JP7739729B2 - Polyester resin, its manufacturing method, and toner - Google Patents

Description

The present invention relates to a polyester resin with good wax dispersibility.

Polyester resins are used in a wide range of applications, such as coating materials, adhesives, films, and electrophotographic toners, and are blended with a variety of functional materials depending on the application.
For example, when a polyester resin is used as a binder resin for a toner, it is known to blend a wax into the polyester resin in order to impart releasability and sharp melting properties.
However, since the compatibility between polyester resin and wax is poor, the dispersion state of the wax component tends to be uneven, and therefore, improvements in the dispersibility of wax in polyester resin have been studied.

For example, Patent Document 1 discloses a technology for providing a toner having good fixing performance, anti-offset properties, image stability, and durability, as well as excellent color development and color reproducibility usable for color printing, by using a polyester resin with high light transmittance polymerized in the presence of a long-chain alkyl group having a specific functional group at its terminal. Patent Document 2 discloses a technology for providing a toner having good fixing performance, anti-offset properties, image stability, and durability by using a toner binder resin composition containing a polyester resin containing a structural unit derived from oxidized polyolefin and an oxidized polyolefin. Patent Document 3 discloses a technology for providing a toner having excellent both hot offset resistance and charging properties by using a toner polyester obtained in the presence of a wax having a polar group.

Japanese Patent Application Laid-Open No. 2007-133391 Japanese Patent Application Laid-Open No. 2008-158502 Japanese Patent Application Laid-Open No. 2006-18032

However, in the methods described in Patent Documents 1 and 2, modifier particles having a particle size larger than the toner particle size tend to remain in the resin, and the modifier particles themselves become a cause of problems, particularly in toners produced by a production method that does not involve melt-kneading, such as a chemical method. Also, the polyester resins described in Patent Documents 1, 2, and 3 do not have sufficient dispersibility for wax.

Therefore, an object of the present invention is to provide a polyester resin that does not leave any modifier particles of 10 μm or more in size at the stage before the melt-kneading step.
Another object of the present invention is to provide a polyester resin having good wax dispersibility.

The present invention has the following aspects.
[1] A polycarboxylic acid-derived structural unit (C1) and a polyhydric alcohol-derived structural unit (D
1), a constituent portion (A1) derived from an aliphatic hydrocarbon-based modifier (modifier A) having a melting point of 90°C or higher and a functional group capable of reacting with an acid or alcohol, and a constituent portion (A2) derived from an aliphatic hydrocarbon-based modifier (modifier B) having a melting point of less than 90°C and a functional group capable of reacting with an acid or alcohol.
and a constituent moiety (B1) derived from (A1), wherein the mass ratio of the constituent moiety (A1) to the constituent moiety (B1) is in the range of 1:2 to 12.
[2] The polyester resin according to [1], wherein the melting point of the modifier A is 120°C or less.
[3] The polyester resin according to [1] or [2], wherein the modifier A contains at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol.
[4] The polyester resin according to any one of [1] to [3], wherein the amount of the constituent moiety (A1) is in the range of 0.2% by mass to 3% by mass based on 100% by mass of the polyester resin.
[5] The polyester resin according to any one of [1] to [4], wherein the melting point of the modifier B is 60°C or higher.
[6] The modifier B contains at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. [1] Polyester resin according to any one of [5] to [6].
[7] The polyester resin according to any one of [1] to [6], wherein the amount of the constituent moiety (B1) is in the range of 0.5% by mass to 8% by mass based on 100% by mass of the polyester resin.
[8] A toner using the polyester resin according to any one of [1] to [7].
[9] A method for producing a polyester resin in which a monomer mixture containing a polycarboxylic acid and a polyhydric alcohol is polycondensed in the presence of an aliphatic hydrocarbon-based modifier (modifier A) having a melting point of 90 ° C. or higher and a functional group capable of reacting with an acid or alcohol, and an aliphatic hydrocarbon-based modifier (modifier B) having a melting point of less than 90 ° C. and a functional group capable of reacting with an acid or alcohol, wherein the amount of modifier B added is in the range of 1 to 6, where the amount of modifier A added is 1.
A method for producing polyester resin.
[10] The method for producing a polyester resin according to [9], wherein the melting point of the modifier A is 120°C or less.
[11] The method for producing a polyester resin according to [9] or [10], wherein the modifier A contains at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol.
[12] The method for producing a polyester resin according to any one of [9] to [11], wherein the amount of modifier A added is in the range of 0.5% by mass to 5% by mass based on 100% by mass of the resulting polyester resin.
[13] The method for producing a polyester resin according to any one of [9] to [12], wherein the melting point of the modifier B is 60°C or higher.
[14] The method for producing a polyester resin according to any one of [9] to [13], wherein the modifier B contains either a substance having an acid or alcohol at one end of a linear alkyl group, or an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol.
[15] The method for producing a polyester resin according to any one of [9] to [14], wherein the amount of modifier B added is in the range of 0.5% by mass to 8% by mass based on 100% by mass of the resulting polyester resin.
[16] A polycarboxylic acid-derived structural unit (C1) and a polyhydric alcohol-derived structural unit (
D1), a constituent portion (at least one of a12 to a15) having a carbon number (16+2n, n is at least one integer from 12 to 15) derived from modifier A, and constituent portions (ab3 to ab8) having a carbon number (16+2m, m is all integers from 3 to 8) derived from modifier A and modifier B,
A polyester resin in which the detection signal intensity derived from ab8 is 0.01 or more and 0.05 or less when the detection signal intensity derived from ab4 is taken as 1 in a chromatogram at m/z=87 in reaction PyGC-MS measurement.
[17] The polyester resin according to [16], wherein the modifier A includes constituent moieties (a0 to a15) having a carbon number (16+2n, n is an integer from 0 to 15).
[18] The polyester resin according to [16], wherein the modifier B has a constituent moiety (at least one of b3 to b5) having a carbon number (16 + 2p, where p is at least one integer from 3 to 5).
[19] Modifier B does not have a constituent moiety derived from a carbon chain having more than 40 carbon atoms, [1
8] The polyester resin according to [8].
[20] A toner using the polyester resin according to any one of [16] to [19].

