WO1999008159A1

WO1999008159A1 - Toner composition

Info

Publication number: WO1999008159A1
Application number: PCT/JP1998/003474
Authority: WO
Inventors: Takashi Ito
Original assignee: Teijin Limited
Priority date: 1997-08-05
Filing date: 1998-08-04
Publication date: 1999-02-18
Also published as: JP3862763B2; AU8463798A; CA2267551A1; EP0930544A1; KR20000068695A; EP0930544A4

Abstract

A toner composition which comprises a color former and at least one polymer selected from the group consisting of A and B, is excellent in melt flowability, fixability, anti-offset properties, and blocking resistance, and can be positively electrified, wherein A is a noncross-linked polyesterimide comprising specific ester units E and imide units I, and B is a cross-linked polyesterimide comprising the units E and I and cross-linking units C.

Description

Specification

Technical field of toner composition

The present invention relates to a toner composition useful as a full-color printer for high-speed copying machines. More specifically, the toner composition is excellent in blocking resistance, low-temperature fixing property, and melt fluidity, and is used for developing an electrostatic image or a magnetic latent image in electrophotography or magnetic printing, for example. And a polyesterimide resin that provides the toner composition. Background art

In the electrophotographic method, that is, in a method of obtaining a permanent visible image by an electrostatic image, an electrostatic image formed on a photoconductive semiconductor or an electrostatic recording medium is developed with a toner charged by friction in advance. And then settled. In the case of a magnetic latent image, the latent image on the magnetic drum is developed and fixed by toner containing a magnetic material. For fixing, the toner image obtained by the development is directly fused on a photoconductive photoreceptor or an electrostatic recording material, or the toner image is transferred onto paper or a film and then fused on a transfer sheet. This is done by letting The fusion of the toner image is usually performed by applying pressure and heating. There are two types of heating method: non-contact heating method using an electric oven or flash light, and pressure heating method using a pressure roller.In recent years, where high speed and simplification of the fixing process are required, the latter method is used. Is mainly used. The above method is generally called "dry development method".

The toner composition used in the dry development method is prepared by melt-kneading a binder resin as a base, a colorant, a charge control agent, a magnetic powder and other necessary additives, sufficiently dispersing them, and then pulverizing. Manufactured. This resin is the main component of the toner and greatly affects the performance required of the toner. That is, the binder resin for the toner is required to have a good dispersibility of the colorant and the like in the melt-kneading step and good pulverizability in the pulverizing step. Many performances are required, such as good blocking resistance and good electrical properties. As such resins, epoxy resins, polyester resins, polystyrene resins, acrylic resins, and the like have been generally used. Among them, those which can be fixed at a lower temperature and those which have a PVC-resistant plastic Polyester due to its excellent agent properties, good transparency and compatibility with color Resins have attracted attention.

Japanese Unexamined Patent Publication No. Hei 6—1 2 8 3 67, Japanese Patent Publication No. 59-1-19002, Japanese Patent Publication No. 5-85

No. 91 describes a polyester resin in which a crosslinked structure is introduced using a monomer having three or more functionalities or a monomer having an unsaturated group as one component in order to improve the resistance to fusing in the fixing step. ing. However, this branched or cross-linked polyester resin has reduced flowability and is not suitable for high-speed copying or color copying.

Therefore, a polyester resin having a linear structure has been proposed as a resin for toner having good melt fluidity. In general, linear polyester resins have a problem that when the melt viscosity is lowered to improve the fluidity, T g is lowered, and the storage stability and anti-blocking property of the toner are lowered. Japanese Unexamined Patent Application Publication Nos. Hei 2-2693964, Hei 4-412161, Hei 5-92778, Hei 5-07705 Polyesters containing 1,2,2-bis (4-hydroxyphenyl) propane (bisphenol A) ethylene oxide or propylene oxide adduct as a diol component are described. This resin has a relatively high Tg and excellent melt flowability. However, the adduct of bisphenol A with ethylene oxide or propylene oxide usually includes an adduct having a structure in which at least two molecules of ethylene or propylene oxide are added to the OH group of bisphenol A. . Since the aliphatic ether structure contributes to lowering T g, the effect of improving T g cannot be said to be sufficient. In addition, when this polyester is discarded and left outdoors, the alkylene oxide is easily desorbed due to acid treatment conditions such as sewage treatment and acid rain, and has recently become a problem as an “environmental hormone”. Bisphenol A itself may be released to the environment.

Therefore, as a binder resin for toner, there is no environmental problem and there is no polyester resin satisfying useful melt fluidity, low-temperature adhesion, offset resistance and blocking resistance.

In Japanese Patent Publication No. 8-10358, an attempt was made to introduce an imide structure into a resin for a toner, focusing on aliphatic imide and the positive charge imparting property introduced by the aliphatic imide. It was only added or copolymerized in a small amount as a charge control agent to the resin used.

JP-A-7-16004 and JP-A-8-628-96 disclose flexible diamines. It describes a toner using a polyesterimide resin prepared by melt-polycondensing noalkane ("Jeffamine (JEFFAM IN: manufactured by Texaco Chemical Co., Ltd.)") with trimellitic anhydride.

In addition, Japanese Patent Application Laid-Open No. 7-181,738 describes a polyesterimide resin obtained by polycondensing "difamine" and pyromellitic acid anhydride.

Further, JP-A-7-160047, JP-A-7-219273, and JP-A-7-333907 also disclose unsaturated compounds together with "diphamine". Crosslinked polyesterimide resins are disclosed which are prepared by introducing groups and optionally reacting with free radical initiators.

However, all of these resins use viscous diamine "difamine" at room temperature, and therefore, handling of the resin is poor. Furthermore, `` Since polyesterimide resin obtained by polycondensation of difermin J and acid anhydride has extremely high hygroscopicity, when evaluated as a toner, the charge amount at high temperature and high humidity is not sufficiently increased, and there is a problem in fixing property. This is presumed to be due to the inclusion of ether linkages in the imide constituents.Moreover, the synthesis of diphamine itself goes through many stages, and the cost of the toner as a function of toner is low. The present invention has been problematic in that it can be used as a toner resin that is cost-effective, and an object of the present invention is to provide a novel toner composition.

Another object of the present invention is to provide a toner composition which is excellent in melt fluidity, fixability, offset resistance and blocking resistance, and which can impart a positive charge. Still another object of the present invention is to provide a polyesterimide as a binder resin for toner which provides the above-mentioned toner composition.

It is yet another object of the present invention to provide a toner composition comprising a polyesterimide having a high glass transition temperature (Tg) and a low melt fusing temperature.

Still another object of the present invention is to provide a novel binder resin for toner in which the properties of a polyester resin as a binder resin for toner are improved.

Still another object of the present invention is to provide a toner composition useful as a dry toner applicable to a hot roll fixing system, a flash fixing system and the like.

