercaptan, amino acids, etc. It can be mentioned. These may be used alone or in combination of two or more.
Among these, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned. There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylene diamine, diethyl toluene diamine, 4,4'- diamino diphenylmethane etc. are mentioned. There is no restriction | limiting in particular as said alicyclic diamine, According to the objective, it can select suitably, For example, 4, 4'- diamino 3,3'- dimethyl dicyclohexyl methane, diamino cyclohexane, isophorone diamine etc. are mentioned. Be There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylene diamine, hexamethylene diamine etc. are mentioned.
The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
There is no restriction | limiting in particular as said amino alcohol, According to the objective, it can select suitably, For example, ethanolamine, hydroxyethyl aniline etc. are mentioned.
There is no restriction | limiting in particular as said amino mercaptan, According to the objective, it can select suitably, For example, aminoethyl mercaptan, aminopropyl mercaptan etc. are mentioned.
There is no restriction | limiting in particular as said amino acid, According to the objective, it can select suitably, For example, amino propionic acid, amino caproic acid, etc. are mentioned.
There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking amino groups by ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone etc. A ketimine compound, an oxazoline compound, etc. are mentioned.

<< R3 part >>
As a method of combining R 2 and R 3, for example, a diol component and a dicarboxylic acid component are subjected to an ester reaction to produce a polyester polyol (R 2) having a terminal hydroxyl group, and the obtained polyester polyol is represented by the general formula The method of making it react with the isocyanate compound represented by I) is mentioned. Incidentally, the diol component and the dicarboxylic acid component referred to here are as described in the item of << R1 part, R2 part >>.
As the isocyanate compound represented by the above general formula (I), diphenylmethane diisocyanate (MDI) is preferable, and, for example, 2,2'- or 2,4'- or 4,4'-diphenylmethane diisocyanate and isomer mixtures of these, etc. Can be mentioned. Although an example of a specific example of an isocyanate compound denoted by the above-mentioned general formula (I) below is shown to (I-1)-(I-3), it is not limited to these.
These compounds may be used alone or in combination of two or more.

In the method of combining R1 and R2 described in the above section << R1 part, R2 part >> for bonding R2 and R3, the compound represented by the general formula (I) as a divalent polyisocyanate is used. An isocyanate compound may be used. Thereby, it is represented by the structural formulas 1) to 3) in which R 1, R 2 and R 3 are combined by the method shown in the method of combining R 1 and R 2 described in the item of << R1 part, R2 part >> A polyester resin having the following structure can be obtained.
Further, depending on the bonding method, in the above structural formulas 1) to 3),
More specifically, the part represented by "-R2-X-R3" is
It contains the aspect represented by "-R3-Y-R2'-X-R3" (However, R2 'is polyester and Y shows a urea bond or a urethane bond.). That is, depending on the bonding method, the modified polyester of R2 may contain an R3 portion, as represented by the above "-R3-Y-R2 '". In that case, in the structural formulas represented by the structural formulas 1) to 3), a group derived from the compound represented by the general formula (I) represented by R3 binds R1 and R2 In addition to being connected to the R2 side opposite to the side, R3 is also connected between R1 and R2.

The glass transition temperature of the polyester resin is preferably -60 ° C or more and 0 ° C or less, and more preferably -40 ° C or more and -20 ° C or less.
When the glass transition temperature is -60 [deg.] C. or higher, the flow of the toner at low temperature can not be suppressed, and the problem that the heat resistant storage stability is deteriorated and the filming resistance is deteriorated can be prevented.
When the glass transition temperature is 0 ° C. or less, the toner can not be sufficiently deformed by heating and pressing at the time of fixing, and the problem that the low-temperature fixability is insufficient can be prevented.

In the above polyester resins, the organic group of R 1 in the above structural formulas 1) to 3) is preferably an organic group having a short carbon number, which is preferable in that the network structure is easily uniformed, and has 20 carbon atoms. The following aliphatic and aromatic organic groups are preferred.
The organic group of R1 may also contain an ester bond.
Among them, aliphatic compounds having an aliphatic group or an ester bond as the organic group of R1 are capable of adjusting the cohesion of the crosslinking points to an appropriate range and easily achieving both high gloss and heat resistant storage stability. Is preferred.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said polyester resin, Although it can select suitably according to the objective, In GPC (gel permeation chromatography) measurement, 30,000 or more and 60,000 or less are preferable. .
The weight average molecular weight of the polyester resin refers to the molecular weight of the reaction product of the reactive precursor and the curing agent.
When the weight average molecular weight is 30,000 or more, the toner easily flows at low temperature, and the problem of poor heat resistant storage stability can be prevented.
Moreover, the viscosity at the time of fusion | melting becomes low, and the problem that high temperature offset property falls can also be prevented.
The weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 6 to 12.
The polyester resin preferably has such a high molecular weight as to be insoluble in tetrahydrofuran (THF).

  As the polyester resin in the present invention, a polyester resin having a structure represented by any one of the structural formulas 1) to 3) may be contained, and in any one of the structural formulas 1) to 3) The polyester resin having the structure represented may be used alone, or the polyester resin having the structure represented by any of the structural formulas 1) to 3) (also referred to as a first polyester resin) In addition, other polyester resins (also referred to as second polyester resins) may be used in combination.

<< Other polyester resin >>
The other polyester resin (second polyester resin) contains, for example, a diol component and a dicarboxylic acid component as constituent components.
The said other polyester resin says the polyester resin of the kind different from the said polyester resin which has a structural formula in any one of said 1)-3).
The other polyester resin is preferably an amorphous polyester resin.
Moreover, it is preferable that said other polyester resin is a linear polyester resin.
Furthermore, the other polyester resin is preferably a non-modified polyester resin.
Here, the unmodified polyester resin is a polyester resin obtained using a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester or a derivative thereof. A polyester resin that is not modified by an isocyanate compound or the like.

As said polyhydric alcohol, diol etc. are mentioned, for example.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct of bisphenol A such as; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Oxide (average added mole number 1 to 10) adducts and the like can be mentioned.
These may be used alone or in combination of two or more.
As said polyvalent carboxylic acid, dicarboxylic acid etc. are mentioned, for example.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and maleic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octyl succinic acid or alkenyls having 2 to 20 carbon atoms Group-substituted succinic acid and the like.
These may be used alone or in combination of two or more.
Further, in order to adjust the acid value and the hydroxyl value, the other polyester resin may contain at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol at the end of the resin chain.
As said trivalent or more carboxylic acid, trimellitic acid, pyromellitic acid, or those acid anhydrides etc. are mentioned, for example.
Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

There is no restriction | limiting in particular as molecular weight of said other polyester resin, Although it can select suitably according to the objective, when molecular weight is too low, the heat resistant storage stability of a toner, the durability with respect to stress, such as stirring in a developing machine, If the molecular weight is too high, the viscoelasticity of the toner during melting may be high and the low temperature fixability may be poor. Therefore, in GPC (gel permeation chromatography) measurement, the weight average molecular weight (Mw) 3 It is preferable that it is 2,000-10,000.
Moreover, it is preferable that a number average molecular weight (Mn) is 1,000-4,000.
Further, Mw / Mn is preferably 1.0 to 4.0.
The weight average molecular weight (Mw) is more preferably 4,000 to 7,000.
The number average molecular weight (Mn) is more preferably 1,500 to 3,000.
The Mw / Mn is more preferably 1.0 to 3.5.
There is no restriction | limiting in particular as an acid value of said other polyester resin, Although it can select suitably according to the objective, 1 mgKOH / g-50 mgKOH / g are preferable, and 5 mgKOH / g-30 mgKOH / g are more preferable.
When the acid value is 1 mg KOH / g or more, the toner tends to be negatively chargeable, and further, the affinity between the paper and the toner is improved at the time of fixation to paper, and the low temperature fixability can be improved. .
When the acid value is 50 mgKOH / g or less, it is possible to prevent a decrease in charge stability, in particular, charge stability against environmental fluctuations.
There is no restriction | limiting in particular as a hydroxyl value of said other polyester resin, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.
40 degreeC or more and 70 degrees C or less are preferable, and, as for the glass transition temperature (Tg) of said other polyester resin, 50 degrees C or more and 60 degrees C or less are more preferable.
When the glass transition temperature is 40 ° C. or higher, the heat resistant storage stability of the toner and the durability against stress such as agitation in a developing machine are inferior, and the problem that the filming resistance is deteriorated can be prevented. .
When the glass transition temperature is 70 ° C. or less, the deformation due to heating and pressure at the time of fixing of the toner is not sufficient, and the problem that the low-temperature fixability becomes insufficient can be prevented.

The molecular structure of the polyester resin (including the single use of the polyester resin having a structure represented by any of the structural formulas 1) to 3) and the combined use with other polyester resins is a solution or It can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement and the like besides NMR measurement with a solid. Conveniently the infrared absorption spectrum, and a method of detecting the one having no absorption based on 965 ± 10 cm ^-1 and 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as the polyester resin.

