JP2015176111A - toner and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage property without inducing filming, and a developer comprising the toner.SOLUTION: The toner at least uses a crystalline polyester Ac and an amorphous polyester Aa, and the toner further contains a copolymer B obtained by reacting an amorphous polyester Ba and a crystalline polyester Bc to have a crystalline polyester unit at a terminal. A dispersion diameter of crystalline polyester domains in the toner is 1.0 μm or less.

Description

  The present invention relates to a toner and a developer using the toner.

  In recent years, toners have been able to withstand high temperature and high humidity during storage and transportation after production, as well as reduction in particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving. High heat-resistant storage stability is required. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.

Therefore, for the purpose of obtaining a high level of low temperature fixability, a toner containing a crystalline polyester resin and a release agent, and a resin and a wax that are incompatible with each other and having a sea-island phase separation structure has been proposed. (For example, Patent Document 1).
In addition, a toner containing a crystalline polyester resin, a release agent, and a graft polymer has been proposed (for example, Patent Document 2).

In addition, in order to improve the dispersibility of the crystalline polyester resin and the release agent in the toner in the toner containing the amorphous polyester resin, the crystalline polyester resin, and the release agent, And that the graft polymer should have an SP value between the SP value of the amorphous polyester resin and the SP value of the crystalline polyester resin graft ( (See Japanese Patent Application Laid-Open No. 2012-53196 in Patent Document 3 and Japanese Patent Application Laid-Open No. 2012-63559 in Patent Document 4.) However, in the graft polymer used as a dispersant in the disclosed techniques of Patent Documents 3 and 4, the portion corresponding to the adsorption unit is a hydrocarbon wax or crystalline polyester, and the portion corresponding to the steric hindrance unit is acrylic or styrene. Acrylic and amorphous polyester, but the structure and arrangement of the adsorption unit and steric hindrance unit in the graft polymer molecule are not particularly controlled. There is a certain probability that the terminal will become a steric hindrance unit. Therefore, the dispersibility, low-temperature fixability, and filming resistance of the crystalline resin are insufficient.
Accordingly, there is a need for a toner that has no filming and has excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability, and a developer containing the toner.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner having no filming and having excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability, and a developer containing the toner.

Means for solving the above-described problems are as follows. That is, the above problem is solved by the “toner” described in (1) below.
(1) “A copolymer obtained by reacting an amorphous polyester Ba and a crystalline polyester Bc so that the terminal is a crystalline polyester unit in a toner using at least the crystalline polyester Ac and the amorphous polyester Aa. A toner further comprising B and having a dispersed diameter of the crystalline polyester domain in the toner of 1.0 μm or less. ”

  As will be apparent from the following detailed and specific description, according to the present invention, the above-mentioned conventional problems can be solved, there is no filming, excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage. And a developer containing the toner.

1 is a diagram illustrating an example of an image forming apparatus of the present invention.

Hereinafter, the present invention will be described in detail.
The present invention relates to the “toner” described in (1) above, and this “toner” includes the modes of “toner” described in the following (2) to (12). Further, the present invention includes the “developer” described in (13) below and the “image forming apparatus” described in (14), and these will be described in detail.
(2) “The toner according to (1) above, wherein a dispersion diameter of the crystalline polyester domain in the toner is 0.5 μm or less.”
(3) “The copolymer B is obtained by copolymerizing an amorphous polyester Ba having an Mw of 3,000 to 20,000 and a crystalline polyester Bc having an Mw of 10,000 to 30,000. The toner according to (1) or (2). "
(4) "The weight ratio (WBc / WBa) of the amorphous polyester Ba unit and the crystalline polyester Bc unit of the copolymer B is 30/70 to 70/30" The toner according to any one of (3). "
(5) “The toner according to any one of (1) to (4) above, wherein the addition amount of the copolymer B to the crystalline polyester Aa is 10 to 100 wt%.”
(6) “The absolute value | SP Bc−SPAc | of the difference between the SP value of the crystalline polyester Bc and the SP value of the crystalline polyester Ac for the dispersant is 0.5 or less,” The toner according to any one of 1) to (5). "
(7) “The absolute value | SPaa−SPBa | of the difference between the SP value of the amorphous polyester Aa and the SP value of the amorphous polyester Ba is 0.2 to 1.0” The toner according to any one of 1) to (6). "
(8) As said amorphous polyester Aa, amorphous polyester Aa1 whose glass transition temperature is 40 degreeC or more and 70 degrees C or less, and has a branched structure, and glass transition temperature is -60 degreeC or more and 0 degrees C or less The toner according to any one of (1) to (7) above, which contains an amorphous polyester resin Aa2.
(9) Any one of (1) to (8) above, wherein the glass transition temperature (Tg1st) at the first temperature increase in the differential scanning calorimetry (DSC) of the toner is 20 ° C. to 50 ° C. The toner described. "
(10) “The crystalline polyester Ac and the crystalline polyester Bc have a melting point of 60 to 80 ° C. and are composed of a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a saturated aliphatic diol having 2 to 12 carbon atoms. The toner according to any one of (1) to (9) above.
(11) “The copolymer is characterized in that the amorphous polyester resin Ba and the crystalline polyester Bc are bonded via a urethane group / urea group”. The toner according to any one of 10). "
(12) “The copolymer is obtained by reacting the amorphous polyester resin Ba and a polyisocyanate compound to form a prepolymer, and then reacting the prepolymer with the crystalline polyester Bc. The toner according to any one of (1) to (11) above.
(13) “Developer using the toner according to any one of (1) to (12)”
(14) “An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. An image development apparatus including a toner that develops a latent image to form a visible image, wherein the toner is the toner according to any one of (1) to (12). Forming equipment. "

(toner)
As described above, the toner of the present invention is a toner further comprising the copolymer B in a toner using at least polyester A as a binder resin component. The polyester A includes a crystalline polyester Ac and an amorphous polyester Aa. The copolymer B has a unit derived from the crystalline polyester Bc and a unit derived from the amorphous polyester Ba. The copolymer B disperses the crystalline polyester Ac well.
That is, the toner of the present invention comprises a copolymer B formed by copolymerizing crystalline polyester Ac and amorphous polyester Aa, and amorphous polyester Ba and crystalline polyester Bc so that the terminal is a crystalline polyester unit. At least, and further contains other components as necessary.
Further, the amorphous polyester Aa can be a mixture of an amorphous polyester Aa1 having a higher glass transition point and an amorphous polyester Aa2 having a lower glass transition point, and is preferable. Details will be described later.

In the toner of the present invention, the dispersion particle diameter of the crystalline polyester Ac in the toner can be reduced by using the copolymer B in the toner using the crystalline polyester Ac. Crystalline polyester achieves low-temperature fixability by melting and plasticizing amorphous polyester Aa with a short heating time (˜100 ms) during fixing, and finely disperse crystalline polyester Ac in the toner. As a result, the toner can be further melted and plasticized rapidly even during a short heating time during fixing, and thus the toner can be further improved in low-temperature fixing property.
Further, at the time of heat melting, the copolymer B serves as a compatibilizing agent for assisting plasticization of the amorphous polyester Aa by the crystalline polyester Ac, so that it is possible to further improve the low-temperature fixability of the toner.

Further, by using the copolymer B, it is possible to prevent the crystalline polyester from being exposed on the toner surface.
Crystalline polyester is inferior in toughness compared to amorphous polyester, so when exposed to the toner surface, for example, the crystalline polyester forms a film on the photoreceptor during the image forming process, and it is spent on the carrier by stirring in the developer. This may cause image defects. In addition, since the electrical resistance is low, the chargeability and charge retention of the toner are deteriorated, for example, the toner adheres to the non-image area and the transfer performance is deteriorated, which causes image defects.
In the present invention, by using the copolymer B, exposure of the crystalline polyester to the toner surface can be suppressed, and these problems can be solved.

(Copolymer B)
The copolymer B used in the present invention is obtained by controlling the structure of an amorphous polyester Ba and a crystalline polyester Bc so that the terminal is a crystalline polyester unit.
In order for the material to function as a dispersant, an adsorption unit for adsorbing to the object to be dispersed (crystalline polyester Bc in the present invention) and a steric hindrance unit for preventing aggregation of the objects to be dispersed ((amorphous in the present invention) Quality polyester Ba) is required.

For the adsorption unit, a material having a high affinity with the material to be dispersed (crystalline polyester Ac in the present invention) is preferably used. In the copolymer B of the present invention, a crystalline polyester having the same structure as the material to be dispersed is used. Unit Bc plays that role.
The steric hindrance unit (unit derived from amorphous polyester Ba) is preferably a material having a certain degree of affinity with the dispersion medium (amorphous polyester Aa in the present invention). When the affinity is too low, the molecular chain of the sterically hindered unit cannot be sufficiently expanded in the dispersion medium, and the sterically hindered unit does not function well, and the dispersed material may aggregate. In addition, when the affinity is too high, the dispersant may not be adsorbed well to the dispersion, and the dispersion may diffuse into the dispersion medium, causing the dispersion to aggregate.