Still other objects and advantages of the present invention will become apparent from the following description. Disclosure of the invention

According to the present invention, if CN, the objects and advantages of the present invention are:

A toner composition comprising a color former and at least one polymer selected from the group consisting of A and B,

A is the following equation (1)

0

, II

-Ar— C- -0- -R] O- (1)

(Here, `` ¹ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and a group consisting of an alkylene group having 2 to 20 carbon atoms, an oxyalkylene group, and a polyxylene alkylene group. At least one selected from)

And an ester unit E represented by the following formulas (2) and (3)

(3)

(Wherein, A r ² is a trivalent or tetravalent aromatic hydrocarbon group having 2 6 carbon atoms, R ² is an alkylene group having 2 to 1 2 carbon atoms, X is, -CO- or And at least one imide unit I selected from the group consisting of units represented by the following formulas: A crosslinked polymer having a number average molecular weight of 2,000 to 10,000, a glass transition temperature of 50 to 90 ° C, a softening temperature of 90 to 160 ° C, and the following formula (A-1)

0. 0 1≤a ₂ / a, ≤0.6 0 (A— 1)

(Here, based on the whole units constituting the non-crosslinked polyesterimide A, a, is the mole percent of ester le unit E, a ₂ is the mole% of the imide units I) Is a non-crosslinked polyesterimide satisfying

B is the ester unit E, the imide unit I, and the following formulas (4) and (5)

A r ^3- (one CO-) _r one (4)

R ³ -(_〇—) _q- (5)

(Where, A r ³ is an r-valent aromatic hydrocarbon group having ⁶ to 12 carbon atoms, R ³ is a q-valent aliphatic group having 3 to 9 carbon atoms, and r and q are 3 or 4)

A cross-linked polymer mainly composed of at least one type of cross-linking unit C selected from the group consisting of the units represented by the following formulas, and in which the above three units (E, I, C) are bonded by ester bonds. The glass transition temperature is 50 to 90 ° C, the softening temperature is 90 to 190 ° C, and the following formulas (B-1) and (B-2)

0. O l ^ b ^ b ^ O. 60 (B-1)

0.0 1≤b ₃ / b ₁ ≤0.40 (B-2)

(Wherein, based on the whole units constituting the crosslinked polyesterimide B, is the mole percent of ester units E, b ₂ is the mole% of the imide units I, b ₃ is a molar% cross units C )

This is achieved by a toner composition which is a crosslinked polyesterimide satisfying the following. BEST MODE FOR CARRYING OUT THE INVENTION

The toner composition of the present invention comprises a color former and a polymer selected from the group consisting of A and B.

The polymer A is a polyesterimide mainly composed of an ester unit E represented by the above formula (1) and an imide unit I selected from the group consisting of the units represented by the above formulas (2) and (3). Resin. These units are not linked by an ether bond but are linked by an ester bond.

In the above formula (1), “ ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a 1,4-phenylene group and a 1,3-phenylene group. Examples include a diene group, a 2-phenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, and a 4,4′-biphenylene group. Among them, 1,4-phenylene group and 1,3-phenylene group are preferable. Usually a group derived from an aromatic dicarboxylic acid component.

In particular, when a 1,4-phenylene group and a 1,3-phenylene group are used in combination, the 1,4-phenylene group accounts for 50 to 80 mol% of the whole, preferably 60 to 80 mol%. 70 mol%.

R ¹ is selected from the group consisting of alkylene groups having 2 to 20 carbon atoms, xylalkylene groups and polyxylalkylene groups.

Examples of such an alkylene group include an ethylene group, a 1,2-propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a neopentylene group (a 2,2-dimethyl-1,3-propylene group), and Examples include groups represented by the following formulas (R l -1) and (R u 2).

These can be used in combination of two or more. Of these, an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group, a 2-propylene group, and a neopentylene group are more preferable.

Examples of such a xyalkylene group include a xydiethylene group and a trioxyethylene group. Among them, a xyxethylene group is preferred.

Examples of the polyxylene alkylene group include a polyxylene ethylene group and a polyoxypropylene group. The molecular weight of the polyxylene alkylene group is usually from 500 to 10,000.

These alkylene groups, substituted xyalkylene groups and polyoxyalkylene groups having 2 to 20 carbon atoms can be used in combination of two or more. In addition, these are usually groups derived from diaryl components.

The ester unit E represented by the above formula (1), for example, A r ¹ is 1, 4 one-phenylene group, 1, 3-phenylene group or a group comprising a combination thereof, and R ¹ Ethylene group, 1,2-propylene group, neopentylene group, ethylenediene or An ester unit using a group obtained by combining these groups is preferred.

In particular, when R ¹ is a xyalkylene group, it is preferably used in combination with an alkylene group. At this time, the content of the oxyalkylene group is preferably from 10 to 99 mol%, more preferably from 20 to 85 mol%, and still more preferably from 30 to 80 mol%, based on the alkylene group. Mol%.

In addition, as the above-mentioned Ar ¹ , a derivative derived from a relatively small amount of another dicarboxylic acid component other than the above may be used. Examples of such other dicarboxylic acid components include the following.

Aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, fumaric acid, adipic acid; cyclohexanedicarboxylic acid, norbornene-2, Alicyclic dicarboxylic acids such as 3-dicarboxylic acid. The proportion of the other dicarboxylic acid component used is preferably 30 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the total acid components constituting the ester unit E. is there.

Further, R ¹ may be derived from another diol component other than the above, to the extent that physical properties are not impaired. Examples of such other diol components include bisphenol A, bisphenol S, bisphenol Z, hydroquinone, 1,4-benzenediol, and 1,3-benzenediol. The amount of such another diol component is preferably 40 mol% or less, more preferably 30 mol% or less, based on the diol component constituting the ester unit E.

Further, the ester unit E may contain a small amount of a unit derived from a hydroxycarboxylic acid such as hydroxybenzoic acid and ε-hydroxyxicuronic acid. The proportion of such units is preferably at most 30 mol%, more preferably at most 20 mol%, particularly preferably at most 10 mol%, based on the ester units Ε. The formula (2), (3), eight ^"2 is a trivalent or tetravalent aromatic hydrocarbon group having 2 1 6 carbon atoms,! ^ ² is an alkylene group having 2 to 2 carbon atoms Yes, X is one CO— or one 0—.

A r ² is a trivalent or tetravalent aromatic hydrocarbon group having 6 to 2 carbon atoms. For example, the following formula (Ar2-1)

A benzene ring bonded to other atoms at 1, 2, and 4 positions represented by the following formula (Ar2-2)

A benzene ring bonded to other atoms at the 1, 2, 4, and 5 positions represented by These are groups derived from trimellitic acid or its anhydride, pyromellitic acid or its anhydride, respectively.

In R ² , examples of the alkylene group having 2 to 12 carbon atoms include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,4-tetramethylene group, and a hexmethylene group. Can be. Among them, an alkylene group having 2 to 6 carbon atoms such as an ethylene group and a 1,3-propylene group is preferable, and an ethylene group is particularly preferable. These are usually groups derived from aliphatic amino alcohols and aliphatic amino carboxylic acids.

X is one CO— or one tenth.

Suitable imide units I represented by the formula (2), for example, A r ² is 1, 2, 4 benzene combined with other atoms in the ring, R ² is an alkylene group having 2-6 carbon atoms And an imide unit in which X is —〇— or 1 CO— can be mentioned as a preferable example.

As the imide units I represented by the formula (3), for example, A r ² is 1, 2, 4, 5 in a bond with the benzene ring with another atom, R ² is 2 carbon atoms Preferred is an imide unit which is an alkylene group of 6 and X is -0- or 1CO-.

Specific examples of the imide unit I include a unit represented by the following formula.