Especially as content of single use of the polyester resin which has a structure represented by either of the said polyester resin (said structural formula 1)-3), and combined use with other polyester resin, it is especially There is no restriction, and it can be selected appropriately according to the purpose, and for example, a polyester resin having a structure represented by any of the above structural formulas 1) to 3)) and another polyester resin In the case where the toner contains two types, the polyester resin having a structure represented by any of the above structural formulas 1) to 3)) is contained in an amount of 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the toner. Preferably, 10 parts by mass to 20 parts by mass are more preferable. When the content is 5 parts by mass or more, the low temperature fixability and the high temperature offset resistance can be prevented from being deteriorated. When the content is 25 parts by mass or less, the heat resistant storage stability is deteriorated, and after fixing It is possible to prevent the problem that the glossiness of the obtained image is reduced. It is advantageous at the point which is excellent in all the low temperature fixability, high temperature offset resistance, and heat-resistant storage stability that the said content is in the more preferable range above.
On the other hand, the amount of the other polyester resin is preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass with respect to 100 parts by mass of the toner. When the content is 50 parts by mass or more, the dispersibility of the pigment and the releasing agent in the toner is deteriorated, and the problem that the image is easily fogged or disturbed can be prevented. If there is, it is possible to prevent the low temperature fixability from being lowered due to the decrease in the content of the crystalline polyester resin described later and the polyester resin having a structure represented by any one of the structural formulas 1) to 3). It is advantageous at the point which is excellent in all of high quality and low temperature fixability as the content is a range more preferable than the above-mentioned.

<Crystalline polyester resin>
The crystalline polyester resin exhibits heat melting characteristics showing a sharp viscosity decrease near the fixing start temperature because it has high crystallinity. By using the crystalline polyester resin having such characteristics together with the polyester resin, the heat-resistant storage property is good due to the crystallinity until just before the melting start temperature, and the viscosity decreases rapidly due to the melting of the crystalline polyester resin at the melting start temperature (Sharp Melt) is caused to be compatible with the polyester resin, and the viscosity is rapidly lowered together to fix the toner, thereby obtaining a toner having both good heat-resistant storage stability and low-temperature fixability. In addition, good results are also shown for the release width (the difference between the lower limit fixing temperature and the high-temperature offset occurrence temperature).
The crystalline polyester resin is obtained using a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester, or a derivative thereof.
In the present invention, as described above, the crystalline polyester resin comprises a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester or a derivative thereof. The resin obtained by modifying the polyester resin, for example, the prepolymer, and the resin obtained by crosslinking and / or elongating the prepolymer do not belong to the crystalline polyester resin.
The presence or absence of crystallinity of the crystalline polyester resin in the present invention can be confirmed by a crystallographic X-ray diffractometer (for example, X'Pert Pro MRD Phillips). The measurement method is described below.
First, a target sample is ground with a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, the sample holder is set in the diffractometer, measurement is performed, and a diffraction spectrum is obtained.
Among the peaks obtained in the range of 20 ° <2θ <25 °, it is judged that the obtained diffraction peak has crystallinity when the peak half width of the peak having the largest peak intensity is 2.0 or less.
In the present invention, a polyester resin which does not exhibit the above-mentioned state with respect to a crystalline polyester resin is referred to as an amorphous polyester resin.
The measurement conditions of X-ray diffraction are described below.
〔Measurement condition〕
Tension kV: 45 kV
Current: 40mA
MPSS
Upper
Gonio
Scanmode: continuos
Start angle: 3 °
End angle: 35 °
Angle Step: 0.02 °
Lucident beam optics
Divergence slit: Div slit 1/2
Difflection beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and alcohol with a trivalent or more are mentioned.
As said diol, a saturated aliphatic diol etc. are mentioned, for example. Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 or more and 12 or less carbon atoms Family diols are more preferred. When the saturated aliphatic diol is a branched type, the crystallinity of the crystalline polyester resin may be reduced and the melting point may be reduced. Therefore, a linear saturated aliphatic diol is preferable. In addition, when the carbon number of the saturated aliphatic diol is 12 or less, it is practically easy to obtain the material. The carbon number is more preferably 12 or less.
Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and the like. 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 18-octadecanediol, 1,14-eicosanedecanediol, etc. are mentioned. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 in view of high crystallinity of the crystalline polyester resin and excellent sharp melt properties. Decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used alone or in combination of two or more.

-Polyvalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and the like. Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and further, anhydrides thereof and lower (1 to 3 carbon atoms) alkyl esters thereof can also be mentioned.
Examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc., and anhydrides thereof, and the like. And lower (C1-C3) alkyl esters of
In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, a dicarboxylic acid having a sulfonic acid group may be contained as the polyvalent carboxylic acid. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used alone or in combination of two or more.

The crystalline polyester resin 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 preferably has a constituent unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a constituent unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.
There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that they are 60 degreeC or more and 80 degrees C or less. When the melting point is 60 ° C. or more, the crystalline polyester resin is easily melted at a low temperature, and the problem that the heat resistant storage stability of the toner is reduced can be prevented. When the melting point is 80 ° C. or less It is possible to prevent the problem that the low temperature fixing property is lowered due to the insufficient melting of the crystalline polyester resin.
There is no restriction | limiting in particular as molecular weight of the said crystalline polyester resin, Although it can select suitably according to the objective, The thing of sharp molecular weight distribution and low molecular weight is excellent in low temperature fixing property, and there are many components with low molecular weight. And soluble matter of the ortho-dichlorobenzene of the crystalline polyester resin has a weight average molecular weight (Mw) of 3,000 to 30,000, and a number average molecular weight (Mn) in GPC measurement. It is preferable that they are 1,000-10,000 and Mw / Mn 1.0-10. Furthermore, it is preferable that they are a weight average molecular weight (Mw) 5,000-15,000, a number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.
There is no restriction | limiting in particular as an acid value of the said crystalline polyester resin, Although it can select suitably according to the objective, From the viewpoint of the affinity of paper and resin, in order to achieve desired low temperature fixability 5 mg KOH / g or more is preferable, and 10 mg KOH / g or more is more preferable. On the other hand, 45 mg KOH / g or less is preferable in order to improve high-temperature offset resistance.
There is no restriction | limiting in particular as a hydroxyl value of the said crystalline polyester resin, Although it can select suitably according to the objective, In order to achieve desired heat-fixing property and achieve a favorable charging characteristic, 0 mgKOH / G to 50 mg KOH / g is preferable, and 5 mg KOH / g to 50 mg KOH / g is more preferable.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement and the like in addition to NMR measurement with a solution or solid. Conveniently the infrared absorption spectrum, and a method of detecting those with absorption based on 965 ± 10 cm ^-1 or 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as a crystalline polyester resin.
There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 3 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, and 5 mass parts -15 mass parts are more preferable. When the content is 3 parts by mass or more, the problem of poor low-temperature fixability can be prevented because the sharp melt formation by the crystalline polyester resin is insufficient, and when it is 20 parts by mass or less, the heat resistant storage resistance Can be prevented, and the problem that the fogging of the image tends to occur can be prevented. When the content is within the above-mentioned preferable range, it is advantageous in that all the high image quality and the low temperature fixability are excellent.

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

-Release agent-
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things.
Examples of mold release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin And natural waxes such as petroleum waxes such as microcrystalline and petrolatum;
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers;
There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toners, 3 mass parts- 8 parts by mass is more preferable.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment etc. are mentioned.
There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toner, and 3 mass parts-10 The parts by mass are more preferred.
The coloring agent can also be used as a master batch complexed with a resin. As the resin to be kneaded with the production or masterbatch of the masterbatch, for example, in addition to the above-mentioned other polyester resin, polystyrene, poly p-chlorostyrene, styrene such as polyvinyl toluene or a polymer of its substitution product, etc. Can be selected appropriately.

  The masterbatch can be obtained by mixing and kneading a resin for masterbatch and a colorant under high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is a method of mixing and kneading an aqueous paste containing water of a coloring agent with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing water and organic solvent components. Since the cake can be used as it is, there is no need to dry it and it is preferably used.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amine, quaternary ammonium salt (including fluorine modified quaternary ammonium salt), alkylamide, simple substance or compound of phosphorus, single substance or compound of tungsten, fluorochemical activator, metal salt of salicylic acid, metal salt of salicylic acid derivative, etc. Can be mentioned.
There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said toners, and 0.. 2 parts by mass to 5 parts by mass is more preferable.

-External additive-
In addition to oxide fine particles, inorganic fine particles or hydrophobized inorganic fine particles can be used in combination as the external additive, but the average particle diameter of the hydrophobized primary particles is preferably 1 nm to 100 nm, and 5 nm to 70 nm. Inorganic fine particles are more preferable.
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably, For example, a silica particle, hydrophobic silica, fatty acid metal salt (for example, zinc stearate, aluminum stearate etc.), metal oxide (For example, titania, alumina, tin oxide, antimony oxide and the like), fluoropolymer and the like.
Suitable additives include hydrophobicized silica, titania, titanium oxide, alumina fine particles.
There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of said toners, and 0.. 3 mass parts-3 mass parts are more preferable.

-Fluidity improver-
The flowability improver is not particularly limited as long as it can perform surface treatment to enhance hydrophobicity and prevent deterioration of flowability and charging characteristics even under high humidity, and is appropriately selected according to the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. Be The silica and the titanium oxide are surface-treated with such a fluidity improver, and it is particularly preferable to use as the hydrophobic silica and the hydrophobic titanium oxide.