In order to adjust the affinity of each of the material to be dispersed, the dispersion medium, and the copolymer B, material design may be performed using, for example, a solubility parameter (SP value) as an index as a chemical affinity factor of each material. Is possible.
Further, in order for the copolymer B to exhibit more functions, it is necessary to arrange the adsorption unit at the end of the molecular chain, and it is important to control the structure of the dispersant.
When the adsorption unit exists inside the molecular chain of the copolymer B, the adsorption to the copolymer B is inhibited by the steric hindrance unit, and the dispersion function is lowered.

  Other factors for adjusting the dispersion function of the copolymer B include the ratio between the steric hindrance unit and the adsorption unit, the length of the molecular chain (molecular weight), and the like. A preferable range of each factor will be described later.

(Structure control method of copolymer B)
As a method of copolymerizing the crystalline polyester Bc and the amorphous polyester Ba for the synthesis of the copolymer B, for example, a method in which the crystalline polyester and the amorphous polyester are reacted under conditions where the crystalline polyester and the amorphous polyester are decomposed and the polymerization is balanced ( Transesterification method), polyester polyol-converted crystalline polyester and amorphous polyester are bonded with an extender such as an isocyanate compound (urethane extension method), etc., but in these methods, the reaction proceeds randomly. For this reason, for example, a combination of crystalline polyesters Bc or amorphous polyesters Ba is included at a certain ratio, so that many components that do not exhibit a dispersing function are included.
In addition, in the combination of amorphous polyester Ba and crystalline polyester Bc, the terminal of crystalline polyester unit and the terminal of amorphous polyester unit are included in a certain ratio, so the terminal is crystalline. There are few components which are a property polyester unit, and the function as a dispersing agent is not enough.

  In the present invention, for example, in order to place the crystalline polyester Bc as an adsorption unit at the terminal, the amorphous polyester Ba and the extender are first reacted to form a prepolymer, and then the crystalline polyester Bc and the prepolymer are reacted. A method (prepolymer method) is preferably used.

(Extender)
As the extender, divalent or higher isocyanate compounds are preferably used.
There is no restriction | limiting in particular as an isocyanate compound more than bivalence, According to the objective, it can select suitably, For example, as diisocyanate, a C6-C20 fragrance | flavor (except the carbon in an NCO group, and the following) Diisocyanate, aliphatic diisocyanate having 2 to 18 carbon atoms, alicyclic diisocyanate having 4 to 15 carbon atoms, araliphatic diisocyanate having 8 to 15 carbon atoms, or modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group) , Urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products), and if necessary, trivalent or higher polyisocyanates may be used in combination. These may be used individually by 1 type and may use 2 or more types together.

  Specific examples of the aromatic diisocyanate (including tri- or higher polyisocyanates) include, for example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate. (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof] A mixture of diaminodiphenylmethane and a small amount (for example, 5% by mass to 20% by mass) of a trifunctional or higher polyamine] Phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-i Cyanatophenyl sulfonyl isocyanate, and the like.

  Specific examples of the aliphatic diisocyanate (including triisocyanate or higher polyisocyanate) include, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl -2,6-diisocyanatohexanoate, and the like.

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

  Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.

  Specifically, a modified product of diisocyanate such as modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, or a mixture of two or more of these (for example, modified MDI and urethane modified). In combination with TDI (isocyanate-containing prepolymer).

  Among these, an aromatic diisocyanate having 6 to 15 carbon atoms, an aliphatic diisocyanate having 4 to 12 carbon atoms, and an alicyclic diisocyanate having 4 to 15 carbon atoms are preferable, and TDI, MDI, HDI, hydrogenated MDI, and IPDI are particularly preferable. preferable.

The molecular weight of the crystalline polyester Bc copolymerized in the copolymer B is preferably Mw 10,000 to 30,000.
If the Mw is less than 10,000, the crystallinity of the crystalline polyester Bc in the copolymer B becomes difficult to be expressed, the adsorption ability to the crystalline polyester Ac as the dispersion is reduced, and the dispersion ability is reduced. It may become difficult to express. In addition, the melt viscosity and mechanical strength of the copolymer B may decrease, and the heat resistant storage stability and filming resistance of the toner may deteriorate.
When Mw exceeds 30,000, the crystallinity of the crystalline polyester Bc in the copolymer B becomes strong, and the copolymers B tend to aggregate in the toner, making it difficult to express the dispersion ability. is there.
Further, the melt viscosity of the copolymer B increases, and the low-temperature fixability of the toner may deteriorate.

The molecular weight of the amorphous polyester Ba serving as a part of the copolymer B is preferably Mw 3,000 to 20,000.
When the Mw is less than 3,000, the amorphous polyester Ba does not sufficiently function as a steric hindrance unit, and the dispersion ability may be lowered.
When Mw exceeds 20,000, the melt viscosity of the copolymer B increases and the low-temperature fixability of the toner may deteriorate.

The weight ratio (W Bc / W Ba) of the weight (W Bc) of the crystalline polyester Bc to the weight (W Ba) of the amorphous polyester Ba in the copolymer B is preferably 30/70 to 70/30.
If it is less than 30/70, the number of adsorbing units may be small and it may be difficult to express the dispersion ability.
If it exceeds 70/30, the number of steric hindrance units may decrease and it may be difficult to express the dispersion ability.

The absolute value | SP Ac-SP Bc | of the difference between the SP value of the crystalline polyester Ac and the SP value of the crystalline polyester Bc is preferably 0.5 or less.
If | SP Ac-SP Bc | is 0.5 or less, the affinity between the substance to be dispersed and the adsorption unit may be low, and it may be difficult to express the dispersion ability.

The absolute value | SP Aa−SP Ba | of the difference between the SP value of the amorphous polyester Aa and the SP value of the amorphous polyester Ba is preferably 0.2 to 1.0.
If it is less than 0.2, the affinity between the steric hindrance unit of the dispersant and the dispersion medium is too high, so that the dispersant tends to diffuse into the dispersion medium, and it may be difficult to express the dispersion ability.
If it exceeds 1.0, the molecular chain of the steric hindrance unit cannot be sufficiently expanded in the dispersion medium, and it may be difficult to express the dispersion ability.

The content of the copolymer B is preferably 20 wt% to 100 wt% with respect to the crystalline polyester Ac.
If it is 20 wt% or less, the dispersion function is not sufficiently exhibited, and the low-temperature fixability and filming resistance may be deteriorated.
If it is 100 wt% or more, the copolymer B may impair the crystallinity of the crystalline polyester, and the low-temperature fixability, filming resistance, and heat storage stability may be deteriorated.

(Amorphous polyester Aa (the amorphous polyester Aa1 + the amorphous polyester Aa2), the amorphous polyester Ba)
As described above, the amorphous polyester Aa can be preferably a mixture of the amorphous polyester Aa1 having a higher glass transition point and the amorphous polyester Aa2 having a lower glass transition point.
Aa1, Aa2 as the amorphous polyester Aa component used in the present invention and the amorphous polyester Ba unit contained in the copolymer B are not particularly limited and can be appropriately selected according to the purpose.
The amorphous polyester Aa may be a combination of an amorphous polyester Aa1 having a glass transition temperature of 70 ° C. or lower, preferably 40 ° C. or higher and 70 ° C. or lower, and an amorphous polyester Aa2 having a lower Tg and having a branched structure. This is preferable in that the low-temperature fixability is further improved.

(Amorphous polyester Aa1)
The amorphous polyester resin Aa1 is preferably an unmodified polyester resin. The unmodified polyester resin is a polyester resin obtained using a polyhydric alcohol, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid such as a polyvalent carboxylic acid ester or a derivative thereof, It is a polyester resin not modified with an isocyanate compound or the like.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Examples include oxide (average added mole number 1 to 10) adducts.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octyl succinic acid, or alkenyl having 2 to 20 carbon atoms. And succinic acid substituted with a group.
These may be used individually by 1 type and may use 2 or more types together.

For the purpose of adjusting the acid value and the hydroxyl value, the amorphous polyester Aa 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.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, or acid anhydrides thereof.
Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the amorphous polyester resin Aa1 is not particularly limited and may be appropriately selected depending on the intended purpose. However, when the molecular weight is too low, the heat resistant storage stability of the toner, stress such as stirring in the developing machine, etc. In some cases, the durability may be inferior, and when the molecular weight is too high, the viscoelasticity at the time of melting of the toner becomes high and the low-temperature fixability may be inferior. ) It is preferable that it is 3,000-10,000. The number average molecular weight (Mn) is preferably 1,000 to 4,000. Moreover, it is preferable that Mw / Mn is 1.0-4.0.
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.

  The acid value of the amorphous polyester resin Aa1 is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1 mgKOH / g to 50 mgKOH / g, more preferably 5 mgKOH / g to 30 mgKOH / g. . When the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved at the time of fixing to paper, and the low-temperature fixability can be improved. . When the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered.

  There is no restriction | limiting in particular as a hydroxyl value of the said amorphous polyester resin Aa1, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

  The glass transition temperature (Tg) of the amorphous polyester resin Aa1 is preferably 40 ° C. or higher and 70 ° C. or lower. When the glass transition temperature is less than 40 ° C., the heat resistant storage stability of the toner and the durability against stress such as stirring in the developing machine may be inferior, and the filming resistance may be deteriorated. When the glass transition temperature exceeds 70 ° C., deformation due to heating and pressurization at the time of fixing the toner is not sufficient, and the low-temperature fixability may be insufficient.