〔twenty one)

Here, R ^{2 1} is an alkylene group having 2 to 6 carbon atoms, an ethylene group is particularly preferred. As the imide unit I, a unit composed of only the unit represented by the above formula (2-1) is particularly preferable.

The imide unit I is introduced into the polymer chain having the ester unit E by an ester bond at random or in a specific amount to give an amorphous polymer, and the polyester comprising only the ester unit E While maintaining the excellent melt fluidity possessed by the above, the polyester resin consisting of only the above ester unit alone increases the insufficient Tg and contributes to the storage stability. Further, the present invention can be applied to a positive charging developing method, which has been difficult to apply with a conventional polyester.

The polyesterimide resin A preferably has a Tg of 50 to 90 ° C and a softening temperature of 90 to 160 ° C for use as a binder resin for a toner. Here, T g is the temperature at which the inflection point rises when measured by differential scanning calorimetry (DSC) at a heating rate of 20 ° CZ. The softening temperature was measured using a Koka type flow tester, 1 g of the sample was filled under a load of 30 kg, and the temperature was gradually raised from room temperature at a rate of 3 ° CZ. 0% The temperature at the time of melting out from a nozzle with a diameter of 1 mm and a land length of 1 O mm. When the Tg of the polyesterimide A is lower than 50 ° C, the blocking resistance becomes insufficient, and when the Tg is higher than 9 (TC, the low-temperature fixability becomes insufficient. The Tg is 55 to 85 ° C When the softening temperature is lower than 90 ° C, the offset resistance becomes insufficient, and when the softening temperature is higher than 60 ° C, the fluidity of the resin decreases. It is preferable that the temperature be 0 to 150 ° C. By having such thermal characteristics, such a polyesterimide A has not only low cost but also excellent fixability derived from low melt fluidity, and resistance to high temperatures. The toner composition of the present invention having blocking properties and excellent storage stability as compared with a conventional binder resin for a toner is provided.

The molecular weight of the polyesterimide A is preferably adjusted so as to satisfy the thermal characteristics. Although depending on the constitutional unit, the number average molecular weight is preferably in the range of 2,000 to 20,000, more preferably 2,000 to 10,000, still more preferably 2,000 to 8,000, and particularly preferably 2,500 to 5,000.

The polyester imide resin A has the following formula (A-1)

0.0 1≤ a ₂ / a 0.6 0 (A- 1) is satisfied. Here, a, is the mole% of the ester unit E based on the whole units constituting the non-crosslinked polyesterimide A, and a ₂ is the mole% of the imide unit I. In the above formula (A- 1), a value of 0.0 smaller than 1 and T g is lower Li a _2, easily occurs blocking upon the Bok na scratch. On the other hand, if it is larger than 0.60, the softening temperature becomes high, and when evaluated as a toner, the fixing property is deteriorated, and the non-aged fset region becomes a high temperature region. The preferable ratio of a 1 and a 2 satisfies the range of the following formula (A-2), and more preferably the range of the following formula (A-3).

0. 05≤a ₂ / a, ≤0.5 0 (A-2)

0.1 0 ≤a ₂ / a, ≤0.40 (A-3)

The polymer B includes an ester unit E represented by the above formula (1), an imide unit I selected from the group consisting of the units represented by the above formulas (2) and (3), and the above formulas (4) and (4). 5) A crosslinked polyesterimide resin mainly composed of a crosslinking unit C selected from the group consisting of: These units are not linked by an ether bond, but are linked by an ester bond.

As the ester unit E and the imide unit I, the same units as described above can be used. The crosslinking unit C is selected from the group consisting of the above formulas (4) and (5).

In the above formula (4), " ³ is an r-valent aromatic hydrocarbon group having 6 to 12 carbon atoms. As such an aromatic hydrocarbon group, for example, 1 represented by the above formula (Ar ² -1) , 2, 4 benzene combined with other atoms in the ring, the formula. (Ar ² - ²⁾ 1 is expressed by, 2, 4, 5-position with can be mentioned benzene ring bonded with other atoms these Is a group derived from a trivalent or tetravalent aromatic polycarboxylic acid or an anhydride thereof.

r is 3 or 4.

In the above formula (5), R ³ is a q-valent aliphatic group having 3 to 9 carbon atoms. These are usually groups derived from trihydric or higher polyhydric aliphatic alcohols.

Examples of the polyhydric aliphatic alcohol component providing such an aliphatic group include glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, and tris (2-hydroxyethyl) isocyanurate. These may be used in combination of two or more. Among them, an aliphatic group having 3 to 6 carbon atoms such as glycerin, pentaerythritol and trimethylolpropane is preferable, and glycerin and pentaerythritol are more preferable.

q is 3 or 4.

The crosslinking unit C is preferably composed of a unit represented by the above formula (5).

The above polyesterimide B is represented by the following formula (B-1)

0.0 1 ≤ b ₂ / b, ≤ 0.6 0 (B-1). Here, b, is the mol% of the ester unit E, and b ₂ is the mol% of the imide unit I, based on the whole units constituting the crosslinked polyesterimide B. If bzZ ^ is smaller than 0.01, the Tg of the polymer becomes low, and blocking tends to occur when the toner is used. On the other hand, if it is larger than 0.60, the softening temperature becomes higher, and when evaluated as a toner, the fixability is poor, and the non-offset region becomes a high temperature region. The ratio between bl and b2 preferably satisfies the following expression (B_1-1), and more preferably satisfies the following expression (B1-1-2).

0.0 S ^ b ^ b ^ O. 5 0 (B-1-1)

0.1 0 ≤ b ₂ / b! ≤ 0.40 (B-1-2) In addition, the polyesterimide B has the following formula (B-2)

0.0 1 ≤ b ₃ / b, ≤ 0.4 0 (B-2) To be satisfied. Here, b, are as defined above, b ₃ is the mole percent of crosslinking units C. When bgZfch is smaller than 0.01, the softening temperature of the polymer becomes low, and the storage elastic modulus G 'measured when the temperature is changed from the softening temperature of the resin to 200 ° C using a rheometer 1 is measured. The value in the temperature range of 50 to 200 ° C is small, and when evaluated as a toner, a problem occurs in the offset resistance. On the other hand, if it is more than 30%, the softening temperature becomes high, and when evaluated as a toner, the fixability becomes poor or the production becomes difficult. The ratio between bl and b2 preferably satisfies the following expression (B-2-1), and more preferably satisfies the following expression (B-2-2).

0. 05≤ b ₃ / b! ≤0. 1 5 (B-2— 2)

The polyesterimide B preferably has a Tg of 50 to 90 ° C. and a softening temperature of 90 to 190 for use as a binder resin for a toner. Here, T g is the same as in the case of the polyesterimide A. When the softening temperature is lower than 90 ° C, the offset resistance becomes insufficient, and when the softening temperature is higher than 190 ° C, the fluidity of the resin decreases. The softening temperature is preferably from 100 to 180 ° C, more preferably from 110 to 160 ° C. By having such thermal properties, such polyesterimide B has not only low cost, but also excellent fixability derived from low melt fluidity, blocking resistance even at high temperatures, and a conventional binder for toner. The present invention provides the toner composition of the present invention which has excellent storage stability as compared with resins.