-Cleanability improver-
The cleaning property improver is not particularly limited as long as it is added to the toner to remove the developer after transfer remaining on the photosensitive member and the primary transfer medium, and may be appropriately selected according to the purpose. For example, metal microparticles of fatty acid such as zinc stearate, calcium stearate, stearic acid, etc., polymer microparticles produced by soap-free emulsion polymerization such as polymethyl methacrylate microparticles, polystyrene microparticles, etc.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably, For example, an iron powder, magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Glass transition temperature (Tg1st)>
The toner preferably has a glass transition temperature (Tg1st) at a first temperature increase in differential scanning calorimetry (DSC) of 20 ° C. or more and 50 ° C. or less.
In the case of the conventional toner, when the Tg is about 50 ° C. or less, toner aggregation is likely to occur due to temperature change in transportation of toner assuming storage in summer or tropical region and in storage environment. As a result, solidification in the toner bottle and fixation of the toner in the developing device occur. In addition, defective supply due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing device are likely to occur.
The toner of the present invention has a lower Tg than conventional toners. However, since the polyester resin having a structure represented by any one of the above structural formulas 1) to 3) which is a low Tg component in the toner is non-linear, the toner of the present invention has a heat resistant storage stability. Can be held. In particular, when the polyester resin having a structure represented by any one of the structural formulas 1) to 3) has a highly cohesive urethane bond or urea bond, the effect of maintaining the heat resistant storage stability becomes more remarkable. .
When the Tg1st is 20 ° C. or higher, problems such as a decrease in heat resistant storage stability, blocking in a developing machine, and filming to a photosensitive member can be prevented, and when 50 ° C. or lower, the toner It is possible to prevent the problem that the low temperature fixability is lowered.

In a preferred embodiment of the present invention, the polyester resin contains two types of polyester resin having a structure represented by any of the above 1) to 3) and the other polyester resin, and the toner contains the polyester resin. The aspect whose Tg1st of these is 20 degreeC or more and 50 degrees C or less is mentioned.
Further, the difference (Tg1st-Tg2nd) between the first temperature rise glass transition temperature (Tg1st) and the second temperature rise glass transition temperature (Tg2nd) in the differential scanning calorimetry (DSC) of the toner is not particularly limited. However, although it can be suitably selected according to the purpose, it is more preferable that it is 10 degreeC or more. The upper limit of the difference is not particularly limited and may be appropriately selected according to the purpose. However, the difference (Tg1st-Tg2nd) is preferably 50 ° C. or less.
A preferable embodiment of the present invention is an embodiment in which the polyester resin further contains a crystalline polyester resin, and the difference (Tg1st−Tg2nd) between Tg1st and Tg2nd of the toner containing these is 10 ° C. or more.
When the difference is 10 ° C. or more, it is advantageous in that the low temperature fixability is more excellent. That the difference is 10 ° C. or more means that the crystalline polyester resin and the polyester resin, which were present in an incompatible state before heating (before the first temperature increase), are heated (temperature increase) It means that it becomes compatible state after the 1st time.
The compatibilized state after heating does not have to be completely compatibilized.
There is no restriction | limiting in particular as melting | fusing point of the said toner, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable.

<Volume average particle size>
There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, It is preferable that they are 3 micrometers or more and 7 micrometers or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain a component having a volume average particle diameter of 2 μm or less in an amount of 1 to 10% by number.

<Method 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 releasing agent may be measured on their own, but gel permeation from an actual toner is possible. The SP value, the Tg, the molecular weight, the melting point, and the mass ratio of the constituent components may be calculated by performing separation by chromatography (GPC) or the like and taking the analysis method described later for each separated component.
Separation of each component by GPC can be performed, for example, by the following method.
In the GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to the desired molecular weight portion of the integral of the elution curve are put together.
The concentrated eluate is concentrated and dried by an evaporator or the like, then the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and ¹ H-NMR measurement is carried out. Calculate the component monomer ratio of
As another method, the eluate is concentrated and then hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio.
In the case where the toner base particles are formed while the method for producing the toner forms a polyester resin by an extension reaction and / or a crosslinking reaction of the non-linear reactive precursor and the curing agent, May be determined from the toner of the present invention by GPC or the like, and the Tg of the polyester resin may be determined. Separately, the polyester resin is obtained by an extension reaction and / or a crosslinking reaction between the non-linear reactive precursor and the curing agent. May be synthesized, and Tg and the like may be measured from the synthesized polyester resin.

<< Means for separating toner components >>
An example of the separation means of each component at the time of analyzing the said toner is shown in detail.
First, 1 g of a toner is placed in 100 mL of THF, and a soluble solution is obtained while stirring for 30 minutes at 25 ° C. to obtain a dissolved solution.
This is filtered with a 0.2 μm membrane filter to obtain THF soluble matter in the toner.
Next, this is dissolved in THF to make a sample for GPC measurement, and injected into GPC used for measuring the molecular weight of each resin described above.
On the other hand, a fraction collector is placed at the elution port of the GPC, and the eluate is separated for each predetermined count, and the eluate is extracted every 5% in area ratio from the elution start of the elution curve (rise of the curve). Get
Next, for each eluate, 30 mg of a sample is dissolved in 1 mL of heavy chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and integration is performed 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.) to obtain a spectrum .
The monomer composition and composition 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.
For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is determined from each integral ratio.
The attribution of the peak is, for example,
Around 8.25 ppm: derived from the benzene ring of trimellitic acid (one hydrogen)
8.07 ppm to around 8.10 ppm: From the benzene ring of terephthalic acid (for four hydrogens)
7.1 ppm-around 7.25 ppm: Benzene ring origin of bisphenol A (for four hydrogens)
Near 6.8 ppm: derived from benzene ring of bisphenol A (4 hydrogens) and from double bond of fumaric acid (2 hydrogens)
5.2 ppm to around 5.4 ppm: The methine origin of bisphenol A propylene oxide adduct (one hydrogen)
3.7 ppm to about 4.7 ppm: derived from methylene of bisphenol A propylene oxide adduct (two hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (four hydrogens)
Near 1.6 ppm: derived from methyl group of bisphenol A (for six hydrogens)
It can be done.
From these results, for example, the extract recovered in the fraction in which the polyester resin having a structure represented by any one of the structural formulas 1) to 3) occupies 90% or more is made of the structural formulas 1) to 3). It can be treated as a polyester resin having a structure represented by either.
Also, the extract recovered in the fraction in which the other polyester resin accounts for 90% or more can be treated as the other polyester resin.
Moreover, the extract collect | recovered in the fraction which the said crystalline polyester resin occupies 90% or more can be handled as said crystalline polyester resin.

<< Measurement method of hydroxyl value and acid value >>
A hydroxyl value can be measured using the method based on JISK0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL measuring flask, and 5 mL of an acetylation reagent is added thereto. Next, after heating in a 100 ± 5 ° C. water bath for 1 to 2 hours, the flask is removed from the water bath and allowed to cool. Further, water is added and shaken to decompose acetic anhydride.
Next, in order to completely decompose acetic anhydride, the flask is again heated for 10 minutes or more in a warm water bath and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. Furthermore, the hydroxyl value is measured at 23 ° C. using a potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and an electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using. In addition, for the calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are as follows.
〔Measurement condition〕
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potential2 No
Stop for reevaluation
An acid value can be measured using the method based on JISK0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g for ethyl acetate soluble matter) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to make a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used.
Furthermore, the acid value is measured at 23 ° C. using a potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and an electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using.
In addition, for the calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the case of the above-mentioned hydroxyl value.
The acid value can be measured as described above, but specifically, titration with a 0.1N potassium hydroxide / alcohol solution which has been standardized in advance, and from the titration amount, the acid value [mg KOH / g] = The acid value is calculated by titration volume [mL] × N × 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Method of measuring melting point and glass transition temperature (Tg) >>
The melting point and the glass transition temperature (Tg) in the present invention can be measured, for example, using a DSC system (differential scanning calorimeter) ("Q-200", manufactured by TA Instruments).
Specifically, the melting point and the glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is raised from -80 ° C to 150 ° C at a temperature rising rate of 10 ° C / min (first temperature rise). Then, it is made to cool to -80 degreeC by temperature-fall rate 10 degreeC / min from 150 degreeC, and also it heats to 150 degreeC by 10 degreeC / min of temperature rising rates (2nd temperature rise). A DSC curve is measured using a differential scanning calorimeter ("Q-200", manufactured by TA Instruments) at each of the first temperature increase and the second temperature increase.
From the obtained DSC curve, using an analysis program in the Q-200 system, the DSC curve at the first temperature rise can be selected to 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 to determine the glass transition temperature of the target sample at the second temperature rise.
Also, from the DSC curve obtained, select the DSC curve at the first temperature rise using the analysis program in the Q-200 system, and find the endothermic peak top temperature at the first temperature rise of the target sample as the melting point Can. Similarly, the DSC curve at the second temperature rise can be selected, and the endothermic peak top temperature at the second temperature rise of the target sample can be determined as the melting point.
In this specification, the glass transition temperature at the first temperature rise when using toner as the target sample is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
Further, in the present specification, the glass transition temperature and the melting point of the other components such as the polyester resin, the crystalline polyester resin, and the release agent are the heat absorption at the second temperature rise unless otherwise noted. The peak top temperature and Tg are taken as the melting point and Tg of each target sample.

<< Measurement method of particle size distribution >>
The volume average particle diameter (D4), the number average particle diameter (Dn), and the ratio (D4 / Dn) of the toner are, for example, Coulter Counter TA-II, Coulter Multisizer II (all manufactured by Coulter, Inc.), etc. Can be measured.
In the present invention, 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 an electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1% by mass aqueous NaCl solution prepared using first-grade sodium chloride, and for example, ISOTON-II (manufactured by Coulter, Inc.) can be used. Here, 2 mg to 20 mg of the measurement sample is further added.
The electrolytic aqueous solution in which the sample is suspended is subjected to dispersion processing for about 1 minute to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured using the 100 μm aperture as an aperture with the measuring device. , Volume distribution and number distribution are calculated.
From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be determined.
As a channel, 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm; 8.00 μm to less than 10.08 μm; 10.08 μm to less than 12.70 μm; 12.70 μm to less than 16.00 μm; 16.00 μm to less than 20.20 μm; Using 13 channels less than 40 μm; 25.40 μm or more but less than 32.00 μm; 32.00 μm or more but less than 40.30 μm, particles of 2.00 μm or more but less than 40.30 μm are targeted.