The content of the amorphous polyester Aa1 is preferably 50 parts by weight or more.
When the amount is less than 50 parts by weight, the content of the amorphous polyester as a dispersion medium is small, so that the crystalline polyester Ac is difficult to finely disperse, and the amount of the crystalline polyester Ac is relatively large. Deterioration, electrical resistance, filming resistance, and heat storage stability may be deteriorated.

The molecular structure of the amorphous polyester resin Aa1 can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. Conveniently in the infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on? Ch (out-of-plane bending vibration) of olefin as an amorphous polyester resin Aa1 It is done.

  There is no restriction | limiting in particular as content of the said amorphous polyester resin Aa1, Although it can select suitably according to the objective, 50 mass parts-90 mass parts are more preferable with respect to 100 mass parts of the said toner, 60 mass parts-80 mass parts are still more preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and the release agent in the toner may be deteriorated, and the image may be easily fogged or disturbed. Since the content of the polyester Ac, the copolymer B, and the amorphous polyester Aa2 is reduced, the low temperature fixability may be inferior. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Amorphous polyester Aa2>
The amorphous polyester resin Aa2 is preferably obtained by a reaction between a non-linear reactive precursor and a curing agent, and has a glass transition temperature of −60 ° C. or higher and 0 ° C. or lower.

  The amorphous polyester resin Aa2 preferably has at least one of a urethane bond and a urea bond from the viewpoint of better adhesion to a recording medium such as paper. Further, since the amorphous polyester resin Aa2 has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, and the amorphous polyester Aa2 has rubber-like properties. And the toner has better heat-resistant storage stability and high-temperature offset resistance.

-Non-linear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with the curing agent (hereinafter sometimes referred to as “prepolymer”). Can be selected as appropriate.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples of the group capable of reacting with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferable because a urethane bond or a urea bond can be introduced into the amorphous polyester resin.

The prepolymer is non-linear. The non-linear means having a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid.
As the prepolymer, a polyester resin containing an isocyanate group is preferable.

-Polyester resin Aa21 containing an isocyanate group-
There is no restriction | limiting in particular as polyester resin Aa21 containing the said isocyanate group for the synthesis | combination of amorphous polyester Aa2, It can select suitably according to the objective, For example, polyester resin and polyisocyanate which have an active hydrogen group, The reaction product of is mentioned. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensation of diol, dicarboxylic acid, trivalent or higher alcohol and trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin containing the isocyanate group.

--- Diol ---
The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol Diols having an oxyalkylene group such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols, ethylene oxide, propylene Bisphenols such as bisphenol A, bisphenol F, bisphenol S, etc .; bisphenols such as those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to bisphenols Examples thereof include alkylene oxide adducts. 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 ---
There is no restriction | limiting in particular as said dicarboxylic acid, 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) alkyl esterified material 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 intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, 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, a 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 having a valence of 3 or more ---
The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trihydric or higher aliphatic alcohol, trivalent or higher polyphenol, trivalent or higher polyphenol alkylene Examples include oxide adducts.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

--Carboxylic acid having a valence of 3 or more ---
There is no restriction | limiting in particular as said trivalent or more carboxylic acid, According to the objective, it can select suitably, For example, trivalent or more aromatic carboxylic acid etc. are mentioned. Moreover, these anhydrides may be used, a lower (C1-C3) alkyl esterified material may be used, and a halide may be used.
The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples of the trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

--- 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 blocked with phenol derivatives, oximes, caprolactams, and the like.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.
The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it is a curing agent that can react with the non-linear reactive precursor and generate the amorphous polyester Aa2, and can be appropriately selected according to the purpose. Examples thereof include active hydrogen group-containing compounds.

-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 individually by 1 type and may use 2 or more types together.

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.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher valent amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of a 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, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane etc. are mentioned. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. It is done. There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine etc. are mentioned.

  The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

  The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.

  The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

  The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

  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 an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketimine compounds and oxazoline compounds.

  In order to lower the Tg of the amorphous polyester Aa2 and easily impart the property of deforming at low temperatures, the amorphous polyester resin Aa2 contains a diol component as a constituent component, and the diol component has 4 carbon atoms. It is preferable to contain 50% by mass or more of an aliphatic diol of 12 or less.

  In order to lower the Tg of the amorphous polyester Aa2 and to easily impart the property of deforming at low temperatures, the amorphous polyester Aa2 contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component has a carbon number. It is preferable to contain 50% by mass or more of 4 to 12 aliphatic dicarboxylic acids.

  The glass transition temperature of the amorphous polyester Aa2 is preferably −60 ° C. or more and 0 ° C. or less. When the glass transition temperature is less than −60 ° C., the flow of the toner at a low temperature cannot be suppressed, the heat resistant storage stability is deteriorated, and the filming resistance is sometimes deteriorated. When the glass transition temperature exceeds 0 ° C., the toner due to heating and pressurization at the time of fixing cannot be sufficiently deformed, and the low-temperature fixability may be insufficient.

  There is no restriction | limiting in particular as a weight average molecular weight of the said amorphous polyester Aa2, Although it can select suitably according to the objective, In GPC (gel permeation chromatography) measurement, 20,000 or more and 1,000,000 or less Is preferred. The weight average molecular weight of the amorphous polyester Aa2 is a molecular weight of a reaction product obtained by reacting the nonlinear reactive precursor and the curing agent. When the weight average molecular weight is less than 20,000, the toner tends to flow at a low temperature and the heat-resistant storage stability may be inferior. Moreover, the viscosity at the time of melting may be lowered, and the high temperature offset property may be lowered.

The molecular structure of the amorphous polyester Aa2 can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

  There is no restriction | limiting in particular as content of the said amorphous polyester Aa2, Although it can select suitably according to the objective, 5 mass parts-25 mass parts are preferable with respect to 100 mass parts of said toner, 10 masses. Part-20 mass parts is more preferable. When the content is less than 5 parts by mass, the low-temperature fixability and the high-temperature offset resistance may be deteriorated. When the content is more than 25 parts by mass, the heat-resistant storage stability is deteriorated, and the glossiness of the image obtained after fixing is obtained. The degree may decrease. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

(Amorphous polyester Ba)
The amorphous polyester Ba, which is a raw material for forming the copolymer B, uses a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. The resulting polyester resin.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Examples include oxide (average added mole number 1 to 10) adducts.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octyl succinic acid, or alkenyl having 2 to 20 carbon atoms. And succinic acid substituted with a group.
These may be used individually by 1 type and may use 2 or more types together.

(Crystalline polyester Ac, Bc)
The crystalline polyester Ac used in the present invention and the crystalline polyester Bc serving as a structural site in the copolymer B are polyhydric alcohol, polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, polyhydric carboxylic acid ester, etc. And a polyvalent carboxylic acid or a derivative thereof.

-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 trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyesters Ac and Bc may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material. The number of carbon atoms 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, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, the crystalline polyesters A and B have high crystallinity and are excellent in sharp melt properties, and thus ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1 , 10-decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

-Multivalent 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, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, 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 anhydrides and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained.
These may be used individually by 1 type and may use 2 or more types together.

  The crystalline polyesters Ac and Bc are 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 polyesters Ac and Bc have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. Is preferred. 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.

  The crystalline polyesters Ac and Bc are not particularly limited in melting point and can be appropriately selected according to the purpose, but are preferably 60 ° C. or higher and 80 ° C. or lower. When the melting point is less than 60 ° C., the crystalline polyester resin Aa2 is likely to melt at a low temperature, and the heat-resistant storage stability of the toner may be reduced. The melting of Aa2 is insufficient and the low-temperature fixability may deteriorate.

The molecular weight of the crystalline polyester resin Ac is not particularly limited and may be appropriately selected according to the purpose. A component having a sharp molecular weight distribution and a low molecular weight is excellent in low-temperature fixability and has a low molecular weight. From the viewpoint that the heat-resistant storage stability is lowered if the amount is too large, the soluble content of the orthodichlorobenzene of the crystalline polyester resin C has a weight average molecular weight (Mw) of 3,000 to 30,000, a number average molecular weight ( Mn) 1,000 to 10,000 and Mw / Mn 1.0 to 10 are preferable.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 5,000-15,000, 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 A, Although it can select suitably according to the objective, In order to achieve desired low-temperature fixability from a viewpoint of affinity with paper and resin. Is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. On the other hand, 45 mgKOH / g or less is preferable in order to improve the high temperature offset resistance.

  The hydroxyl value of the crystalline polyester resin Ac is not particularly limited and can be appropriately selected according to the purpose. In order to achieve a desired temperature fixability and to achieve good charging characteristics, 0 mgKOH / g to 50 mgKOH / g is preferable, and 5 mgKOH / g to 50 mgKOH / g is more preferable.

The molecular structures of the crystalline polyesters Ac and Bc can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. Conveniently in the infrared absorption spectrum, and a method of detecting those with absorption based on olefin? Ch (out-of-plane deformation vibration) to 965 ± 10 cm ^-1 or 990 ± 10 cm ^-1 as a crystalline polyester A and B .