The above polymers A and B may contain, if necessary, a small amount of units functioning as heat stabilizers, oxidation stabilizers, light stabilizers, pigment dispersants, dye-fixing agents, flame retardants, etc. It may be contained in the polymer chain in an amount of at most mol%. For example, the agents represented by the following formulas (Other-1), (Other-2), and (Other-3) can be used as an easy fixing agent, a dispersant, and a flame retardant for a colorant, respectively. The desired performance of each agent can be imparted to the polymer by adding them and reacting them at the time of polymer production.

(Other-1)

(Other-2)

(Other-3)

The method for producing the polyesterimides A and B in the present invention is not particularly limited, and a conventionally known production method in the art can be employed.

For example, after the imide constituent raw materials are reacted in advance, an imide unit may be synthesized, and then the dehydration condensation may be performed simultaneously with the esterification method for producing the ester unit E, or the imide precursor may be reacted with the imide precursor. And then subjecting it to dehydration condensation simultaneously with the esterification method for producing the ester unit E, or the raw material for the ester unit and the raw material for the imide unit are placed in the same reaction system. In preparation, the formation of the imide unit I and the formation of the ester unit E may be performed simultaneously. These methods can be used as appropriate.

As the esterification method for producing the ester unit E, for example, a direct polymerization method using a dicarboxylic acid component and each glycol component as raw materials, an ester exchange polymerization method using a dicarboxylic acid ester and each daricol component as raw materials, and the like are used. can do. The imide unit I can be produced by reacting an aromatic polycarboxylic acid component with an amino alcohol component or an aminocarboxylic acid. Examples of the aromatic polycarboxylic acid component include trimellitic anhydride and pyromellitic anhydride. Of these, trimellitic anhydride is preferred in that it gives a more amorphous polyesterimide.

Examples of the amino alcohol component include ethanolamine, 2-aminopropanol, and 3-aminopropanol. Among them, ethanolamine has good reactivity, gives a more amorphous polyesterimide as described above, and when it remains as an unreacted product, it has a low boiling point, so that it can be easily removed at the latter stage of polymerization. It is good.

Examples of the amino carboxylic acid component include 3-amino carboxylic acid, amino carboxylic acid, and the like. Acid, δ-aminocarboxylic acid, and ε-aminocarboxylic acid. Among them, ε-amino carboxylic acid is preferred because it is easy to handle and can be used more inexpensively as a toner resin.

Further, the ester unit Ε can be produced by reacting an aromatic dicarboxylic acid component with a diol component. Such aromatic dicarboxylic acid components include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and alkyl esters thereof. Of these, terephthalic acid and isophthalic acid are preferred because they can be used as a toner resin at lower cost.

Examples of the diol component include, for example, alkylene glycols such as ethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propylene glycol, xyalkylene glycols such as ethylene glycol and triethylene glycol, and polyoxyethylene glycol. , Polyoxypropylene glycol and polytetraethylene glycol. Among these, ethylene glycol and 2-dimethyl-1,3-propylene glycol are preferred in that they do not lower the Tg of the obtained toner, and diethylene glycol is preferable in terms of increasing the melt fluidity of the obtained toner.

As a method for producing the polymer A, specifically, for example, a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride which is a raw material constituting the imide unit I and an aliphatic component such as ethanolamine are used. Amino alcohol and a diol component such as ethylene glycol, which is one of the raw materials constituting the ester unit E, are first mixed, and reacted at a temperature of 100 ° C or less to form an amide carboxylic acid. A method of adding an aromatic dicarboxylic acid component such as terephthalic acid, which constitutes the ester unit E, which is a raw material component, together with an oxyalkylene glycol component and / or a polyalkylene glycol component, if necessary, followed by dehydration and polycondensation. No. The amount of each raw material used is usually from 0.01 to 0.9% by mole of the diol component and from 0.99 to 0.10% by mole of the trivalent or tetravalent component relative to the aromatic dicarboxylic acid component. And an equivalent amount of an amino alcohol to the polyvalent aromatic carboxylic acid component.

In the polymer B, the imide unit I and the ester unit E can be produced by the same method as described above.

The crosslinking unit C is a trivalent or tetravalent aromatic polycarboxylic acid component, a trivalent or tetravalent polycarboxylic acid component. It can be derived from a polyhydric aliphatic alcohol component.

Specific examples of the method for producing the polymer B include, for example, a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride, which is a raw material constituting the imide unit I, and an aliphatic amino acid such as ethanolamine. Alcohol and a diol component such as ethylene glycol, which is one of the raw materials constituting the ester unit E, are initially charged and mixed, and reacted at a temperature of 100 ° C or less, and then the remaining raw material components The aromatic dicarboxylic acid component constituting the ester unit E and the aromatic polycarboxylic acid or polyaliphatic alcohol component constituting the cross-linking unit C can be combined with the polyalkylene glycol and Z or polyalkylene as required. There is a method of adding together with the recoiling component and performing polycondensation.

When a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride is used as the bridge unit C, it may be mixed at the time of charging.

When trimellitic anhydride is used for the imide unit I and the cross-linking unit C, the charging ratio (molar ratio) between trimellitic anhydride and ethanolamine is such that the trimellitic anhydride is excessive. The amount of trimellitic anhydride used is preferably up to 3 times, more preferably 1 to 2 times the amount of ethanolamine.

The polyesterimides 8 and B in the present invention can be used by being mixed with another crosslinked or non-crosslinked type binder resin for toner. Examples of other toner binder resins to be mixed with the polymer A include the above-mentioned polymer B, bisphenol-based polyester resin, polyester resin having no bisphenol-based component, and styrene-acrylic resin crosslinked resin. Can be mentioned. Examples of other binder resins for toner used by mixing with the above polymer B include the above polymer A, bisphenol-based polyester resins, polyester resins other than bisphenol-based resins, and non-crosslinked resins of styrene-acrylic resins. be able to. As described above, by mixing and using other resins, the physical properties such as Tg and storage elastic modulus G ′ of the above-mentioned polymers A and B can be increased, and the physical properties of the binder as one resin can be further improved. Therefore, when evaluated as a toner, physical properties such as offset resistance can be further improved. Usually, the polymers A and B are used in an amount of preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the whole binder resin.

For example, when the above polymer B is blended with polypropylene terephthalate having a molecular weight of 250 and a molecular weight distribution of 2.0 as another binder resin, The content of the rimer B is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 35% by weight. The resulting mixture (composition) has a number average molecular weight of 3000-50000, a molecular weight distribution of 10-20, a Tg of 60-70C, and a softening temperature of 115-25. It has well-balanced properties as a binder resin for toner at ° C.

The polyesters A and B in the present invention are appropriately mixed with additives such as a color former, a charge regulator, a wax, and a surface treating agent as a binder resin for a toner to form a toner composition.

The amount of the binder resin used in the toner composition is generally 40 to 99% by weight, and preferably 50 to 99% by weight, although it depends on a latent image forming method such as an electrophotographic method and a magnetic method.

Examples of the coloring agent include coloring agents such as pigments and dyes. Examples of pigments include Ripon Black, such as Colombian's Carbon Black Japan's furnace black trade names Raven5250, Raven5750, Raven1250, Raven1255, and magnetites, such as Colombian Magnetite's trade name MAPI CO BL AC KS And other uniform black pigments. In general, 1 to 50% by weight, preferably 1 to 30% by weight, of the star is used for the toner.