<< Molecular weight measurement >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measuring apparatus: GPC-8220GPC (made by Tosoh Corporation)
Column: TSKgel Super HZM-H 15 cm 3 stations (made by Tosoh Corporation)
Temperature: 40 ° C
Solvent: Tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Sample: 0.4 mL injection of a 0.15% by mass sample Pretreatment of the sample: Dissolve the toner in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd. at 0.15% by mass), filter with a 0.2 μm filter, The filtrate is used as a sample.
100 μL of the THF sample solution is injected and measured.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several types of monodispersed polystyrene standard samples and the count number.
As a standard polystyrene sample for preparation of a standard curve, Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used.
As a detector, an RI (refractive index) detector is used.

<Method of manufacturing toner>
There is no restriction | limiting in particular as a manufacturing method of the said toner, Although it can select suitably according to the objective, The said toner contains the said polyester resin, Preferably it further contains the said crystalline polyester resin, and also as needed Preferably, granulation is carried out by dispersing an oil phase containing the mold release agent, the colorant and the like in an aqueous medium. It is more preferable that the said polyester resin contains two types of polyester resin of the polyester resin which has a structure represented by either of said Structural formula 1)-3), and said other polyester resin.
Further, the toner may be a polyester resin (a product of a reaction product of the resin portion of the polyester of R2 and the polyisocyanate, a resin portion of the polyester of R2 and the general formula (I)). Containing the polyester resin which is a reaction product with the isocyanate compound to be reacted, that is, the reaction precursor to be reacted with the curing agent, and the other polyester resin not having a urethane bond and a urea bond, preferably the crystalline polyester It is further preferable to be granulated by dispersing an oil phase containing a resin and, if necessary, the curing agent, the releasing agent, the coloring agent and the like in an aqueous medium.

  Further, in the present invention, when producing a prepolymer comprising a reaction product of the resin portion of the polyester of R2 and the isocyanate compound represented by the general formula (I), it is preferable to pay attention to the following conditions . When diphenylmethane diisocyanate (MDI) is used as the isocyanate compound represented by the general formula (I), (MDI isocyanate group / intermediate when reacting the intermediate polyester containing R2 with the diphenylmethane diisocyanate (MDI) The molar ratio of the hydroxyl group of the polyester may be 1.5 or more and less than 3.0.

  As an example of such a method for producing the toner, a known dissolution and suspension method can be mentioned. As an example of the method for producing the toner, a polyester resin having a structure represented by any one of the structural formulas 1) to 3) is formed by an extension reaction and / or a crosslinking reaction of the polyester prepolymer and the curing agent. While, a method of forming toner base particles is shown below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of a toner material, and removal of an organic solvent are performed.

-Preparation of aqueous medium (water phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. The addition amount of the resin particles in the aqueous medium is not particularly limited and can be appropriately selected according to 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. .
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, the solvent miscible with water, water, these mixtures etc. are mentioned. These may be used alone or in combination of two or more. Among these, water is preferred.
There is no restriction | limiting in particular as a solvent miscible with the said water, According to the objective, it can select suitably, For example, alcohol, a dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, etc. are mentioned. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol etc. are mentioned. The lower ketones are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include acetone and methyl ethyl ketone.

-Preparation of oil phase-
The preparation of the oil phase containing the toner material comprises at least the polyester prepolymer, the other polyester resin, and the crystalline polyester resin, and, if necessary, the curing agent, the release agent, and the like. It can be carried out by dissolving or dispersing a toner material containing a colorant and the like in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which removal is easy.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the purpose. 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 and the like. These may be used alone or in combination of two or more.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be carried out by dispersing an oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the structure represented by any one of the structural formulas 1) to 3) by causing the curing agent and the polyester prepolymer to undergo an extension reaction and / or a crosslinking reaction. A polyester resin is produced.
The polyester resin which has a structure represented by either of said Structural Formula 1)-3) can be produced | generated by the method of the following (1)-(3), for example.
(1) Emulsifying or dispersing an oil phase containing the polyester prepolymer and the curing agent in an aqueous medium, and causing an elongation reaction and / or a crosslinking reaction of the curing agent and the polyester prepolymer in an aqueous medium The method to produce | generate the polyester resin which has a structure represented by either of said Structural Formula 1)-3) by this.
(2) The oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium to which the curing agent is 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. The method of producing | generating the polyester resin which has a structure represented by either of said Structural formula 1)-3) by making it make it.
(3) After the oil phase containing the polyester prepolymer is emulsified or dispersed in the aqueous medium, the curing agent is added to the aqueous medium, and the curing agent and the polyester prepolymer from the particle interface in the aqueous medium And a stretching reaction and / or a crosslinking reaction to form a polyester resin having a structure represented by any one of the structural formulas 1) to 3).
When the curing agent and the polyester prepolymer are subjected to an elongation reaction and / or a crosslinking reaction from the particle interface, the structure represented by any one of the structural formulas 1) to 3) on the surface of the produced toner A polyester resin is formed, and a concentration gradient of the polyester resin having a structure represented by any one of the structural formulas 1) to 3) can be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the polyester resin having a structure represented by any one of the above structural formulas 1) to 3) are not particularly limited, and the curing agent, the polyester pre It can be appropriately selected according to the combination with the polymer.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC are preferable, and 40 degreeC-98 degreeC are more preferable.
The method for stably forming the dispersion containing the polyester prepolymer in the aqueous medium is not particularly limited and may be appropriately selected according to the purpose. For example, in the aqueous medium phase, the toner material may be used. And an oil phase prepared by dissolving or dispersing it in a solvent, and dispersing by a shear force.
There is no restriction | limiting in particular as a dispersion machine for the said dispersion | distribution, According to the objective, it can select suitably, For example, a low speed shearing type dispersing machine, a high speed shearing type dispersing machine, a friction type dispersing machine, a high pressure jet type dispersing machine And ultrasonic dispersion machines.
Among these, a high-speed shear disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shear disperser is used, conditions such as the number of revolutions, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotational speed, Although it can select suitably according to the objective, 1,000-30,000 rpm is preferable and 5,000-20,000 rpm is more preferable.
There is no restriction | limiting in particular as said dispersion time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion temperature, Although it can select suitably according to the objective, Under pressurization, 0 degreeC-150 degreeC are preferable, and 40 degreeC-98 degreeC are more preferable. Generally, the higher the dispersion temperature, the easier the dispersion.
The use amount of the aqueous medium at the time of emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected according to the purpose, but 50 parts by mass to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass are more preferable.
When the amount of use of the aqueous medium is 50 parts by mass or more, the dispersion state of the toner material is deteriorated, and the problem that toner base particles having a predetermined particle diameter can not be obtained can be prevented. Production cost can be held down as it is below the mass part.

When the oil phase containing the toner material is emulsified or dispersed, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets and making it into a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, polymeric protection colloid, etc. are mentioned. These may be used alone or in combination of two or more. Among these, surfactants are preferable.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant etc. are used. be able to.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, the alkyl benzene sulfonate, an alpha-olefin sulfonate, phosphate ester etc. are mentioned. Among these, those having a fluoroalkyl group are preferable.
A catalyst can be used for the extension reaction and / or the crosslinking reaction when producing the polyester resin having a structure represented by any one of the structural formulas 1) to 3).
The catalyst is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

-Removal of organic solvent-
There is no restriction | limiting in particular as a method to remove an organic solvent from dispersion liquid, such as the said emulsification slurry, According to the objective, it can select suitably, For example, the whole reaction system is made to heat up gradually, A method of evaporating the organic solvent, a method of spraying the dispersion into 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 and the like, and further classified and the like. The classification may be carried out by removing fine particle parts in a liquid by means of a cyclone, decanter, centrifugation or the like, or classification operation may be carried out after drying.
The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, it is possible to suppress detachment of particles such as the external additive from the surface of the toner base particles by applying a mechanical impact force.
There is no restriction | limiting in particular as a method of applying the said mechanical impact force, According to the objective, it can select suitably, For example, the method of applying an impact force to a mixture using the blade | wing rotated at high speed And the mixture is accelerated to cause particles or particles to collide with an appropriate collision plate.
There is no restriction | limiting in particular as an apparatus used for the said method, According to the objective, it can select suitably, For example, Ong mill (made by Hosokawa micron company), I type mill (made by Nippon Pneumatic Mfg. Co., , A hybridization system (made by Nara Machinery Co., Ltd.), a Cryptoron system (made by Kawasaki Heavy Industries, Ltd.), an automatic mortar and the like.

(Developer)
The developer of the present invention contains at least the toner, and optionally contains other components such as a carrier appropriately selected.
Therefore, a high quality image can be stably formed with excellent transferability, chargeability and the like. The developer may be a one-component developer or a two-component developer, but when it is used for a high-speed printer or the like compatible with the recent improvement of the information processing speed, the life is short. Two-component developers are preferred because they improve.
<Carrier>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, electrostatic latent image forming means, and developing means, and further has other means as required.
The image forming method relating to the present invention at least includes an electrostatic latent image forming step and a developing step, and further includes other steps as required.
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 unit, and the developing step is the developing unit The other steps can be suitably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the latent electrostatic image bearing member are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photosensitive members such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in view of long life.

<Electrostatic latent image forming means>
The electrostatic latent image forming unit is not particularly limited as long as it is a unit for forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected according to the purpose. The means includes at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier imagewisely.

<Developing means>
The developing unit is not particularly limited as long as it is a developing unit including a toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, according to the purpose. Can be selected appropriately.

<Other means>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a charge removing means, a recycling means, and a control means.