  There is no restriction | limiting in particular as content of the said crystalline polyester Ac, 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 toner, and 5 mass parts. -15 mass parts is more preferable. When the content is less than 3 parts by mass, the low-temperature fixability may be inferior because sharp melting with the crystalline polyester Ac is insufficient, and when it exceeds 20 parts by mass, the heat-resistant storage stability is reduced. In addition, image fogging may occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

  The dispersed particle diameter of the crystalline polyester Ac in the toner is preferably 0.5 μm or less. The dispersed particle diameter here refers to the average value of the particle diameters in the major axis direction of the crystalline polyester Ac when the cross section of the toner is observed using an observation device such as a transmission electron microscope (TEM). When the dispersed particle diameter exceeds 0.5 μm, the crystalline polyester is insufficiently melted and plasticized with respect to heating during fixing, and the low-temperature fixability may be deteriorated.

<Other ingredients>
Examples of the other components include a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property 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 release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; And natural waxes such as petroleum waxes such as paraffin, 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;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. When the melting point is less than 60 ° C., the release agent is likely to melt at a low temperature, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature range, the release agent may not be sufficiently melted, resulting in fixing offset and image loss.

  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 toner, 3 mass parts- 8 parts by mass is more preferable. When the content is less than 2 parts by mass, the high-temperature offset resistance during fixing and the low-temperature fixability may be inferior. When the content exceeds 10 parts by mass, the heat-resistant storage stability is deteriorated, and image fogging occurs. Etc. may occur easily. When the content is within the more preferable range, it is advantageous in terms of improving image quality and improving fixing stability.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and the like.

  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 toners, and 3 mass parts-10 parts. Part by mass is more preferable.

The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin B, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, or a polymer of its substitution product; p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylate Methyl acid copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.
The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shear force and kneading to obtain a masterbatch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Is mentioned. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Is mentioned.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

-External additive-
As the external additive, in addition to oxide fine particles, inorganic fine particles and hydrophobized inorganic particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and 5 nm to 70 nm. The inorganic fine particles are more preferable.
Further, it is preferable that at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment is contained, and at least one kind of inorganic fine particles having a diameter of 30 nm or more is contained. In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate and aluminum stearate), and metal oxides. (For example, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymer, and the like.
Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Moreover, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like can be mentioned.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF- Examples include 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles include, for example, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. It can be obtained by treatment with a silane coupling agent such as octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Examples include modified silicone oil, epoxy-modified silicone oil, epoxy / polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

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 the said toner. 3 mass parts-3 mass parts are more preferable.
There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm or more and 70 nm or less are more preferable. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

-Fluidity improver-
The fluidity improver is not particularly limited as long as it is surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics 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. It is done. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photosensitive member or the primary transfer medium, and is appropriately selected according to the purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

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

<Calculation method and analysis method of various characteristics of toner and toner component>
SP value, Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester Aa1, Ba, Aa2, crystalline polyester Ac, Bc, copolyester B, and release agent are each about itself. Although it may be measured, it is separated from actual toner by gel permeation chromatography (GPC) or the like, and an analysis method described later is applied to each separated component, so that SP value, Tg, molecular weight, melting point, constituent components The mass ratio may be calculated.

Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire surface of the elution curve are collected.
The concentrated eluate is concentrated and dried with an evaporator and the like, and then the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. The constituent monomer ratio is calculated.

  As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) to calculate the constituent monomer ratio.

  When the toner manufacturing method forms toner base particles while generating amorphous polyester C by an extension reaction and / or a crosslinking reaction between the nonlinear reactive precursor and the curing agent. May be separated from the actual toner by GPC or the like to obtain the Tg of the amorphous polyester C, or separately, an elongation reaction between the non-linear reactive precursor and the curing agent and / or Alternatively, amorphous polyester Aa2 may be synthesized by a crosslinking reaction, and Tg and the like may be measured from the synthesized amorphous polyester Aa2.

<< Toner component separation means >>
An example of the separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated 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 a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .
The monomer composition and composition ratio of the amorphous polyesters Aa1, Ba, Aa2, crystalline polyesters Ac, Bc, and copolymer B contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens)
7.1 ppm to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
Around 6.8 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens) and from double bond of fumaric acid (for 2 hydrogens)
5.2 ppm to around 5.4 ppm: methine derived from bisphenol A propylene oxide adduct (one hydrogen)
3.7 ppm to around 4.7 ppm: bisphenol A propylene oxide adduct derived from methylene (for 2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (for 4 hydrogens)
Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)
It can be.

  From these results, for example, an extract collected in a fraction in which the amorphous polyester Aa (= Aa1 + Aa2) occupies 90% or more can be treated as the amorphous polyester Aa.

<< SP value >>
The SP value (solubility parameter / Solubility Parameter) will be described.
The SP value is called a solubility parameter, and is a numerical value of how easily each other is soluble. The SP value is expressed as a square root of an attractive force between molecules, that is, a cohesive energy density (CED). The CED is the amount of energy required to evaporate 1 mL.

The calculation of the SP value in the present invention can be performed using the following formula (I) by the Fedors method.
SP value (dissolution parameter) = (CED value) 1/2 = (E / V) 1/2 Formula (I)
In the calculation formula (I), E is the molecular aggregation energy (cal / mol), V is the molecular volume (cm ³ / mol), and when the evaporation energy of the atomic group is Δei and the molar volume is Δvi, Are represented by the following formula (II) and formula (III).
E = ΣΔei ... Formula (II)
V = ΣΔvi ... Formula (III)

The data described in “Basic Theory of Adhesion” (Akira Imoto, published by Kobunshi Shuppankai, Chapter 5) are used for this calculation method and various data of evaporation energy Δei and molar volume Δvi of each atomic group.
For those not shown, such as —CF 3 group, F. Fedors, Polym. Eng. Sci. 14, 147 (1974).
For reference, 2.046 is converted to SI unit (J / m ³ ) _1/2 when the SP value shown in the calculation formula (I) is converted to (J / cm ³ ) _1/2. If so, 2,046 may be multiplied.
For example, when the amorphous polyesters Aa, Ba, Aa2, crystalline polyesters Ac, Bc, and a dispersing agent for crystalline polyester (polyester copolymer B) are synthesized and mixed, the SP value is Thus, it can be easily calculated.

Usually, it is difficult to calculate the SP value from the charged composition ratio in a resin in which a monomer is added during the polymerization to change the resin skeleton. In addition, the composition of the components contained in the toner is generally unknown, and it is difficult to calculate the SP value.
However, the calculation of the SP value by the Fedors method can be performed by specifying the type and ratio of the monomer constituting the resin or the like.
For example, a mixture of the amorphous polyesters Aa1, Aa2, crystalline polyester Ac, a dispersing agent for crystalline polyester, etc. is separated by GPC, and the above-described analysis method is applied to each separated component. The SP value can be calculated.
Calculation of the SP value by the Fedors method can be performed by specifying the type and ratio of the monomer constituting the resin, but the SP value in the present invention is determined when the monomer type is specified by the above analysis. Each composition ratio was added in order from the highest ratio, and calculated from the monomer composition when the total reached 90 mol% of the total (that is, the SP value was calculated for the remaining monomers). Not to be added).

<< Method for measuring hydroxyl value and acid value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For 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〕
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
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
Measurement 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
Steppes 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
Potentialial No
Stop for revaluation No

The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case where ethyl acetate is soluble) 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 prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For 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 hydroxyl value described above.

  The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and 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, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, the DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).
From the obtained DSC curve, the DSC curve at the first temperature rise can be selected using the analysis program in the Q-200 system, and the glass transition temperature at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the glass transition temperature at the second temperature increase of the target sample can be obtained.
Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, a DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.

In this specification, when the toner is used as the target sample, the glass transition temperature at the first temperature rise is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
In this specification, the amorphous polyesters Aa1, Ba, Aa2, crystalline polyesters Ac, Bc, dispersants for crystalline polyesters, and glass transition temperatures and melting points of other components such as the release agent Unless otherwise specified, the endothermic peak top temperature at the second temperature rise and Tg are the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
For the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, the ratio (D4 / Dn) is, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Co., Ltd.) or the like. Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Measurement of molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (made by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 mL / min
Sample: 0.4 mL injection of 0.15% by mass sample Pretreatment of sample: Toner was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass and filtered through 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 a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD 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. An RI (refractive index) detector is used as the detector.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, the toner includes the amorphous polyester Aa, crystalline polyester Ac, copolymer B, and further if necessary. It is preferable to granulate by dispersing an oil phase containing the reactive precursor, the curing agent, a release agent, the colorant and the like in an aqueous medium.

An example of such a method for producing the toner is a known dissolution suspension method.
As an example of the method for producing the toner, toner base particles are produced while generating an amorphous polyester resin Aa (= Aa1 + Aa2) by an extension reaction and / or a crosslinking reaction between the nonlinear reactive precursor and the curing agent. The method of forming is shown below. In such a method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended 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, water, the solvent miscible with water, these mixtures etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. 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. There is no restriction | limiting in particular as said lower ketone, According to the objective, it can select suitably, For example, acetone, methyl ethyl ketone, etc. are mentioned.