As the coloring pigments other than black, known pigments of cyan, magenta, blue, red, green, brown, yellow or mixtures thereof can be used in the same amount as the above-mentioned black pigment.

As the charge control agent, a known charge control agent can be used. Typical examples include azo metal complexes, Nigguchi syn pigments, ammonium salts, aliphatic metal salts, and the like. Generally, the amount is preferably from 15 to 15% by weight based on the toner. Can be used in amounts from 10% to 10% by weight.

As the surface treating agent, a known surface treating agent can be used. Typical examples include hydrophobic silica, alumina, titanium oxide, resin ultrafine particles, and the like. Generally, 0.1 to 10% by weight, preferably 0.1 to 7% by weight based on the toner. Can be used.

Known waxes can be used as the wax. Typically, for example, polypropylene, polyethylene (molecular weight 1 000-10000), higher fatty acid salts, etc. In general, an amount of 0.5 to 10% by weight, preferably 55% by weight, based on the toner can be used.

The above-mentioned toner composition, after containing the above-mentioned additives, is subjected to known pulverization, pulverization and classification steps, and then adjusted as toner particles having an average particle diameter of 7 to 20 m as measured by a Coulter Counter. You can do it.

The toner composition of the present invention may contain a small amount of a heat stabilizer, an oxidation stabilizer, a light stabilizer, a pigment dispersant, a dye easy fixing agent, a flame retardant, and a dye, if necessary, for example, 20% by weight of the whole. It may be included below.

The invention's effect

The toner composition of the present invention is particularly excellent in melt fluidity, fixability, offset resistance, and blocking resistance by using the above-mentioned polyester imide resin having both high Tg and low softening temperature as a binder resin. Is good. Therefore, this toner composition is extremely useful for electrophotographic printers, magnetic printers and the like.

In particular, the polyesterimide of the present invention has a feature that it can be used as a binder resin for a positively charged toner. For example, conventional polyester resins could only use the negative charging method due to the characteristics of the polymer. Since such a polyesterimide has a specific imide unit, it is easy to impart a brush charging property as compared with a conventional polyester resin, and can be used as a positive charging type toner. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. In the examples, “parts” means “parts by weight”.

The reduced viscosity (7? SpZC) of the polymer was measured using a phenol Z1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 64) at a polymer concentration of 1.2 g / d I and a temperature of 35 ° C. did.

The Tg of the polymer was determined as follows using a differential scanning calorimeter “DSC220” manufactured by Seiko Instruments Inc. First, when heated to 200 ° C in 20 ° C for 20 minutes, rapidly cooled with dry ice, and then heated again at a rate of 2 (measured around the baseline of the chart and Tg when measured at TC / min). The temperature at the intersection of the tangents to the endothermic curve was defined as Tg.

The softening temperature is 1 mm * X 10 mm using “K0KA FLOW TESTER” manufactured by Shimadzu Corporation. The measurement was performed under the conditions of a nozzle with a load of 30 kgf. This refers to the temperature at which 1/2 of 1 g of the sample melted out at an isothermal rate of 3 ° CZ for the sample.

The average molecular weight (Mw and Mn) was adjusted by dissolving 2 Omg of each sample with 1 OmI of THF, and using GPC column `` Shodex KF-80MJ in series of 4 The molecular weight of each sample was measured using a connected Shodex “GPC system-11j” and converted to standard polystyrene.

The polyesterimide resin was subjected to the following toner tests (1) to (3) and evaluated as a resin for a toner binder.

(1) Simple fixability test

Using a generally used hot-roller type fixing tester, it was examined whether or not an offset phenomenon in which the resin or toner composition adhered to the roller occurred. When the roller temperature is 160 ° C, whether the polymer does not melt and adheres to the heat roller as toner powder and print stains occur (cold offset). Each sample was tested to determine whether it was melted and adhered to the heat roller side without fixing to the test printing paper side to cause printing stains (hot offset).場合 indicates that the offset phenomenon did not occur, and X indicates that it occurred.

(2) Fixing rate test

The print density of the printed matter obtained by the simple fixing test is measured. Next, apply a sticky cellophane tape to the same place, rub it back and forth with a 1 kg roller 20 times, measure the print density after peeling off the tape, and compare the print density ratio before and after peeling the tape. The fixing rate (%) was used. The print density was measured using a reflection densitometer.

(3) Blocking test

After filling the powder sample in the container and leaving it in a 45 ° C atmosphere for one week, the powder sample was dropped from the container into a 20-mesh sieve. The case where the mass of the powder sample remaining in the sample was broken by hitting the sieve and did not remain was designated as “△”, and the condition where the mass of the powder sample remained without breaking after striking the sieve was designated as “X”.

Examples 1 to 3, Comparative Example 1

A predetermined amount of aminoethanol, trimellitic anhydride, and propylene glycol shown in the table are placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel is replaced with nitrogen gas at room temperature. Then, the reaction vessel was heated to 50 ° C. under normal pressure. After reacting for 30 minutes, Predetermined amounts of dimethyl terephthalate and diethylene glycol shown in Table 1 were added, and 4 parts of tetrabutyl titanate were further added, and the reaction vessel was heated to 200 ° C under normal pressure. After maintaining the reaction temperature at 200 ° C. for 3 hours, the temperature was raised to 220 ° C., and the reaction was further performed for 1.5 hours. At this point 36 parts of water and 560 parts of methanol were distilled off. Furthermore, the reaction was carried out at 240 ° C for 1 hour in a nitrogen stream under normal pressure, for 15 minutes under a weak vacuum of about 20 mmHg, and further for 120 minutes under a high vacuum of 1 mmHg or less. As a result, a pale yellow transparent non-crosslinked polyesterimide resin was obtained.

Table 1 shows the results of the number average molecular weight, Tg, and softening temperature of the polymer thus obtained.

In addition, 94 parts by weight of the polyesterimide resin were melt-kneaded with a twin-screw extruder while adding 5 parts by weight of carbon black and 1 part of a charge control agent. The obtained pellet was pulverized by a jet mill and classified by a classifier to obtain a toner composition having a particle size of 10 to 15 tm. Table 1 also shows the results of the evaluation of this toner composition by the above method. table 1

Example Ί 2 3 Comparative example 1 part / mole

Raw material preparation DMT 1940/100 1940/100 1940/100 1940/100

T M A 384/20 192/10 384/20

Etano-lamine 122/20 61/10 122/20

P G 1522g 1522g 1522g 1522g

D E G 637/60 637/60 739/70 637/60 Resin properties M π 7900 7900 7500 8000

T g (.C) 65 59 61 48

Softening temperature (° c) 148 1 4 138 150

Toner test i) Simple fixability

'' 〇〇セット

(2) Fixing property) 95 95 99 95

(3) r Locking property 〇〇〇 X DMT: y methyl perphthalate

ΤΜΑ: Trimellitic anhydride

P G: Huh. Lopirengeliol

D E G: S'ethylene glycol '

The polyesterimide resin of the present invention has a low Tg and a low softening temperature due to the introduction of an aromatic imide group, and is excellent in offset properties, fixing properties and blocking resistance. Has excellent characteristics.