Next, one aspect of carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. 1 includes a photosensitive drum 10 (hereinafter sometimes referred to as "photosensitive member 10") as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and An exposure device 30 as an exposure means, a developing device 40 as the development means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a charge removal lamp 70 as the charge removal means .
The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 51 disposed inside and stretching it. A portion of the three rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. In the vicinity of the intermediate transfer member 50, a cleaning device 90 having a cleaning blade is disposed. Further, in the vicinity of the intermediate transfer body 50, a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) the developed image (toner image) onto a transfer paper 95 as a recording medium. , And is disposed to face the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is formed between the photosensitive member 10 and the intermediate transfer member 50 in the rotational direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.
The developing device 40 includes a developing belt 41 as the developer carrying member, 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 accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer accommodating portion 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt, and is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.
In the color image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive 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 member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photosensitive member 10 is removed by the cleaning device 60, and the charge on the photosensitive member 10 is removed once by the charge removal lamp 70.

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus shown in FIG. 2 includes a copying apparatus main body 150, a sheet feeding table 200, a scanner 300, and an automatic document feeder (ADF) 400.
In the copying machine main body 150, an endless belt-like intermediate transfer member 50 is provided at the central portion. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 2. In the vicinity of the support roller 15, an intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed. The intermediate transfer member 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are opposed and juxtaposed along the conveyance direction. The developing device 120 is disposed. In the vicinity of the tandem developing unit 120, an exposure device 21 which is the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. 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 sheet conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 contact each other. It is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 which is the fixing unit is disposed. The fixing device 25 includes a fixing belt 26 which is an endless belt, and a pressure roller 27 which is disposed to be pressed by the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form an image on both sides of the transfer paper. .

Next, full color image formation (color copy) using the tandem developing device 120 will be described. That is, first, the original is set on the original table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the original is set on the contact glass 32 of the scanner 300. Close 400
When the start switch (not shown) is pressed, when the document is set in the automatic document feeder 400, the document is conveyed and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, the light from the light source is irradiated by the first traveling body 33, and the reflected light from the document surface is reflected by the mirror in the second traveling body 34, and is received by the reading sensor 36 through the imaging lens 35 An original (color image) is read and used as black, yellow, magenta and cyan image information.
The image information for each of black, yellow, magenta, and cyan is transferred to each image forming unit 18 in the tandem developing unit 120 (image forming unit for black, image forming unit for yellow, image forming unit for magenta, and image for cyan). Respectively). Then, black, yellow, magenta and cyan toner images are formed in each image forming means. That is, each image forming unit 18 (image forming unit for black, image forming unit for yellow, image forming unit for magenta, and image forming unit for cyan) in the tandem type developing device 120 is the electrostatic latent image carrier 10 ( Electrostatic latent image carrier 10K for black, electrostatic latent image carrier 10Y for yellow, electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier 10C for cyan, and the electrostatic latent image carrier 10, the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information, and the charging device 160 which is the charging means for uniformly charging 10; An exposure device for forming an electrostatic latent image corresponding to each color image, and the electrostatic latent image is developed using each color toner (black toner, yellow toner, magenta toner, and cyan toner) to A developing device 61 which is the developing means for forming a toner image by, and a transfer charger 62 for transferring the toner image on the intermediate transfer member 50, a cleaning device 63, and a discharger 64. Then, each image forming unit 18 can form an image (black image, yellow image, magenta image, and cyan image) of each single color based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this manner are respectively transferred onto the intermediate transfer member 50 rotationally moved by the support rollers 14, 15 and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier for yellow 10Y, magenta image formed on electrostatic latent image carrier for magenta 10M, electrostatic latent image carrier for cyan The cyan image formed on 10 C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).
On the other hand, in the sheet feeding table 200, one of the sheet feeding rollers 142 is selectively rotated, and a sheet (recording sheet) is fed out from one of the sheet feeding cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separating roller 145 and fed to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, butted against the registration roller 49 and stopped. Be Alternatively, the sheet feed roller 142 is rotated to feed the sheet (recording sheet) on the manual feed tray 54, and the sheet is separated one by one by the separation roller 52 and put into the manual feed path 53 and similarly stopped against the registration roller 49. . Although the registration roller 49 is generally used while being grounded, it may be used in a state where a bias is applied for removing paper dust of the sheet. Then, the registration roller 49 is rotated in time with the composite color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) between the intermediate transfer member 50 and the secondary transfer device 22. And the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member 50 after the image transfer is cleaned by the intermediate transfer member cleaning device 17.
The sheet (recording paper) on which the color image is transferred and formed is conveyed by the secondary transfer device 22 and sent out to the fixing device 25, and the fixing device 25 mixes the color image (color image) by heat and pressure. The transfer image is fixed on the sheet (recording paper). Thereafter, the sheet (recording sheet) is switched by the switching claw 55, discharged by the discharge roller 56, and stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, inverted by the sheet reversing device 28, guided to the transfer position again, recorded on the back side of the image, discharged by the discharge roller 56, and stacked on the discharge tray 57. Be done.

EXAMPLES Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. The term "parts" refers to "parts by mass" unless otherwise specified. "%" Represents "% by mass" unless otherwise specified.
Each measured value in the following examples was measured by the method described in the present specification. The Tg and molecular weight of the polyester resin having a structure represented by any one of the structural formulas 1) to 3), the other polyester resin, the crystalline polyester resin, etc. are measured from each resin obtained in the production example. did.

(Production Example 1)
<Synthesis of ketimine>
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged in a reaction vessel set with a stirring rod and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1].
The amine value of [ketimine compound 1] was 418.

(Production Example A-1)
<Synthesis of Polyester Resin A-1>
-Synthesis of Prepolymer A-1-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-1.
The Tg of the resulting intermediate polyester A′-1 was −45 ° C., Mw 10,000, and Mw / Mn 2.3.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-1 and lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction mixture was charged at 0.2, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-1 solution.
The Tg of the resulting intermediate polyester A-1 was -40 ° C, Mw 12,000, and Mw / Mn 2.5.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of the intermediate polyester A-1 solution and diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was charged at 0.5 ° C., diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-1 solution.
-Synthesis of polyester resin A-1-
The obtained prepolymer A-1 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in the prepolymer A-1 An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-1.
Physical properties of the obtained polyester resin A-1 are shown in Table 1-1.

(Production Example A-2)
<Synthesis of Polyester Resin A-2>
-Synthesis of Prepolymer A-2-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-2.
The Tg of the resulting intermediate polyester A′-2 was −45 ° C., Mw 10,000, and Mw / Mn 2.3.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-2 and diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was charged at 0.5, diluted with ethyl acetate to a 50% ethyl acetate solution, and allowed to react at 100 ° C. for 5 hours to obtain an intermediate polyester A-2 solution.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester solution A-2 to trimethylolpropane (TMP) (isocyanate group of intermediate polyester A-2 / TMP The reaction product was charged with a hydroxyl group of 5.0), diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-2.
-Synthesis of polyester resin A-2-
The obtained prepolymer A-2 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in the prepolymer A-2 An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-2.
Physical properties of the obtained polyester resin A-2 are shown in Table 1-1.

(Production Example A-3)
<Synthesis of Polyester Resin A-3>
-Synthesis of Prepolymer A-3-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-3.
The Tg of the resulting intermediate polyester A′-3 was −45 ° C., Mw 10,000, and Mw / Mn 2.3.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-3 to diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 The reaction solution was charged at 0.5, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-3 solution.
Tg of the obtained intermediate polyester A-3 was −25 ° C., Mw 40,000, and Mw / Mn 8.0.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A-3 to lysine triisocyanate (RTI) (isocyanate group of RTI / isocyanate group of intermediate polyester) 0.2 was added and diluted to a 50% ethyl acetate solution with ethyl acetate, and then pure water having a molar ratio of 0.5 to the amount of NCO present in the reaction system was dropped The mixture was reacted at 100 ° C. for 5 hours to obtain a prepolymer A-3 solution.
-Synthesis of polyester resin A-3-
The obtained prepolymer A-3 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further relative to the amount of isocyanate in prepolymer A-3. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-3.
Physical properties of the obtained polyester resin A-3 are shown in Table 1-1.

(Production Example A-4)
<Synthesis of Polyester Resin A-4>
-Synthesis of Prepolymer A-4-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-4.
The Tg of the resulting intermediate polyester A′-4 was −35 ° C., Mw 18,000, and Mw / Mn 2.0.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-4 to lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction mixture was charged at 0.2, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-4 solution.
The Tg of the obtained intermediate polyester A-4 was -35 ° C, Mw 20,000, and Mw / Mn 2.5.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of the intermediate polyester A-4 solution and diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was charged at 0.5, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-4 solution.
-Synthesis of polyester resin A-4-
The obtained prepolymer A-4 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in the prepolymer A-4. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-4.
Physical properties of the obtained polyester resin A-4 are shown in Table 1-1.

(Production Example A-5)
<Synthesis of Polyester Resin A-5>
-Synthesis of prepolymer A-5-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-5.
Tg of the obtained intermediate polyester A′-5 was −35 ° C., Mw 18,000, and Mw / Mn 2.0.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-5 to lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction mixture was charged at 0.2, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-5 solution.
Tg of the obtained intermediate polyester A-5 was -35 ° C, Mw 20,000, and Mw / Mn 2.5.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of the intermediate polyester A-5 solution to diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 ., And diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-5 solution.
-Synthesis of polyester resin A-5-
The obtained prepolymer A-5 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in prepolymer A-5. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-5.
Physical properties of the obtained polyester resin A-5 are shown in Table 1-2.