-Preparation of oil phase-
Preparation of the oil phase containing the toner material includes the amorphous polyester Aa, the crystalline polyester Ac, a dispersant for the crystalline polyester, and further, if necessary, a reactive precursor, the curing agent, a release agent, The toner material containing a colorant can be dissolved or dispersed 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 is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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 individually by 1 type and may use 2 or more types together.
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 performed by dispersing the oil phase containing the toner material in the aqueous medium.
Then, when the toner material is emulsified or dispersed, the amorphous polyester C is generated by subjecting the curing agent and the nonlinear reactive precursor to an extension reaction and / or a crosslinking reaction.

The amorphous polyester Aa2 can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor in the aqueous medium A method of producing the amorphous polyester resin Aa2 by subjecting to elongation reaction and / or crosslinking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are added in the aqueous medium. A method for producing the amorphous polyester resin A by subjecting the body to an extension reaction and / or a crosslinking reaction.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is added from the particle interface in the aqueous medium. A method of producing the amorphous polyester resin Aa2 by subjecting the non-linear reactive precursor to an extension reaction and / or a crosslinking reaction.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester Aa2 are not particularly limited, and are appropriately determined depending on the combination of the curing agent and the non-linear reactive precursor. You can choose.
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.
The reaction temperature is not particularly limited and may be appropriately selected depending on the intended purpose.
0 degreeC-150 degreeC is preferable, and 40 degreeC-98 degreeC is more preferable.

  The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the aqueous medium phase Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added and dispersed by shearing force.

The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing 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 shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution 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, According to the objective, it can select suitably.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. It is 50 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 is more preferable.
When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained, and the amount exceeds 2,000 parts by mass. The production cost may increase.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain 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 slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together.
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, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an 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, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the amorphous polyester Aa2.
The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples include a method of evaporating the organic solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion into a dry atmosphere.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed 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, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, For example, a method may be used in which the mixture is charged and accelerated to cause the particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited and may be appropriately selected depending on the purpose. And a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the toner particle diameter, and the filming of the toner on the developing roller and a member such as a blade for thinning the toner The toner is less fused to the toner, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.

<Career>
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.

−Core material−
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 50 emu / g to 90 emu / g manganese-strontium-based material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable.
When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause scattering of the carrier. In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Part is preferable, and 93 parts by mass to 97 parts by mass is more preferable.

[Image forming apparatus]
The image forming apparatus using the toner of the present invention includes 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 carrier. A developing unit including a toner that develops the electrostatic latent image formed on the body to form a visible image, wherein the toner is the toner according to any one of (1) to (12). It is characterized by being.
The developing unit is a unit that develops an electrostatic latent image using the toner of the present invention to form a visible image.
FIG. 1 is a schematic view showing an example of a two-component developing apparatus using a two-component developer comprising a toner and a carrier of the present invention. In this image forming apparatus, first, the electrostatic latent image carrier (20) is rotationally driven at a predetermined peripheral speed, and the peripheral surface of the electrostatic latent image carrier (20) is positive or negative by the charging device (32). It is uniformly charged to a predetermined negative potential. Next, the peripheral surface of the electrostatic latent image carrier (20) is exposed by the exposure device (33), and electrostatic latent images are sequentially formed. Therefore, the electrostatic latent image forming means in this image forming apparatus includes a charging device (32) and an exposure device (33). Further, the electrostatic latent image formed on the peripheral surface of the electrostatic latent image carrier (20) is developed by the developing device (40) using the developer containing the toner and carrier of the present invention, and the toner image is formed. It is formed. Next, the toner image formed on the peripheral surface of the electrostatic latent image carrier (20) is synchronized with the rotation of the electrostatic latent image carrier (20), and the electrostatic latent image carrier (20 ) And the transfer device (50), the images are sequentially transferred onto the transfer paper fed between them. Further, the transfer paper onto which the toner image has been transferred is separated from the peripheral surface of the electrostatic latent image carrier (20), introduced into the fixing device and fixed, and then copied as a copy (copy) of the image forming apparatus. Printed out. On the other hand, the surface of the electrostatic latent image carrier (20) after the toner image is transferred is cleaned by removing the residual toner by the cleaning device (60), and then removed by the static eliminator (70). And used repeatedly for image formation.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Synthesis of Amorphous Polyester Aa1-1>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is mixed with bisphenol A propylene oxide 2-mol adduct, terephthalic acid, and adipic acid, and a molar ratio of terephthalic acid and adipic acid (isophthalic acid). Acid / adipic acid), 80/20, charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1.2, and is always used together with titanium tetraisopropoxide (500 ppm with respect to the resin component). The reaction was carried out at 230 ° C. for 8 hours, and further after 4 hours of reaction at a reduced pressure of 10 mmHg to 15 mmHg. Reacting for a time, amorphous polyester Aa1-1 was obtained.
The obtained amorphous polyester Aa1-1 had SP values of 11.0, Mw 9,000, and Tg 60 ° C.

<Synthesis of Amorphous Polyester Aa1-2>
A four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple is mixed with bisphenol A propylene oxide 2-mol adduct, terephthalic acid, and adipic acid, and a molar ratio of terephthalic acid and adipic acid (isophthalic acid). Acid / adipic acid) is 80/20, and OH / COOH, which is the molar ratio of the hydroxyl group to the carboxyl group, is charged to 1.3, and is always added together with titanium tetraisopropoxide (500 ppm with respect to the resin component). The reaction was carried out at 230 ° C. for 8 hours, and further after 4 hours of reaction at a reduced pressure of 10 mmHg to 15 mmHg. Reacting for a time, amorphous polyester Aa1-2 was obtained.
The resulting amorphous polyester Aa1-2 had SP values of 11.0, Mw 4,500, and Tg 48 ° C.

<Synthesis of Amorphous Polyester Ba-1>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 40/60, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged to 1.2, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. In addition, the reaction is performed at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. To obtain the quality polyester Ba-1.
The resulting amorphous polyester Ba-1 had SP values of 11.5, Mw 12,500, and Tg 55 ° C.

<Synthesis of Amorphous Polyester Ba-2>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 80/20, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged to 1.2, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. In addition, the reaction is performed at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. To obtain the quality polyester Ba-2.
The obtained amorphous polyester Ba-2 had SP values of 11.3, Mw 10,500, and Tg 53 ° C.

<Synthesis of Amorphous Polyester Ba-3>
A four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple is mixed with bisphenol A ethylene oxide side 2 mol adduct, isophthalic acid, and adipic acid, and a molar ratio of isophthalic acid and adipic acid ( 80/20 (isophthalic acid / adipic acid), and charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1.2, together with titanium tetraisopropoxide (500 ppm relative to the resin component) The reaction was carried out at 230 ° C. for 8 hours under normal pressure, and further for 4 hours under reduced pressure of 10 mmHg to 15 mmHg to obtain amorphous polyester Ba-3.
The obtained amorphous polyester Ba-3 had SP values of 11.2, Mw 9,500, and Tg 55 ° C.

<Synthesis of Amorphous Polyester Ba-4>
Into a four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2-mole adduct, propylene glycol, and terephthalic acid were added to bisphenol A ethylene oxide side 2-mole adduct. Propylene glycol was charged so that the molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) was 25/75, and OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was 1.3. It reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester Ba-4.
The obtained amorphous polyester Ba-4 had SP values of 11.9, Mw 9,000, and Tg 53 ° C.

<Synthesis of Amorphous Polyester Ba-5>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol and terephthalic acid so that OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group, is 1.3. The resulting mixture was reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C. for 8 hours at normal pressure, and further reacted for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg to obtain amorphous polyester Ba-5.
The obtained amorphous polyester Ba-5 had SP values of 12.1, Mw 10,000, and Tg 53 ° C.

<Synthesis of Amorphous Polyester Ba-6>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 40/60, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. And charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1.4, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. In addition, it reacts for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, To obtain the quality polyester Ba-6.
The obtained amorphous polyester Ba-6 had SP values of 11.5, Mw 3,500, and Tg 48 ° C.

<Synthesis of Amorphous Polyester Ba-7>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 40/60, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged to 1.5 and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. In addition, it reacts for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, To obtain the quality polyester Ba-7.
The obtained amorphous polyester Ba-7 had SP values of 11.5, Mw 2,800, and Tg 46 ° C.

<Synthesis of Amorphous Polyester Ba-8>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 40/60, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. And charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1.05, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. Furthermore, it reacts for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, To give the amorphous polyester Ba-8.
The obtained amorphous polyester Ba-8 had an SP value of 11.5, Mw 28,000, and Tg 60 ° C.

<Synthesis of Amorphous Polyester Ba-9>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with 2 mol of bisphenol A ethylene oxide side adduct, propylene glycol, isophthalic acid, and adipic acid, and 2 mol of bisphenol A ethylene oxide side. The adduct and propylene glycol have a molar ratio (bisphenol A ethylene oxide side 2 mol adduct / propylene glycol) of 40/60, and isophthalic acid and adipic acid have a molar ratio (isophthalic acid / adipic acid) of 80/20. The OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged to 1.03, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. Furthermore, it reacts for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, To give the amorphous polyester Ba-9.
The SP value of the obtained amorphous polyester Ba-9 was 11.5, Mw 32,000, and Tg 62 ° C.