Example 4

22 parts (20 moles) of aminoethanol, 480 parts (25 moles) of trimellitic anhydride, and 522 parts of propylene glycol were placed in a reaction vessel having a distilling system through a stirrer and a rectification column, and were placed at room temperature. The reaction vessel was replaced with nitrogen gas, and the reaction vessel was heated to 50 ° C under normal pressure. After reacting for 30 minutes, 1940 parts (100) of dimethyl terephthalate, 637 parts (60 mol) of ethylene glycol and 4 parts of tetrabutyl titanate were added, and the reaction vessel was further heated to 200 ° C under normal pressure. . After maintaining the reaction temperature at 200 ° C for 3 hours, the temperature was raised to 220 ° C and the reaction was further performed for 1.5 hours. At this point 36 parts of water and 560 parts of methanol had been distilled off. In addition, the reaction was carried out at 240 ° C for 1 hour in a nitrogen stream under normal pressure, for 15 minutes under a weak vacuum of about 20 mmHg, and for another 120 minutes under a high vacuum of 1 mmHg or less. A crosslinked polyesterimide resin was obtained.

Table 2 shows the results of the number average molecular weight, Tg, and softening temperature of the polymer thus obtained.

Comparative Example 2

1522 parts of propylene glycol, 1940 parts of dimethyl terephthalate and 4 parts of tetrabutyl titanate were added, and the mixture was placed in a reaction vessel having a distilling system via a stirrer and a rectification column.The reaction vessel was replaced with nitrogen gas at room temperature. The reaction vessel was further heated to 200 ° C. under normal pressure. After maintaining the reaction temperature at 200 ° C for 3 hours, the temperature was raised to 220 ° C and the reaction was further performed for 1.5 hours. At this point 36 parts of water and 560 parts of methanol had been distilled off. In addition, the reaction was carried out at 240 ° C for 1 hour in a nitrogen gas stream under normal pressure, for 15 minutes under a weak vacuum of about 2 OmmHg, and further for 120 minutes under a high vacuum of 1 mmHg or less. A non-crosslinked polyester resin was obtained.

Table 2 shows the number average molecular weight, Tg, and softening temperature of the polymer thus obtained. Show.

Example 5

Using 40 parts of the polyesterimide resin obtained in Example 4 and 60 parts of the polyester resin obtained in Comparative Example 2, using a twin-screw extruder (PCM 30 manufactured by Ikegai Iron Works Co., Ltd.), the cylinder temperature was 1 The mixture was melt-extruded at 70 ° C. to obtain a yellow transparent blend polymer.

Table 2 shows the results of the number average molecular weight, Tg, and softening temperature of the blend polymer obtained in this manner.

Further, to 94 parts by weight of the polyester (imide) resins of Examples 4 and 5 and Comparative Example 2, 5 parts by weight of carbon black and 1 part of a charge control agent were added and melt-kneaded by a twin-screw extruder. The obtained pellet was pulverized by a jet mill and classified by a classifier to obtain a toner having a particle diameter of 10 to 15 m.

Table 2 shows the results of evaluation of this toner by the above method.

Table 2

The polyesterimide resin for a toner according to the present invention may have an aromatic imide group introduced therein. It has a low softening temperature despite its high Tg, and has excellent offset properties, fixing properties, and blocking resistance, and has well-balanced properties as a binder resin for toner.

Examples 6 to 13

A predetermined amount of aminoethanol, trimellitic anhydride, and propylene glycol shown in Table 3 were put into a reaction vessel having a distilling system through a stirrer and a rectification column, and the reaction vessel was filled with nitrogen gas at room temperature. The reaction vessel was replaced, and the reaction vessel was heated to 50 ° C under normal pressure. After reacting for 30 minutes, predetermined amounts of dimethyl terephthalate, diethylene glycol and polyhydric diol shown in Table 3 were added, 60 parts of tetrabutyl titanate was further added, and the reaction vessel was heated to 200 ° C under normal pressure. After maintaining the reaction temperature at 200 ° C for 8 hours, the temperature was raised to 230 ° C and the reaction was further performed for 2 hours. At this point 550 parts of water and 910 parts of methanol had been distilled off. Furthermore, the pressure was reduced from 760 mm Hg to 5 mm Hg over 1 hour, and the reaction was further performed under a high vacuum of 3 mm Hg or less for 1.5 hours to finally obtain a crosslinked polyesterimide resin.

The obtained polymer was pale yellow and transparent, was insoluble in THF, and the molecular weight could not be measured.

Tables 3 and 4 show the results of the number average molecular weight, Tg, and softening temperature of this polymer. Table 3

Example 6 7 8 9

Parts / mole

Raw material preparation D T 29 100/100 29 100/100 29 100/100 29 100/100

TM A 5910 / 20.5 8790 / 30.5 5910 / 20.5 5910 / 20.5 Ethano-lamine 1830/20 2745/30 1830/20 1830/20

P G 22830g 22830g 22830g 22830g

D E G 9550/60 9550/60 9550/60 9550/60

Gericerin 1380/10 1380/10 2072/15

Trimetyro-Ruf. Loha. 1006/5

What. Center I restrol

Resin properties T g (.C) 63 67 61 62

Softening temperature C) 179 158 158 150 Table 4

Reference example 1

1522 parts of propylene glycol, 1940 parts of dimethyl terephthalate, and 4 parts of tetrabutyl titanate were added, and the mixture was placed in a reaction vessel having a distilling system via a stirrer and a rectification column. Then, the reaction vessel was further heated to 200 ° C. under normal pressure. After maintaining the reaction temperature at 200 ° C. for 3 hours, the temperature was raised to 220 ° C. and further reacted for 1.5 hours. At this point 36 parts of water and 560 parts of methanol were distilled off. Furthermore, the reaction was carried out at 240 ° C for 1 hour in a nitrogen stream under normal pressure, for 15 minutes under a weak vacuum of about 20 mmHg, and further for 120 minutes under a high vacuum of 1 mmHg or less. To obtain a non-crosslinked polyester resin. The obtained polymer was colorless and transparent, had a number average molecular weight of 250, Tg of 61 ° C, and a softening temperature of 11 ° C.

Examples 14 to 17

Each of the polyesterimide resins obtained in Examples 6 to 8 and the polyester resin obtained in Reference Example 1 were subjected to a biaxial extruder (PCM 3 manufactured by Ikekai Iron Works Co., Ltd.) in a specific composition ratio shown in Table 5 below. Using 0), the composition was melt-extruded and mixed at a cylinder temperature of 230 ° C. to produce a composition.

The obtained blend polymer (composition) was yellow and transparent. Number average molecular weight, glass Table 5 shows the transition temperature and softening temperature.

To 94 parts by weight of each of the above compositions, 5 parts by weight of carbon black and 1 part of a charge control agent were respectively added and melt-kneaded by a twin screw extruder. The obtained pellets were pulverized by a jet mill and classified by a classifier to obtain a toner having a particle size of 10 to 15 m.

Table 5 shows the results of the evaluation of this toner by the above method.