(Production Example A-6)
<Synthesis of Polyester Resin A-6>
-Synthesis of Prepolymer A-6-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-6.
The Tg of the obtained intermediate polyester A′-6 was −35 ° C., Mw 18,000, and Mw / Mn 2.0.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-6 to lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction solution was charged at 0.3, diluted to a 50% ethyl acetate solution with ethyl acetate, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-6 solution.
The Tg of the obtained intermediate polyester A-6 was -30 ° C, Mw 24,000, and Mw / Mn 2.5.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of the intermediate polyester A-6 solution to diphenylmethane diisocyanate (MDI) (isocyanate group of MDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was then charged with ethyl acetate, diluted to a 50% ethyl acetate solution with ethyl acetate, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-6 solution.
-Synthesis of polyester resin A-6-
The obtained prepolymer A-6 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in prepolymer A-6. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-6.
The physical property values of the obtained polyester resin A-6 are shown in Table 1-2.

(Production Example A-7)
<Synthesis of Polyester Resin A-7>
-Synthesis of Prepolymer A-7-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-7.
The Tg of the resulting intermediate polyester A′-7 was −40 ° C., Mw 15,000, and Mw / Mn 2.0.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-7 to lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction mixture was charged at 0.2, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-7 solution.
The Tg of the resulting intermediate polyester A-7 was -35 ° C, Mw 20,000, and Mw / Mn 2.2.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A-7 solution to isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was then charged with ethyl acetate, diluted to a 50% ethyl acetate solution with ethyl acetate, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-7 solution.
-Synthesis of polyester resin A-7-
The obtained prepolymer A-7 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in prepolymer A-7. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-7.
Physical property values of the obtained polyester resin A-7 are shown in Table 2.

Production Example A-8
<Synthesis of Polyester Resin A-8>
-Synthesis of Prepolymer A-8-
97 mol% of 3-methyl-1,5-pentanediol as alcohol component and 3 mol% of trimethylolpropane (TMP) in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, and adipine as an acid component It was added with titanium tetraisopropoxide (300 ppm to resin component) so that the acid was 50 mol% and terephthalic acid 50 mol%, and the molar ratio of hydroxyl group to carboxyl group was OH / COOH = 1.1. .
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was performed until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A-8.
Tg of the obtained intermediate polyester A-8 was -39 ° C, Mw 12,000, and Mw / Mn 2.5.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A-8 and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2. The reaction mixture was charged at 1 and diluted with ethyl acetate to a 48% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain a non-linear prepolymer A-8.
-Synthesis of polyester resin A-8-
The obtained prepolymer A-8 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in prepolymer A-8. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain an amorphous polyester resin A-8.
Physical properties of the obtained polyester resin A-8 are shown in Table 2.

(Production Example A-9)
<Synthesis of Polyester Resin A-9>
-Synthesis of Prepolymer A-9-
3-methyl-1,5-pentanediol, terephthalic acid, adipic acid in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1 Titanium tetraisopropoxide such that the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol and the composition of the dicarboxylic acid component is 90 mol% of terephthalic acid and 10 mol% of adipic acid It was charged together with (1,000 ppm with respect to the resin component).
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'-9.
The Tg of the resulting intermediate polyester A′-9 was −5 ° C., Mw 13,000, and Mw / Mn 2.2.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of intermediate polyester A'-9 and lysine triisocyanate (RTI) (isocyanate group of RTI / hydroxyl group of intermediate polyester) The reaction mixture was charged at 0.2, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A-9 solution.
Tg of the obtained intermediate polyester A-9 was 0 ° C., Mw 19,000, and Mw / Mn 2.4.
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of the intermediate polyester A-9 solution and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 1 The reaction mixture was then charged with ethyl acetate, diluted to a 50% ethyl acetate solution with ethyl acetate, and reacted at 100 ° C. for 5 hours to obtain a prepolymer A-9 solution.
-Synthesis of polyester resin A-9-
The obtained prepolymer A-9 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introducing tube, and the amount of amine of [ketimine compound 1] is further based on the amount of isocyanate in prepolymer A-9. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and after 10 hours of stirring at 45 ° C., the prepolymer extension was taken out.
The obtained prepolymer extension was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate became 100 ppm or less, to obtain an amorphous polyester resin A-9.
Physical properties of the obtained polyester resin A-9 are shown in Table 2.

(Production Example B-1)
<Synthesis of Polyester Resin B-1>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, isophthalic acid, and adipic acid, bisphenol A: The ethylene oxide side 2 mol adduct and the bisphenol A propylene oxide 3 mol adduct are 85/15 in molar ratio (bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 3 mol adduct), and terephthalic acid It is charged so that the molar ratio of terephthalic acid and adipic acid is 80/20 (terephthalic acid / adipic acid) and the molar ratio OH / COOH of hydroxyl group to carboxyl group is 1.2, titanium tetraisopropoxide ( Together with 500 ppm of resin component) After reacting for 8 hours at 230 ° C with pressure, and further for 4 hours at 10mmHg to 15mmHg, trimellitic anhydride is added to the reaction vessel in an amount of 1 mol% with respect to all resin components, 3 at 180 ° C and normal pressure. The reaction occurred for time to obtain an amorphous polyester resin B-1.
Physical property values are listed in Tables 1-1, 1-2, and 2.

(Production Example C-1)
<Synthesis of Crystalline Polyester Resin C-1>
Dodecanedioic acid and 1,6-hexanediol in a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple: OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group The reaction is carried out at 180 ° C. for 10 hours with titanium tetraisopropoxide (500 ppm relative to the resin component), then the temperature is raised to 200 ° C. and the reaction is carried out for 3 hours. The mixture was reacted at a pressure of 3 kPa for 2 hours to obtain a crystalline polyester resin C-1.
Physical property values are listed in Tables 1-1, 1-2, and 2.

Example 1
<Preparation of Masterbatch (MB)>
Add 1,200 parts of water, carbon black (made by Printex 35 Dexa) (DBP oil absorption = 42 mL / 100 mg, pH = 9.5) and 500 parts of the polyester resin B-1 and add a Henschel mixer (Mitsui Mining Co., Ltd.) The mixture was mixed using a two-roll mill at 150 ° C. for 30 minutes, rolled, cooled, and crushed using a pulper to obtain [master batch 1].
<Preparation of WAX Dispersion>
50 parts of paraffin wax as mold release agent 1 (NNP manufactured by Seisei Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8), and acetic acid in a container in which a stirrer and a thermometer are set Charge 450 parts of ethyl, raise the temperature to 80 ° C with stirring, maintain at 80 ° C for 5 hours, cool to 30 ° C at 1 hour, and feed using a bead mill (Ultravisco mill, manufactured by Imex Co., Ltd.) Dispersion was carried out under the conditions of a liquid velocity of 1 kg / hr, a disk peripheral velocity of 6 m / sec, a diameter of 0.5 mm filled with zirconia beads at 80% by volume, and 3 passes to obtain [WAX dispersion 1].
<Preparation of Crystalline Polyester Resin Dispersion>
50 parts of crystalline polyester resin C-1 and 450 parts of ethyl acetate are charged in a container in which a stirring rod and a thermometer are set, the temperature is raised to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours, then 1 hour Cooled to 30 ° C., using a bead mill (Ultravisco Mill, manufactured by Imex Co., Ltd.), liquid transfer speed 1 kg / hr, disc peripheral speed 6 m / sec, diameter 0.5 mm filled with zirconia beads 80 volume%, 3 passes Dispersion was carried out under the conditions [crystalline polyester resin dispersion 1].

<Preparation of oil phase>
[WAX dispersion 1] 500 parts, [prepolymer A-1] 200 parts, [crystalline polyester resin dispersion 1] 500 parts, [polyester resin B-1] 750 parts, [master batch 1] 100 parts, Two parts of [ketimine compound 1] was placed in a container as a curing agent, and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for 60 minutes to obtain [Oil phase 1].
<Synthesis of organic fine particle emulsion (fine particle dispersion)>
683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfuric acid ester (Eleminol RS-30: manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, in a reaction vessel set with a stirring rod and a thermometer 138 parts and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The mixture was heated to a system temperature of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% aqueous ammonium persulfate solution is added, followed by aging at 75 ° C. for 5 hours to obtain an aqueous dispersion of vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [fine particles Dispersion 1] was obtained.
The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 (manufactured by HORIBA) was 0.14 μm. A part of the [fine particle dispersion 1] was dried to isolate the resin component.
<Preparation of water phase>
A mixture of 990 parts of water, 83 parts of [fine particle dispersion], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate is mixed and stirred to obtain milky white color. Got the liquid. This was designated as [water phase 1].

<Emulsification and desolvation>
1,200 parts of [aqueous phase 1] was added to a container containing [oil phase 1], and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain [emulsified slurry 1].
[Emulsified slurry 1] was put in a container in which a stirrer and a thermometer were set, and after desolvation at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [dispersed slurry 1].
<Washing and drying>
After filtration under reduced pressure of 100 parts of [Dispersion slurry 1],
(1): 100 parts of ion exchanged water was added to the filter cake, mixed with a TK homomixer (rotational speed of 12,000 rpm for 10 minutes) and filtered.
(2): 100 parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed 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), mixed with a TK homomixer (rotational speed of 12,000 rpm for 10 minutes) and filtered.
(4): 300 parts of ion-exchanged water is added to the filter cake of (3), and it is filtered after being mixed (rotational speed 12,000 rpm for 10 minutes) with a TK homomixer. Was carried out twice to obtain [filtered cake].
[Filtered cake] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm mesh to obtain [Toner base particle 1].
The composition ratio of the obtained [toner base particle 1], Tg1st, and Tg2nd are shown in Table 1-1.
<External processing>
To 100 parts by mass of toner base particles 1, 0.6 parts by mass of hydrophobic silica having an average particle diameter of 100 nm, 1.0 parts by mass of titanium oxide having an average particle diameter of 20 nm, and hydrophobic silica fine powder having an average particle diameter of 15 nm Toner 1 was obtained by mixing 0.8 parts with the body with a Henschel mixer.