<Synthesis of ketimine>
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer 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.

<Synthesis of Amorphous Polyester Aa2-1>
-Synthesis of prepolymer Aa2-1-
3-Methyl-1,5-pentanediol, terephthalic acid, adipic acid, and trimethylolpropane are in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. OH / COOH is 1.2, the diol component is 3-methyl-1,5-pentanediol 100 mol%, the dicarboxylic acid component is terephthalic acid 50 mol% and adipic acid 50 mol%, and all monomers Titanium tetraisopropoxide (1,000 ppm with respect to the resin component) was added so that the amount of trimethylolpropane in the mixture was 1 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Thereafter, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester Aa2-1.
Next, a molar ratio of the intermediate polyester Aa2-1 and isophorone diisocyanate (IPDI) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2. The solution was added at 0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain prepolymer Aa2-1.

-Synthesis of amorphous polyester Aa2-1-
The obtained prepolymer Aa2-1 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introduction tube, and the amine amount of [ketimine compound 1] was larger than the isocyanate amount in the prepolymer Aa2-1. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and the prepolymer extension product was taken out after stirring at 45 ° C. for 10 hours. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain amorphous polyester Aa2-1.
The obtained amorphous polyester Aa2-1 had Mw 35,000 and Tg-20 ° C.

<Synthesis of Amorphous Polyester Aa2-2>
-Synthesis of prepolymer Aa2-2-
Propylene glycol, isophthalic acid, adipic acid, and trimethylolpropane were mixed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe with an OH / COOH molar ratio of 1.2 to 1.2. And the composition of the diol component is 100 mol% of propylene glycol, the composition of the dicarboxylic acid component is 90 mol% of isophthalic acid and 10 mol% of adipic acid, and the amount of trimethylolpropane in all monomers is 1 mol%. It was charged together with tetraisopropoxide (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 until the effluent water disappeared. Thereafter, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester Aa2-2.
Next, a molar ratio of the intermediate polyester Aa2-2 and isophorone diisocyanate (IPDI) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe (IPDI isocyanate group / intermediate polyester hydroxyl group) 2. The solution was added at 0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain prepolymer Aa2-2.

-Synthesis of amorphous polyester Aa2-2-
The obtained prepolymer Aa2-2 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introduction tube, and the amine amount of [ketimine compound 1] was larger than the isocyanate amount in the prepolymer Aa2-2. An equimolar amount of [ketimine compound 1] was dropped into the reaction vessel, and the prepolymer extension product was taken out after stirring at 45 ° C. for 10 hours. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain amorphous polyester Aa2-2.
The obtained amorphous polyester Aa2-1 had Mw of 38,000 and Tg of 55 ° C.

<Synthesis of Crystalline Polyester Ac-1>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group. Is made to be 0.9, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. Crystalline polyester Ac-1 was obtained by reaction at a pressure of 3 kPa for 2 hours.
The obtained crystalline polyester Ac-1 had an SP value of 9.6, Mw of 15,000, and a melting point of 72 ° C.

<Synthesis of Crystalline Polyester Ac-2>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with fumaric acid, 1,4-butanediol, and 1,6-hexanediol, and the composition of the diol component is 1. , 4-butanediol 50 mol% and 1,6-hexanediol 50 mol%, and charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 0.9, titanium tetraisopropoxide (resin component) And then reacted at 180 ° C. for 10 hours, heated to 200 ° C. for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester Ac-2. .
The obtained crystalline polyester Ac-2 had an SP value of 10.8, Mw of 15,000, and a melting point of 82 ° C.

<Synthesis of Crystalline Polyester Bc-1>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group. Was made to be 1.1 and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. Reaction was performed at a pressure of 3 kPa for 2 hours to obtain crystalline polyester Bc-1.
Crystalline polyester Bc-1 obtained had an SP value of 9.6, Mw of 16,000, and a melting point of 70 ° C.

<Synthesis of Crystalline Polyester Bc-2>
Dodecanedioic acid and 1,4 butanediol are placed in a 5-L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and the molar ratio of hydroxyl group to carboxyl group is OH.
/ COOH was set to 1.1 and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, Reaction was performed at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester Bc-2.
Crystalline polyester Bc-2 obtained had an SP value of 10.0, Mw of 18,000, and a melting point of 65 ° C.

<Synthesis of Crystalline Polyester Bc-3>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, dodecanedioic acid and ethylene glycol were added at a OH / COOH molar ratio of hydroxyl group to carboxyl group of 1.1. Then, after reacting with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and the pressure was further increased to 8.3 kPa. For 2 hours to obtain crystalline polyester Bc-3.
Crystalline polyester Bc-3 obtained had an SP value of 10.2, Mw of 12,000, and a melting point of 73 ° C.

<Synthesis of Crystalline Polyester Bc-4>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group. Is made to be 1.4, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. Reaction was performed at a pressure of 3 kPa for 2 hours to obtain crystalline polyester Bc-4.
The obtained crystalline polyester Bc-4 had an SP value of 9.6, Mw of 3,200, and a melting point of 65 ° C.

<Synthesis of Crystalline Polyester Bc-5>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group. Is made to be 1.5, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours. Reaction was performed at a pressure of 3 kPa for 2 hours to obtain crystalline polyester Bc-5.
The obtained crystalline polyester Bc-5 had an SP value of 9.6, Mw of 2,8000, and a melting point of 63 ° C.

<Synthesis of Crystalline Polyester Bc-6>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group. Is made to be 1.04, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. Reaction was performed at a pressure of 3 kPa for 2 hours to obtain crystalline polyester Bc-6.
The obtained crystalline polyester Bc-6 had an SP value of 9.6, Mw of 28,000, and a melting point of 73 ° C.

<Synthesis of Crystalline Polyester Bc-7>
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, dodecanedioic acid and 1,10-dodecanediol are OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group. Is made to be 1.02 and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. Crystalline polyester Bc-7 was obtained by reacting for 2 hours at a pressure of 3 kPa.
The obtained crystalline polyester Bc-7 had an SP value of 9.6, Mw of 32,000, and a melting point of 74 ° C.

<Synthesis of Crystalline Polyester Bc-8>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with fumaric acid, 1,4-butanediol, and 1,6-hexanediol, and the composition of the diol component is 1. , 4-butanediol 50 mol% and 1,6-hexanediol 50 mol%, and charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1.1, titanium tetraisopropoxide (resin component) In addition, after reacting at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester Bc-8. .
The obtained crystalline polyester Bc-8 had an SP value of 10.8, Mw of 18,000, and a melting point of 81 ° C.

<Synthesis of Copolymer B-1>
-Synthesis of Prepolymer D-1-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, amorphous polyester B-1 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0. The resultant was diluted with ethyl acetate to a 50% ethyl acetate solution and reacted at 100 ° C. for 5 hours to obtain a prepolymer D-1.

-Synthesis of copolymer B-1-
The obtained prepolymer D-1 and crystalline polyester Bc-1 were mixed with a weight ratio of amorphous polyester Ba-1 to crystalline polyester Bc-1 (amorphous polyester Ba-1 / crystalline polyester Bc-1). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain a copolymer B-1.

<Synthesis of copolymer B-2>
-Synthesis of Prepolymer D-2-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-2 and isophorone diisocyanate (IPDI) are in a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2.0. The resultant was diluted with ethyl acetate to a 50% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours to obtain a prepolymer D-2.

-Synthesis of copolymer B-2-
The obtained prepolymer D-2 and crystalline polyester Bc-1 were obtained by changing the weight ratio of amorphous polyester Ba-2 to crystalline polyester Bc-1 (amorphous polyester Ba-2 / crystalline polyester Bc-1). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-2.

<Synthesis of copolymer B-3>
-Synthesis of Prepolymer D-3-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-3 and isophorone diisocyanate (IPDI) were in a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2.0. The resultant was diluted with ethyl acetate to a 50% ethyl acetate solution and reacted at 100 ° C. for 5 hours to obtain a prepolymer D-3.

-Synthesis of copolymer B3-
The obtained prepolymer D-3 and crystalline polyester Bc-1 were mixed with a weight ratio of amorphous polyester Ba-3 to crystalline polyester Bc-1 (amorphous polyester Ba-3 / crystalline polyester Bc-1). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-3.

<Synthesis of copolymer B-4>
-Synthesis of Prepolymer D-4-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-4 and isophorone diisocyanate (IPDI) are in a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2.0. The resultant was diluted with ethyl acetate to a 50% ethyl acetate solution and reacted at 100 ° C. for 5 hours to obtain a prepolymer D-4.

-Synthesis of copolymer B-4-
The obtained prepolymer D-4 and the crystalline polyester Bc-1 were mixed with the amorphous polyester Ba-4 and the crystalline polyester Bc-1 in a weight ratio (amorphous polyester Ba-4 / crystalline polyester Bc-1). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-4.

<Synthesis of Copolymer B-5>
-Synthesis of Prepolymer D-5-
Amorphous polyester Ba-5 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. The mixture was diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain Prepolymer D-5.

-Synthesis of dispersant 5 for crystalline polyester-
The obtained prepolymer D-5 and crystalline polyester Bc-1 were used in a weight ratio of amorphous polyester Ba-5 to crystalline polyester Bc-1 (amorphous polyester Ba-5 / crystalline polyester Bc-1). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain a copolymer-B5.