Table 5

Example 18 to 20

A predetermined amount of aminoethanol, polycarboxylic anhydride, and ethylene glycol shown in Table 6 were placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel was filled with nitrogen gas at room temperature. The reaction vessel was replaced, and the reaction vessel was heated to 50 ° C under normal pressure. After reacting for 30 minutes, add the prescribed amounts of dimethyl terephthalate, diethylene glycol or neopentyl glycol, and glycerin shown in Table 6 and then add 60 parts of tetrabutyltyl titanate. Heated to C. After maintaining the reaction temperature at 200 ° C. for 8 hours, the temperature was raised to 230 ° C., and the reaction was further performed for 2 hours. At this point, water and methanol were distilled off. Further, the pressure was reduced from 76 Omm Hg to 5 mm Hg over 1 hour, and further reduced to 3 mm Hg The mixture was reacted under the following high vacuum for 1.5 hours to finally obtain a crosslinked polyesterimide resin. C The obtained polymer was pale yellow and transparent, and was insoluble in THF, and its molecular weight could not be measured.

Table 6 shows the results of the number average molecular weight, Tg, and softening temperature of this polymer. Table 6

P M A: Hyromellitic anhydride Example 21 to 22

A predetermined amount of aminoethanol, trimellitic anhydride, and ethylene glycol shown in Table 7 were placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel was replaced with nitrogen gas at room temperature. Then, the reaction vessel was heated to 50 ° C. under normal pressure. After reacting for 30 minutes, add the specified amount of dimethyl terephthalate, dimethyl isophthalate, diethylene dalichol or neopentyl dalicol shown in Table 7, and further add 4 parts of tetrabutyl titanate. Was heated to 2000C. After maintaining the reaction temperature at 200 ° C. for 3 hours, the temperature was raised to 220 ° C., and the reaction was further performed for 1.5 hours. At this point, 36 parts of water and 560 parts of methanol were distilled off. Further, the reaction was carried out at 240 ° C for 1 hour in a nitrogen stream under normal pressure, for 15 minutes under a weak vacuum of about 20 mm Hg, and further for 120 minutes under a high vacuum of 1 mmHg or less. Finally, a pale yellow transparent non-crosslinked polyesterimide resin was obtained. Table 7 shows the results of the number average molecular weight, Tg, and softening temperature of the polymer thus obtained.

DM I: methyl isophthalate

Claims

The scope of the claims

1-a toner composition comprising a color former and at least one polymer selected from the group consisting of A and B,

A is the following equation (1)

0 0

II, II

C—— Ar— C- -0 R ¹ —— 0- (1)

(Where, A r ¹ is a divalent aromatic hydrocarbon group having 6 to 2 carbon atoms, and R ¹ is a group consisting of an alkylene group, an oxyalkylene group and a polyoxyalkylene group having 2 to 20 carbon atoms. At least one selected)

And an ester unit E represented by the following formulas (2N) and (3)

0

II

-C- -Ar 'N- -R-X- (2)

(Wherein, A r ² is a trivalent or tetravalent aromatic hydrocarbon group having 2 6 carbon atoms, R ² is an alkylene group of 2 to 1 2 carbon atoms, X is one CO- or — 0—) and at least one imide unit I selected from the group consisting of units represented by the general formula (I), wherein the two units (E, I) are linked by an ester bond. A cross-linked polymer having a number average molecular weight of 2000-10000, a glass transition temperature of 50-90 ° C, a softening temperature of 90-160 ° C, and the following formula (A-1)

0.01≤a ₂ / a ^ 0.60 (A- 1)

(Here, based on the whole units constituting the non-crosslinked polyesterimide A, a, is the mole percent of ester le unit E, a ₂ is the mole% of the imide units I)

Is a non-crosslinked polyesterimide satisfying

B is the ester unit E, the imide unit I, and the following formulas (4) and (5) A r ³ -(-CO-) _r- one (4)

R ³ — (-0-) _q — (5)

(Where, A r ³ is an r-valent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is a q-valent aliphatic group having 3 to 9 carbon atoms, and r and q are 3 or 4)

A cross-linked polymer mainly composed of at least one type of cross-linking unit C selected from the group consisting of units represented by the following formula, and wherein the above three units (E, I, C) are linked by an ester bond: The glass transition temperature is 50 to 90 ° C, the softening temperature is 90 to 190 ° C, and the following formulas (B-1) and (B-2)

0.0 1 ≤ b ₂ / b, ≤ 0.60 (B-1)

0.0 1 ≤ b ₃ / b, ≤ 0.40 (B-2)

(Here, based on the whole units constituting the crosslinked polyesterimide B, 13, is the mole percent of ester units E, b ₂ is the mole% of the imide units I, b ₃ is molar% cross units C Is)

A crosslinked polyesterimide that satisfies the following.

2. The toner composition according to claim 1, wherein R ¹ in the formula (1) is at least one selected from the group consisting of an alkylene group having 2 to 6 carbon atoms and a xyalkylene group.

3. A r ¹ in the formula (1) is 1, 4 one phenylene group and 1, is at least one selected from 3-phenylene group, claim 1 toner composition.

4. The toner composition according to claim 1, wherein R ² in the above formula (2) is an alkylene group having 2 to 6 carbon atoms, and X is —.

5. Ar ² in the above equation (2) is the following equation (Ar2-1)

The toner composition according to claim 1, which is a benzene ring bonded to another atom at the 1, 2, and 4 positions represented by

6. The non-crosslinked polyesterimide A has the following formula (A-2)

0.05 ≤ a ₂ / a, ≤ 0.50 (A— 2)

(Here, the definition of a ,, a ₂ are as defined above)

The toner composition according to claim 1, which satisfies the following.

7. The crosslinking unit C has the following formula (5-1)

R ³¹ -(-0-) 3-(5-1) (where R ³¹ is a trivalent aliphatic group having 3 to 6 carbon atoms)

The toner composition according to claim 1, which is represented by the following formula.

8. The crosslinked polyesterimide B has the following formula (B-1-1) and (B-2-1)

0. 05≤ b no b ^ O. 50 (B-1-Ί)

0. 0 3≤ b ₃ / b, ≤ 0.20 (B- 2-1)

(Where the definitions of b ₂ and b ₃ are the same as above)

The toner composition according to claim 1, which satisfies the following.

9. The toner composition according to claim 1, wherein the number average molecular weight of the non-crosslinked polyesterimide A is from 2,500 to 8,000.

10. The toner composition according to claim 1, wherein the proportion of the polymer in the toner composition is 40 to 99% by weight.

11. A toner composition comprising a color former and at least one polymer selected from the group consisting of A and B,

A is the following formula (111)

0 0

II ^ II

c 夺 0- -R ¹¹ — 0- (1 -1)

(Where R ¹¹ is a group consisting of an alkylene group having 2 to 6 carbon atoms and At least one selected from

And an ester unit E represented by the following formula (2-1)

(2-1)

(Where R ²¹ is an alkylene group having 2 to 5 carbon atoms)

The above two units (E, I) are non-crosslinked polymers linked by an ester bond, have a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of 55 to 85 ° C, softening temperature 90 to 50 ° C, and the following formula (A-2)

0.0 S ^ a ^ a ^ O. 50 (A-2)

(Here, based on the total moles of units constituting the non-crosslinked polyesterimide A, a, is the mole percent of ester units E, a ₂ is the mole% of the imide units I)

Is a non-crosslinked polyesterimide satisfying

B is an ester unit E represented by the above formula (1 -1), an imide unit I represented by the above formula (2-1), and an imide unit I represented by the following formula (5-1)

R ³¹ -(-0-) 3-(5-1)

(Here, R ³¹ is an aliphatic group having 3 to 6 carbon atoms.)