<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 are added to 100 parts by mass of toluene, and dispersed for 20 minutes with a homomixer The resin layer coating solution was prepared. The resin layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite having an average particle diameter of 50 μm using a fluidized bed type coating apparatus to prepare a carrier.
<Preparation of developer>
A developer was prepared by mixing 5 parts by mass of the toner 15 and 95 parts by mass of the carrier using a ball mill. Next, evaluation of various characteristics was performed as follows using each of the produced developers. The results are shown in Table 1-1.

<Chargeability>
In an environment of 23 ° C. and humidity 53 ± 3%, 0.35 g of toner base particles and 5 g of carrier are put in a cylindrical container made of SUS (inner diameter 25 mm, height 30 mm) and conditioned after 12 hours or more Was sealed, and the container was rotated for 5 minutes at a rotational speed of 300 rpm. The mixture of the toner and the carrier was sampled from the container, placed in a 400 mesh blow-off gauge, air-blown at an air pressure of 5 KPa for 3 minutes, and then measured using an Epping Q / M meter (manufactured by EPPING). As a setting of the Q / M meter, the mesh size is 400 mesh (made of stainless steel), and the soft blow pressure (1050 V) suction time is 90 seconds. The charge amount can be calculated by the following equation.
Charged amount (μC / g) = Total electric amount after 90 seconds (μC) / Suctioned toner amount (g)
An appropriate value exists for the charge amount determined in this way, and it is not good if it is too high or too low. In the present invention, the charge amount of a conventional toner base particle (a cyan toner base particle mounted on a digital full-color multifunction device Imagio MP C4002 (manufactured by Ricoh Co., Ltd.)) is used as a reference value, and evaluation is made according to the following evaluation criteria.
〔Evaluation criteria〕
:: Charge equivalent to that of conventional toner (reference value −40 μC / g or more and less than −30 μC / g)
○: Slightly low charge but usable (−30 μC / g or more and less than −20 μC / g)
Δ: Low charge level, difficult to use (−20 μC / g or more and less than −10 μC / g)
X: The charge amount is too low to use (−10 μC / g or more)

<Image gloss>
A copying test was performed on a POD gloss coat 128 g / m ² (manufactured by Oji Paper Co., Ltd.) using an apparatus obtained by modifying the fixing unit of imagioMP C5002 (manufactured by Ricoh Co., Ltd.).
Specifically, the glossiness of the image passed at a fixing temperature of 140 degrees was determined. The image after the copying test was measured for 60 degree gloss using a gloss meter VG-7000 (manufactured by Nippon Denshoku Co., Ltd.).
As the fixing evaluation conditions, the linear velocity of paper feeding was 100 mm / sec, the surface pressure was 1.0 kgf / cm ² , and the nip width was 7 mm.
〔Evaluation criteria〕
:: Gloss 20% or more ○: Gloss 15% or more and less than 20% Δ: Gloss 10% or more and less than 15% ×: Gloss less than 10%

<Fixability>
A copy test was performed on Type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus obtained by modifying the fixing unit of imageo MP C5002 (manufactured by Ricoh Co., Ltd.).
Specifically, the fixing temperature was changed to obtain a cold offset temperature (fixing lower limit temperature) and a high temperature offset temperature (fixing upper limit temperature).
The evaluation conditions for the lower limit temperature of fixing were a linear speed of paper feeding of 200 mm / sec, a surface pressure of 1.0 kgf / cm ² , and a nip width of 7 mm.
The evaluation conditions for the upper limit fixing temperature were 100 mm / sec for the linear speed of paper feeding, 1.0 kgf / cm ² for the surface pressure, and 7 mm for the nip width.
The lower the fixing lower limit temperature, the better the low temperature fixability. The lower limit of fixation was evaluated according to the following criteria. On the other hand, if the fixing upper limit temperature is 170 ° C. or more, it is sufficient as the effect of the high temperature offset resistance obtained in the present invention.
〔Evaluation criteria〕
A: Fixing lower limit temperature is 109 ° C. or less ○: Fixing lower limit temperature is 110 ° C. or more and 114 ° C. or less Δ: Fixing lower limit temperature is 115 ° C. or more and 119 ° C. or less ×: Fixing lower limit temperature is 120 ° C or more

<Heat resistant storage stability>
10 g of toner is filled in a 50 mL glass container, sufficiently tapped until the change in apparent density of the toner powder disappears, the container is covered, left in a thermostat of 50 ° C. for 24 hours, and cooled to 24 ° C. The penetration degree (mm) was measured by a penetration degree test (JIS K2235-1991), and the heat resistant storage stability was evaluated based on the following criteria. The larger the penetration, the better the heat resistant storage stability, and the one having a penetration of less than 15 mm is likely to cause problems in use.
〔Evaluation criteria〕
:: Penetration is 25 mm or more ○: Penetration is 20 mm or more and less than 25 mm Δ: Penetration is 15 mm or more and less than 20 mm ×: Penetration is less than 15 mm

(Example 2)
[Toner base particle 2] was obtained in the same manner as in Example 1 except that Prepolymer A-2 was replaced with Prepolymer A-2 in Example 1, and [Toner Base Particle 2] was used [ The toner 2] was evaluated in the same manner as in Example 1. The results are shown in Table 1-1.
(Example 3)
[Toner base particle 3] was obtained in the same manner as in Example 1 except that Prepolymer A-1 was changed to Prepolymer A-3 in Example 1, and [Toner Base Particle 3] was used [ The toner 3] was evaluated in the same manner as in Example 1. The results are shown in Table 1-1.
(Example 4)
[Toner base particle 4] was obtained in the same manner as in Example 1 except that Prepolymer A-4 was replaced with Prepolymer A-4 in Example 1, and [Toner Base Particle 4] was used [ The toner 4] was evaluated in the same manner as in Example 1. The results are shown in Table 1-1.
(Example 5)
[Toner base particle 5] was obtained in the same manner as in Example 1 except that Prepolymer A-5 was changed to Prepolymer A-5 in Example 1, and [Toner Base Particle 5] was used [[5]. The toner 5] was evaluated in the same manner as in Example 1. The results are shown in Table 1-2.
(Example 6)
[Toner base particle 6] was obtained in the same manner as in Example 1 except that Prepolymer A-1 was changed to Prepolymer A-6 in Example 1, and [Toner Base Particle 6] was used [ The toner 6] was evaluated in the same manner as in Example 1. The results are shown in Table 1-2.

(Comparative example 1)
[Toner base particle 7] was obtained in the same manner as in Example 1 except that Prepolymer A-1 was changed to Prepolymer A-7 in Example 1, and [Toner Base Particle 7] was used [ The toner 7] was evaluated in the same manner as in Example 1. The results are shown in Table 2.
(Comparative example 2)
[Toner base particle 8] was obtained in the same manner as in Example 1 except that Prepolymer A-1 was changed to Prepolymer A-8 in Example 1, and [Toner Base Particle 8] was used. The toner 8] was evaluated in the same manner as in Example 1. The results are shown in Table 2.
(Comparative example 3)
[Toner base particle 9] was obtained in the same manner as in Example 1 except that the prepolymer A-1 was replaced with the prepolymer A-9 in Example 1, and the [toner base particle 9] was used. The toner 9] was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The aspect of the present invention is, for example, as follows.
<1> A toner containing at least a polyester resin, wherein the polyester resin has a structure represented by any one of the following structural formulas 1) to 3).
1) R1- (NHCONH-R2-X-R3) n-
2) R1- (NHCOO-R2-X-R3) n-
3) R1- (OCONH-R2-X-R3) n-
(In the above formula, n = 3
R1: aromatic or aliphatic organic group,
R2: a polyester derived from at least one of a polycarboxylic acid and a polyol, and a group derived from any resin of a modified polyester in which the polyester is isocyanate-modified
X: urea bond or urethane bond,
R3 represents a group derived from a compound represented by the following general formula (I).
[In the above general formula (I), T ₁ , T ₂ , T ₃ , T ₄ and T ₅ each independently represent a hydrogen atom or an isocyanate group, at least one of which is an isocyanate group, U ₁ , U ₂ , U ₃ , U ₄ and U ₅ each represent either a hydrogen atom or an isocyanate group, and at least one is an isocyanate group. ])
<2> The polyester resin contains a diol component as a constituent component, and the diol component contains 50 mol% or more of an aliphatic diol having 4 to 12 carbon atoms, and the carbon number of the portion to be the main chain of the diol component The toner according to <1>, wherein the diol component has an alkyl group in a side chain.
<3> The weight average molecular weight (Mw) of the polyester resin is 30,000 to 60,000, the weight average molecular weight / number average molecular weight (Mw / Mn) is 6 to 12, and the glass transition temperature is −60 ° C. The toner according to any one of <1> to <2>, wherein the temperature is 0 ° C. or less.
<4> Using diphenylmethane diisocyanate (MDI) as the compound represented by the general formula (I), the intermediate polyester containing the R2 is reacted with the diphenylmethane diisocyanate (MDI) to obtain the structural formulas 1) to 3). When manufacturing the polyester resin which has a structure represented by either of these, the polyester resin which has a structure represented by either of said Structural formula 1)-3) is said intermediate polyester and said diphenylmethane diisocyanate (MDI) And (MDI isocyanate group / intermediate polyester hydroxyl group) molar ratio is 1.5 or more and less than 3.0, any of the above <1> to <3> It is the toner described in.
The glass transition temperature (Tg1st) calculated | required from the temperature rising 1st DSC curve of the differential scanning calorimetry (DSC) of the <5> said toner is 20 degreeC or more and 50 degrees C or less in any one of said <1> to <4> It is the toner described in.
<6> The toner according to any one of <1> to <5>, wherein the polyester resin is insoluble in tetrahydrofuran (THF).
<7> Any one of the above <1> to <6>, wherein the polyester resin contains a dicarboxylic acid component as a component, and the dicarboxylic acid component contains 30 mol% or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms It is a toner as described in.
<8> Furthermore, a second polyester resin having a glass transition temperature of 40 ° C. to 70 ° C. is contained, and the glass transition temperature (Tg1st) at the first temperature elevation of differential scanning calorimetry (DSC) of the toner is 20. The toner according to any one of <1> to <7>, wherein the toner has a temperature of from 50 ° C. to 50 ° C.
<9> Furthermore, a crystalline polyester resin is contained, and the melting point of the crystalline polyester resin is 60 ° C. or more and 80 ° C. or less, and the glass transition temperature of the first temperature elevation in differential scanning calorimetry (DSC) of the toner The toner according to any one of <1> to <8>, wherein the difference (Tg1st-Tg2nd) between (Tg1st) and the second temperature increase in glass transition temperature (Tg2nd) is 10 ° C. or more.
The <10> said crystalline polyester resin is described in said <9> comprised from C4 or more and 12 or less linear saturated aliphatic dicarboxylic acid, and C2 or more and 12 or less linear saturated aliphatic diol. Toner.
<11> The toner according to any one of <1> to <10>, wherein the isocyanate compound represented by the general formula (I) is diphenylmethane diisocyanate (MDI).
<12> The toner according to any one of <1> to <11>, wherein the structural formulas 1) to 3) are represented by the following structural formulas a) to c).
1) R1- (NHCONH-R3-Y-R2'-X-R3) n-
2) R1- (NHCOO-R3-Y-R2'-X-R3) n-
3) R1- (OCONH-R3-Y-R2'-X-R3) n-
(In the above formula, n, R 1, R 3 and X represent the same as described in Structural Formulas 1) to 3). Further, R2 ′ is a group derived from polyester, and Y represents a urea bond or a urethane bond. )
<13> A developer comprising the toner according to any one of <1> to <12>.
<14> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier Developing means with toner to develop the image to form a visible image;
The image forming apparatus is characterized in that the toner is the toner according to any one of <1> to <12>.