<Synthesis of Copolymer B-6>
-Synthesis of copolymer B-6-
The prepolymer D-1 and the crystalline polyester Bc-2 were mixed with an amorphous polyester Ba-1 and the crystalline polyester Bc-2 in a weight ratio (amorphous polyester Ba-1 / crystalline polyester Bc-2) of 50/50. The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-6.

<Synthesis of Copolymer B-7>
-Synthesis of copolymer B-7-
The prepolymer D-1 and the crystalline polyester Bc-3 are 50/50 by weight ratio of the amorphous polyester Ba-1 and the crystalline polyester Bc-3 (amorphous polyester Ba-1 / crystalline polyester Bc-3). The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-7.

<Synthesis of Copolymer B-8>
-Synthesis of dispersant 8 for crystalline polyester-
The weight ratio of the prepolymer D-1 and the crystalline polyester Bc-1 to the amorphous polyester Ba-1 and the crystalline polyester Bc-1 (amorphous polyester Ba-1 / crystalline polyester Bc-1) is 68/32 The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-8.

<Synthesis of Copolymer B-9>
-Synthesis of copolymer B-9-
The prepolymer D-1 and the crystalline polyester Bc-1 are 72/28 in weight ratio of the amorphous polyester Ba-1 and the crystalline polyester Bc-1 (amorphous polyester Ba-1 / crystalline polyester Bc-1). The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-9.

<Synthesis of Copolymer B-10>
-Synthesis of copolymer B-10-
Prepolymer D-1 and crystalline polyester Bc-1 were mixed with amorphous polyester Ba-1 and crystalline polyester Bc-1 in a weight ratio (amorphous polyester Ba-1 / crystalline polyester Bc-1) of 32/68. The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-10.

<Synthesis of Copolymer B-11>
-Synthesis of copolymer B-11-
The prepolymer D-1 and the crystalline polyester Bc-1 are 72/28 in weight ratio of the amorphous polyester Ba-1 and the crystalline polyester Bc-1 (amorphous polyester Ba-1 / crystalline polyester Bc-1). The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-11.

<Synthesis of copolymer B12>
-Synthesis of Prepolymer D-6-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-6 and isophorone diisocyanate (IPDI) are in a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0. The mixture was diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain Prepolymer D-6.

-Synthesis of copolymer B-12-
The resulting prepolymer D-6 and crystalline polyester Bc-4 were used in a weight ratio of amorphous polyester Ba-6 to crystalline polyester Bc-4 (amorphous polyester Ba-6 / crystalline polyester Bc-4). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-12.

<Synthesis of Copolymer B-13>
-Synthesis of Prepolymer D-7-
Amorphous polyester Ba-7 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. The mixture was diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain Prepolymer D-7.

-Synthesis of copolymer B-13-
The resulting prepolymer D-7 and crystalline polyester Bc-5 were used in a weight ratio of amorphous polyester Ba-7 to crystalline polyester Bc-5 (amorphous polyester Ba-7 / crystalline polyester Bc-5). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain a copolymer B-13.

<Synthesis of Copolymer B-14>
-Synthesis of Prepolymer D-8-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-8 and isophorone diisocyanate (IPDI) are in a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0. The mixture was diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain Prepolymer D-8.

-Synthesis of copolymer B-14-
The obtained prepolymer D-8 and crystalline polyester Bc-6 were used in a weight ratio of amorphous polyester Ba-8 to crystalline polyester Bc-6 (amorphous polyester Ba-8 / crystalline polyester Bc-6). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-14.

<Synthesis of Copolymer B-15>
-Synthesis of Prepolymer D-9-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the amorphous polyester Ba-9 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0. The mixture was diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain Prepolymer D-8.

-Synthesis of copolymer B-15-
The resulting prepolymer D-9 and crystalline polyester Bc-7 were used in a weight ratio of amorphous polyester Ba-9 to crystalline polyester Bc-7 (amorphous polyester Ba-9 / crystalline polyester Bc-7). The prepolymer elongation product was taken out by reacting at 50 ° C. for 50 hours at 100 ° C. in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-15.

<Synthesis of Copolymer B-16>
-Synthesis of dispersant 16 for crystalline polyester-
The weight ratio of the prepolymer D-1 and the crystalline polyester Bc-8 to the amorphous polyester Ba-1 and the crystalline polyester Bc-8 (amorphous polyester Ba-1 / crystalline polyester Bc-8) was 50/50. The reaction was carried out at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the prepolymer extension was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-16.

<Synthesis of Copolymer B-17>
Copolymer B-17 was synthesized by a transesterification method.

-Synthesis of copolymer B-17-
The weight ratio of amorphous polyester Ba-1 and crystalline polyester Bc-8 to amorphous polyester Ba-1 and crystalline polyester Bc-8 (amorphous polyester Ba-1 / crystalline polyester Bc-8) was 50. / 50, titanium tetraisopropoxide (500 ppm with respect to the resin component), and reaction in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube at 230 ° C. under reduced pressure of 1 kPa for 5 hours. -17 was obtained.

<Synthesis of Copolymer B-18>
Copolymer B-18 was prepared by the urethane elongation method.

-Synthesis of copolymer B-18-
The weight ratio of amorphous polyester Ba-1 to crystalline polyester Bc-1 to amorphous polyester Ba-1 to crystalline polyester Bc-1 (amorphous polyester Ba-1 / crystalline polyester Bc-1) was 50. / 50, amorphous polyester Ba-1 and crystalline polyester Bc-1 and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate group of IPDI / hydroxyl group of amorphous polyester and crystalline polyester) of 1.0 The solution was added, diluted with ethyl acetate to a 50% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. The obtained extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a copolymer B-18.

Example 1
<Synthesis of master batch (MB)>
1,200 parts of water, carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] and 500 parts of amorphous polyester resin Aa1-1 were added, and Henschel mixer (Mitsui Mine) was added. The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion>
Paraffin wax 50 parts (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as a mold release agent 1 in a container equipped with a stir bar and a thermometer, and ethyl acetate 450 The temperature was raised to 80 ° C. with stirring and held at 80 ° C. for 5 hours, then cooled to 30 ° C. at 1 hour, and the liquid feeding speed was measured using a bead mill (Ultra Visco Mill, manufactured by IMEX). Dispersion was performed under the conditions of 1 kg / hr, disk peripheral speed 6 m / sec, 0.5% zirconia beads 80% by volume, and 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester dispersion>
A container equipped with a stir bar and a thermometer was charged with 50 parts of crystalline polyester Ac-1 and 450 parts of ethyl acetate, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then 30 ° C. for 1 hour. Then, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / sec, 80% by volume of 0.5 mm zirconia beads are filled, and dispersion is performed under the condition of 3 passes. To obtain [Crystalline Polyester Dispersion 1].

<Preparation of oil phase>
[WAX Dispersion 1] 500 parts, [Prepolymer Aa2-1] 240 parts, [Crystalline Polyester Dispersion 1] 1000 parts, [Amorphous Polyester Aa1-1] 580 parts, [Copolymer B-1] 50 parts, 100 parts of [Masterbatch 1] and 2 parts of [ketimine compound 1] were put in a container and mixed with TK homomixer (manufactured by Special Machine) for 60 minutes at 8,000 rpm to obtain [Oil Phase 1]. .

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

<Preparation of aqueous phase>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This was designated as [Aqueous Phase 1].

<Emulsification / desolvation>
1,200 parts of [Aqueous phase 1] was added to a container containing [Oil phase 1], and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), 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 (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): The operation of (1) to (5) above, wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. Was performed twice to obtain [Filter cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1]. Table 1 shows the Tg of the toner and the dispersion diameter of the crystalline polyester domain in the toner (the measurement method is described below).

(Measurement method of dispersion diameter)
The toner is embedded in an epoxy resin, cut into ultrathin sections of about 100 nm, and dyed with ruthenium tetroxide. Next, observation is performed at a magnification of 10,000 times using a transmission electron microscope (TEM), and the photographed images are evaluated. Thereby, the dispersion state of crystalline polyester can be observed and a dispersion diameter can be measured. The dispersion diameter was defined as the length in the major axis direction as the dispersion diameter. Further, the section was adjusted so that a section of about 50 toner particles was included in one section, the dispersed particle diameter of at least 50 crystalline polyesters was measured, and the average value was defined as the dispersed domain diameter of the crystalline polyester. .

(Judgment method of crystalline polyester)
In the toner, the crystalline polyester resin and the release agent were judged from the contrast and shape. Since the binder resin other than the release agent has many double bond portions and is dyed with ruthenium tetroxide, the release agent portion can be distinguished from the resin portion other than the release agent. That is, the release agent is dyed lightest by ruthenium dyeing, then the crystalline polyester resin is dyed, and the non-crystalline polyester resin is dyed most intensely. In contrast, a whiter contrast portion was determined as a release agent, and a contrast between the amorphous polyester and the release agent was determined as a crystalline polyester.