A cross-linked polymer mainly composed of a cross-linking unit C represented by the following formula, wherein the above three units (E, I, C) are bonded by an ester bond, and have a glass transition temperature of 55 to 85. And a softening temperature of 110 to 160 ° C., and the following formulas (B-1-1) and (B-2-1)

0.0 S ^ b ^ b ^ O. 50 (B-1-1)

0.03≤b ₃ / b ₁ ≤0.20 (B-2-1)

(Here, based on the total moles of units constituting the crosslinked polyesterimide B, b, is the mole percent of ester units E, b ₂ is the mole% of the imide units I, b ₃ is the bridging unit

C mole%)

A crosslinked polyesterimide that satisfies the following. Three

Below

1 2. The method according to claim 1, wherein the proportion of the polymer in the toner composition is 40 to 99% by weight.

Item 11. The toner composition according to Item 11.

—

(Where, is a divalent aromatic hydrocarbon group having 6 to ¹² carbon atoms, and R ¹ is selected from the group consisting of an alkylene group having 2 to 20 carbon atoms, a xylylene group and a polyxylene group. At least one

And an ester unit E represented by the following formulas (2) and (3)

Ar; N IT-I X- (2)

(3)

(Where ₁ « ² is a trivalent or tetravalent aromatic hydrocarbon group having 6 to ¹² carbon atoms, R ² is an alkylene group having 2 to 2 carbon atoms, and X is one CO— or — 0—) and at least one imide unit I selected from the group consisting of units represented by the general formula (I), wherein the two units (E, I) are linked by an ester bond. It is a crosslinked polymer having a number average molecular weight of 2000-10000, a glass transition temperature of 50-90C, a softening temperature of 90-160 ° C, and the following formula (A-1)

0.0 1≤ a ₂ / a 0.60 (A- 1)

(Here, based on the total number of moles of the units constituting the non-crosslinked polyesterimide A, a, is the mole% of the ester unit E, and a ₂ is the mole% of the imide unit I)

Non-crosslinked polyesterimide suitable for toner which satisfies the following.

1 4. In the above formula (1), R ¹ is at least one selected from the group consisting of an alkylene group having 2 to 6 carbon atoms and a methoxyalkylene group, and Ar ¹ is a 1,4-phenylene group and 14. The non-crosslinked polyesterimide suitable for toner according to claim 13, which is at least one member selected from 1,3-phenylene groups.

1 5. R ² in the above formula (2) is an alkylene group having 2 to 5 carbon atoms, X is —0—, and Ar ² is the following formula (Ar2-1)

14. The non-crosslinked polyesterimide suitable for toner according to claim 13, which is a benzene ring bonded to another atom at the 1, 2, and 4 positions represented by

1 6. R ¹ in the above formula (1) is at least one selected from the group consisting of an alkylene group having 2 to 6 carbon atoms and a substituted xyalkylene group, wherein is 1,4-phenylene group and 1,3 - at least one selected from phenylene group, R ² is an ethylene group that put in the equation (2), X gar is O-, a r ² is represented by the following formula (Ar @ 2 - 1)

Is a benzene ring bonded to other atoms at the 1, 2, and 4 positions, with a number average molecular weight of 2500 to 8000, a glass transition temperature of 55 to 85 ° C, and a softening temperature of 95 to 13 0 ° C and the following formula (A-2)

0.05≤a ₂ / a ₁ ≤0.5 0 (A-2)

(Here, the definition of a ,, a ₂ are as defined above)

14. A non-crosslinked polyesterimide suitable for a toner according to claim 13, which satisfies the following.

1 7. alkylene group is an ethylene group having 2 to 6 carbon atoms in R ^1, 1, 2-propylene is a group or a neopentylene group, suitable non-crosslinked Polje Suteruimido for toners according to claim 1 6, wherein. 8 l

(1)

(Where, 8 is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹ is an alkylene group having 2 to 20 carbon atoms) / one group, a xyalkylene group and a polyoxyalkylene group. At least one selected from)

Represented by and (3)

(2)

No

X- -R-one N 'Ar: N R—— X- (3)

(Where ² is a trivalent or tetravalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² is an alkylene group having 2 to 12 carbon atoms, and X is one CO— or At least one imide unit I selected from the group consisting of units represented by the following formulas (4) and (5)

A r ³ — (—CO—) _r- (4)

R ³ -(-0-). - (Five)

(Where A r ³ is an r-valent aromatic hydrocarbon group having ⁶ to 12 carbon atoms, R ³ is a q-valent aliphatic group having 3 to 9 carbon atoms, and r and q are 3 or 4)

And at least one type of cross-linking unit selected from the group consisting of units represented by the following formulas. Further, the above-mentioned three units (E, I, C) are cross-linked polymers linked by ester bonds. Has a glass transition temperature of 50 to 90 ° C, a softening temperature of 90 to 190 ° C, and the following formulas (B-1) and (B-2)

0.1 O ^ b ^ b ^ O. 60 (B-1)

0.0 1≤b ₃ / b ₁ ≤0.30 (B-2)

(Here, b, is based on the total number of moles of the units constituting the crosslinked polyesterimide B. B ₂ is the mole% of the imide unit I, and b ₃ is the mole% of the cross-linking unit C.

A crosslinked polyesterimide suitable for toner satisfying the following conditions.

1 9. R ¹ in the above formula (1) is at least one selected from the group consisting of an alkylene group having 2 to 6 carbon atoms and a substituted xyalkylene group, and Ar is 1,4-phenylene group and The crosslinked polyesterimide for toner according to claim 18, wherein the crosslinked polyesterimide is at least one selected from 1,3-phenylene groups.

20. In the above formula (2), R ² is an alkylene group having 2 to 5 carbon atoms, X is —0—, and Ar ² is the following formula (Ar2-1)

19. The crosslinked polyesterimide suitable for toner according to claim 18, which is a benzene ring bonded to another atom at the 1, 2, and 4 positions represented by

2 1. Is at least one R ¹ is selected from the group consisting of an alkylene group and old Kishiarukire emissions groups from 2 to 6 carbon in the formula (1), A r ¹ is 1, 4 one phenylene group and At least one selected from 1,3-phenylene groups, R ^{2 in} the above formula (2) is an ethylene group, X is —0—, and Ar ² is the following formula (Ar2- 1)

And a benzene ring bonded to other atoms at the 2- and 4-positions, and the bridging unit C is represented by the following formula (5-1)

3 ¹ -(-0-) _3- (5-1) (where R ³¹ is an aliphatic group having 3 to 6 carbon atoms)

Having a glass transition temperature of 55 to 85 ° C, a softening temperature of 110 to 160 ° C, and the following formulas (B-1-1) and (B-2 — 1)

0.0 ≤ b ₂ /. 50 (B-1-1)

0.03≤ b ₃ / b τ≤0.20 (B- 2-1)

(Where bb ₂ and b ₃ are defined as above)

A crosslinked polyesterimide suitable for a toner according to claim 18, which satisfies the following.

22. The crosslinked polyesterimide suitable for toner according to claim 21, wherein the alkylene group having 2 to 6 carbon atoms in R ¹ is an ethylene group, a 1,2-propylene group or a neopentylene group.