  The toner according to any one of <1> to <12>, the developer according to <13>, and the image forming apparatus according to <14> solve the various problems in the related art, and the following objects To achieve the goal. That is, a toner having excellent low-temperature fixability, high-temperature offset resistance, high gloss, high color reproducibility, excellent charging characteristics and heat resistant storage stability, a developer having the toner, and an image forming apparatus using the developer Intended to provide.

10 electrostatic latent image carrier 21 exposure device 25 fixing device 61 developing device 160 charging device

Japanese Patent Application Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Patent No. 2579150 gazette JP 2001-158819 A Unexamined-Japanese-Patent No. 2004-46095 Unexamined-Japanese-Patent No. 2007-271789 Patent No. 5408210 gazette

Claims (10)

A toner containing at least a polyester resin, the polyester resin is less structural formulas 1) to 3) Ri Der either further second polyester resin having a glass transition temperature of 70 ° C. or less 40 ° C. or higher And a crystalline polyester resin .
1) The diol component and the dicarboxylic acid component are ester-reacted to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reacted with a trivalent or higher polyisocyanate (R1) to obtain The polyester resin 2) having a structure represented by the following structural formula; R1-NHCOO-), after ester-reacting a diol component and a dicarboxylic acid component to obtain a polyester polyol (R2) having a terminal hydroxyl group, the polyester The polyol (R2) is reacted with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2), which is obtained by reacting the isocyanate-modified polyester (R2) with a trivalent or higher alcohol (R1). Polyester resin 3 having a structure represented by the formula: R 1 -OCONH- The diol component and the dicarboxylic acid component are ester-reacted to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reacted with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2) After being obtained, it is obtained by reacting the isocyanate-modified polyester (R2) with a trivalent or higher polyisocyanate (R1) in the presence of pure water, and having a structure represented by the following structural formula; R1-NHCONH- resin A toner containing at least a polyester resin, the polyester resin is less structural formulas 1) to 3) Ri Der either further second polyester resin having a glass transition temperature of 70 ° C. or less 40 ° C. or higher And a crystalline polyester resin .
1) The diol component and the dicarboxylic acid component are ester-reacted to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reacted with a trivalent or higher polyisocyanate (R1) to obtain an isocyanate After the modified polyester (R2) is obtained, it is obtained by reacting the isocyanate-modified polyester (R2) with a polyisocyanate having a valence of 2 or more represented by the following general formula (I). Polyester resin (2) having a structure to be represented is esterified with a diol component and a dicarboxylic acid component to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reduced to the following general formula (I) These compounds are reacted with polyisocyanates of 2 or more valences represented by After obtaining the ester (R2), the polyester resin 3 having the structure represented by the following structural formula; R1-OCONH- is obtained by reacting the isocyanate-modified polyester (R2) with a trivalent or higher alcohol (R1). 2.) The ester component of the diol component and the dicarboxylic acid component is subjected to an ester reaction to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is represented by the following general formula (I): After reacting with an isocyanate to obtain an isocyanate-modified polyester (R2), the isocyanate-modified polyester (R2) is reacted with a trivalent or higher polyisocyanate (R1) in the presence of pure water to obtain the following structural formula; Polyester resin having a structure represented by R1-NHCONH-
[In the above general formula (I), T ₁ , T ₂ , T ₃ , T ₄ and T ₅ each independently represent a hydrogen atom or an isocyanate group, at least one of which is an isocyanate group, U ₁ , U ₂ , U ₃ , U ₄ and U ₅ each represent either a hydrogen atom or an isocyanate group, and at least one is an isocyanate group. ]   The polyester resin contains the diol component as a component, and the diol component contains 50 mol% or more of an aliphatic diol having 4 to 12 carbon atoms, and the carbon number of the portion to be the main chain of the diol component is odd The toner according to any one of claims 1 to 2, wherein the diol component has an alkyl group in a side chain.   The polyester resin has a weight average molecular weight (Mw) of 30,000 to 60,000, a weight average molecular weight / number average molecular weight (Mw / Mn) of 6 to 12, and a glass transition temperature of -60 ° C to 0 ° C. The toner according to any one of claims 1 to 3, which is the following. A method for producing a toner containing at least a polyester resin, comprising:
The polyester resin is less structural formulas 1) to 3) Ri Der either,
1) The diol component and the dicarboxylic acid component are ester-reacted to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reacted with a trivalent or higher polyisocyanate (R1) to obtain an isocyanate After the modified polyester (R2) is obtained, it is obtained by reacting the isocyanate-modified polyester (R2) with a polyisocyanate having a valence of 2 or more represented by the following general formula (I). Polyester resin (2) having a structure to be represented is esterified with a diol component and a dicarboxylic acid component to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is reduced to the following general formula (I) These compounds are reacted with polyisocyanates of 2 or more valences represented by After obtaining the ester (R2), the polyester resin 3 having the structure represented by the following structural formula; R1-OCONH- is obtained by reacting the isocyanate-modified polyester (R2) with a trivalent or higher alcohol (R1). 2.) The ester component of the diol component and the dicarboxylic acid component is subjected to an ester reaction to obtain a polyester polyol (R2) having a terminal hydroxyl group, and then the polyester polyol (R2) is represented by the following general formula (I): After reacting with an isocyanate to obtain an isocyanate-modified polyester (R2), the isocyanate-modified polyester (R2) is reacted with a trivalent or higher polyisocyanate (R1) in the presence of pure water to obtain the following structural formula; Polyester resin having a structure represented by R1-NHCONH-
[In the above general formula (I), T ₁ , T ₂ , T ₃ , T ₄ and T ₅ each independently represent a hydrogen atom or an isocyanate group, at least one of which is an isocyanate group, U ₁ , U ₂ , U ₃ , U ₄ and U ₅ each represent either a hydrogen atom or an isocyanate group, and at least one is an isocyanate group. ]
Any of the structural formulas 1) to 3) is obtained by reacting the intermediate polyester containing the R2 with the diphenylmethane diisocyanate (MDI) using diphenylmethane diisocyanate (MDI) as the compound represented by the general formula (I) When manufacturing the polyester resin which has a structure represented by these, the polyester resin which has a structure represented by either of said Structural Formula 1)-3) is said intermediate polyester and said diphenylmethane diisocyanate (MDI) ( A method for producing a toner, wherein the reaction is carried out such that the molar ratio of isocyanate group of MDI / hydroxyl group of intermediate polyester is 1.5 or more and less than 3.0. The toner according to any one of claims 1 to 4, wherein a glass transition temperature (Tg1st) determined from a DSC curve of the first temperature elevation of differential scanning calorimetry (DSC) of the toner is 20 ° C to 50 ° C. The toner according to any one of claims 1 to 5 , wherein the polyester resin is insoluble in tetrahydrofuran (THF). The toner according to any one of claims 1 to 6 , wherein the polyester resin contains the dicarboxylic acid component as a component, and the dicarboxylic acid component contains 30 mol% or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. A developer comprising the toner according to any one of claims 1 to 4 and 6 to 8. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image formed on the electrostatic latent image carrier Developing means for forming a visible image, comprising toner;
An image forming apparatus, wherein the toner is the toner according to any one of claims 1 to 4 and 6 to 8.