(Example 2)
Example 1 <Example 1> except that 50 parts of [Copolymer B-1] was replaced with 12 parts and 580 parts of [Amorphous Polyester Aa1-1] were replaced with 618 parts in <Preparation of oil phase> in Example 1. In the same manner as described above, [Toner 2] was obtained.

(Example 3)
In Example 1 <Preparation of oil phase>, Example 1 except that 50 parts of [Copolymer B-1] was replaced with 8 parts and 580 parts of [Amorphous Polyester Aa1-1] were replaced with 622 parts. In the same manner as described above, [Toner 3] was obtained.

Example 4
In Example 1 <Preparation of oil phase>, Example 1 was performed except that 50 parts of [Copolymer B-1] was replaced with 95 parts and 580 parts of [Amorphous Polyester Aa1-1] were replaced with 535 parts. In the same manner as described above, [Toner 4] was obtained.

(Example 5)
Example 1 <Example 1> except that 50 parts of [Copolymer B-1] was replaced with 105 parts and 580 parts of [Amorphous Polyester Aa1-1] was replaced with 525 parts in <Preparation of oil phase> in Example 1. In the same manner as described above, [Toner 5] was obtained.

(Example 6)
[Toner 6] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-2] in <Preparation of oil phase> in Example 1. .

(Example 7)
[Toner 7] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-3] in <Preparation of oil phase> in Example 1. .

(Example 8)
[Toner 8] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-4] in <Preparation of oil phase> in Example 1. .

Example 9
[Toner 9] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-5] in <Preparation of oil phase> in Example 1. .

(Example 10)
[Toner 10] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-6] in <Preparation of oil phase> in Example 1. .

(Example 11)
[Toner 11] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-7] in <Preparation of oil phase> in Example 1. .

(Example 12)
[Toner 12] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-8] in <Preparation of oil phase> in Example 1. .

(Example 13)
[Toner 13] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-9] in <Preparation of oil phase> in Example 1. .

(Example 14)
[Toner 14] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-10] in <Preparation of oil phase> in Example 1. .

(Example 15)
[Toner 15] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-11] in <Preparation of oil phase> in Example 1. .

(Example 16)
[Toner 16] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-12] in <Preparation of oil phase> in Example 1. .

(Example 17)
[Toner 13] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-13] in <Preparation of oil phase> in Example 1. .

(Example 18)
[Toner 18] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-14] in <Preparation of oil phase> in Example 1. .

(Example 19)
[Toner 19] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-15] in <Preparation of oil phase> in Example 1. .

(Example 20)
In <Preparation of oil phase> in Example 1, [Crystalline Polyester Ac-1] is replaced with [Crystalline Polyester Ac-2] and [Copolymer B-1] is replaced with [Copolymer B-16]. Except for the above, [Toner 20] was obtained in the same manner as in Example 1.

(Example 21)
In <Preparation of oil phase> in Example 1, [amorphous polyester Aa1-1] is replaced with [amorphous polyester Aa1-2] and [prepolymer Aa2-1] is replaced with [prepolymer Aa2-2]. Except for the above, [Toner 21] was obtained in the same manner as in Example 1.

(Comparative Example 1)
In Example 1 <Preparation of oil phase>, Example 1 except that 50 parts of [Copolymer B-1] was replaced with 0 part and 580 parts of [Amorphous Polyester Aa1-1] was replaced with 630 parts. In the same manner as described above, [Toner 22] was obtained.

(Comparative Example 2)
[Toner 23] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-17] in <Preparation of oil phase> in Example 1. .

(Comparative Example 3)
[Toner 24] was obtained in the same manner as in Example 1 except that [Copolymer B-1] was replaced with [Copolymer B-18] in <Preparation of oil phase> in Example 1. .

(Comparative Example 4)
In Example 21 <Preparation of oil phase>, Example 1 was performed except that 50 parts of [Copolymer B-1] was replaced with 0 part and 580 parts of [Amorphous polyester Aa1-2] were replaced with 630 parts. In the same manner as described above, [Toner 25] was obtained.

<Evaluation>
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in Table 1.

<< Preparation of developer >>
-Production of carrier-
Add 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black to 100 parts of toluene, disperse with a homomixer for 20 minutes, and apply resin layer A liquid was prepared. Using a fluid bed type coating device, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.

-Production of developer-
Using a ball mill, 5 parts of toner and 95 parts of the carrier were mixed to prepare a developer.

<< Low-temperature fixability and high-temperature offset resistance >>
A copy test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus in which the fixing unit of imgioMP C5002 (manufactured by Ricoh Co., Ltd.) was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) and the high temperature offset temperature (fixing upper limit temperature) were determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm / second to 150 mm / second, a surface pressure of 1.2 kgf / cm 2, and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
When the fixing lower limit temperature is 110 ° C. or lower, the low temperature fixing effect obtained by the present invention is sufficient.

<< Heat resistant storage stability >>
The toner was stored at 50 ° C. for 8 hours and then sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was measured. At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
The evaluation criteria for heat resistant storage stability were as follows.
◎: Residual rate is less than 10% ○: Residual rate is 10% or more and less than 20% △: Residual rate is 20% or more and less than 30% ×: Residual rate is 30% or more

<< Filming >>
Using an image forming apparatus Ricoh pro 6001 (manufactured by Ricoh Co., Ltd.), the photoreceptor after forming 30,000 sheets of images is visually inspected, and toner components, mainly a release agent, are fixed to the photoreceptor. Whether or not it occurred was evaluated according to the following evaluation criteria.
A: The toner component is not fixed to the photoconductor. A: The toner component is fixed to the photoconductor. However, this is not a practical problem. Δ: The toner component is fixed to the photoconductor. , Is a level that causes a problem in practical use ×: The toner component can be firmly fixed to the photoconductor, and is a level having a large problem in practical use.

<< Cover >>
Using Ricoh pro 6001 (manufactured by Ricoh Co., Ltd.), after outputting 30000 A4 horizontal charts (image pattern A) in which black solid and white solid are repeated at intervals of 1 cm in a direction perpendicular to the rotation direction of the developing sleeve A blank paper image was output, the presence or absence of fogging was visually confirmed, and evaluation was performed according to the following evaluation criteria.
◎: No fogging at all ○: Although there is a fogging, there is no problem in actual use △: There is a fogging and there is a possibility of causing problems in actual use ×: There is a fogging and it is a serious problem in actual use At the level

  From the results of Examples 1 to 21 and Comparative Examples 1 to 4, it is confirmed that the toner of the present invention has no filming and image fogging, and has excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability. did it.

20 Electrostatic latent image carrier 32 Charging device 33 Exposure device 40 Development device 50 Transfer device 60 Cleaning device 70 Static elimination device

JP 2004-46095 A JP 2007-271789 A JP 2012-53196 A JP 2012-63559 A

Claims (14)

In the toner using at least the crystalline polyester Ac and the amorphous polyester Aa, the toner further includes a copolymer B obtained by reacting the amorphous polyester Ba and the crystalline polyester Bc so that the terminal is a crystalline polyester unit. A toner having a dispersion diameter of crystalline polyester domains in the toner of 1.0 μm or less.
The toner according to claim 1, wherein a dispersion diameter of the crystalline polyester domain in the toner is 0.5 μm or less.
The copolymer B is obtained by copolymerizing an amorphous polyester Ba having an Mw of 3,000 to 20,000 and a crystalline polyester Bc having an Mw of 10,000 to 30,000. The toner described in 1.
The weight ratio (WBc / WBa) of the amorphous polyester Ba unit and the crystalline polyester Bc unit of the copolymer B is 30/70 to 70/30. The toner described.
The toner according to any one of claims 1 to 4, wherein an addition amount of the copolymer B to the crystalline polyester Aa is 10 to 100 wt%.
The absolute value | SP Bc-SPAc | of the difference between the SP value of the crystalline polyester Bc and the SP value of the crystalline polyester Ac for the dispersant is 0.5 or less. The toner according to any one of the above.
The absolute value | SPa-SPBa | of the difference between the SP value of the amorphous polyester Aa and the SP value of the amorphous polyester Ba is 0.2 to 1.0. The toner according to any one of the above.
As the amorphous polyester Aa, an amorphous polyester Aa1 having a glass transition temperature of 40 ° C. to 70 ° C. and an amorphous polyester having a branched structure and having a glass transition temperature of −60 ° C. to 0 ° C. The toner according to claim 1, comprising a polyester resin Aa2.
9. The toner according to claim 1, wherein the glass transition temperature (Tg1st) at the first temperature increase in differential scanning calorimetry (DSC) of the toner is 20 ° C. to 50 ° C. 10.
The crystalline polyester Ac and the crystalline polyester Bc have a melting point of 60 to 80 ° C., and are composed of a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a saturated aliphatic diol having 2 to 12 carbon atoms. The toner according to claim 1.
11. The copolymer according to claim 1, wherein the amorphous polyester resin Ba and the crystalline polyester Bc are bonded via a urethane group / urea group. Toner.
The copolymer is obtained by reacting the amorphous polyester resin Ba and a polyisocyanate compound to form a prepolymer, and then reacting the prepolymer with a crystalline polyester Bc. The toner according to claim 1.
A developer using the toner according to claim 1.
  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 An image forming apparatus comprising: a developing unit that includes a toner that forms a visible image, wherein the toner is the toner according to claim 1.

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