According to the present invention, it is possible to provide a polyester resin that does not leave any components of 10 μm or more at the stage before the melt-kneading process. By using a polyester resin that does not leave any components of 10 μm or more at the stage before the melt-kneading process, it is possible to provide a toner that reduces defects caused by the particle size of particles contained in the polyester resin.
Furthermore, the present invention can provide a polyester resin having good wax dispersibility. The polyester resin of the present invention has good wax dispersibility, and therefore can provide a toner having good low-temperature fixability and blocking resistance.

Reaction PyGC-MS measurement results of polyester resin 1 at m/z=87. 1 is an enlarged view of the results of reactive PyGC-MS measurement of polyester resin 1 at m/z=87. Reaction PyGC-MS measurement results for Modifier A at m/z=87. Reaction PyGC-MS measurement results for Modifier B at m/z=87. Reaction PyGC-MS measurement results for Modifier B at m/z=87.

<Polyester resin>
The polyester resin of the present invention has a constituent moiety (C1) derived from a polycarboxylic acid, a constituent moiety (D1) derived from a polyhydric alcohol, a constituent moiety (A1) derived from an aliphatic hydrocarbon-based modifier (modifier A) having a melting point of 90°C or higher and a functional group capable of reacting with an acid or alcohol, and a constituent moiety (B1) derived from an aliphatic hydrocarbon-based modifier (modifier B) having a melting point of less than 90°C and a functional group capable of reacting with an acid or alcohol, and the mass ratio of the constituent moiety (A1) derived from modifier A to the constituent moiety (B1) derived from modifier B is in the range of 1:2 to 12.
The constituent moiety (C1) includes not only polycarboxylic acids but also those derived from their acid anhydrides and lower alkyl esters (hereinafter referred to as "equivalent raw materials"). Hereinafter, polycarboxylic acids and their equivalent raw materials will be collectively referred to as "polycarboxylic acid raw materials." Furthermore, when the term "carboxylic acid raw material" is used with a valence number, the equivalent raw materials will also be included.

<Polycarboxylic acid raw material>
The polycarboxylic acid raw material includes dicarboxylic acids, tricarboxylic or higher carboxylic acids, and equivalent raw materials thereof.
Examples of dicarboxylic acid raw materials include terephthalic acid, isophthalic acid, and isomers of naphthalenedicarboxylic acid (specifically, 1,4-, 1,5-, 1,6-, 1,7-, 2,5-
, 2,6-, 2,7-, 2,8-) and other aromatic dicarboxylic acids, as well as raw materials equivalent thereto; succinic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid,
Examples of the lower alkyl esters of terephthalic acid and isophthalic acid include dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, and the like.
Examples include dibutyl terephthalate and dibutyl isophthalate.
Of these, terephthalic acid, isophthalic acid, and adipic acid are preferred as divalent carboxylic acid raw materials in terms of ease of handling and cost.
These divalent carboxylic acid raw materials may be used alone or in combination of two or more kinds, and may also be used in combination with a trivalent or higher carboxylic acid raw material described below.

Examples of the trivalent or higher carboxylic acid raw material include trimellitic acid, pyromellitic acid, 1,
2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,
2,4-naphthalenetricarboxylic acid, and 1,2,5-hexanetricarboxylic acid, 1,2
, 7,8-octanetetracarboxylic acid, and their equivalent raw materials.
As the trivalent or higher carboxylic acid raw material, trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride are preferred in terms of excellent handleability and cost, and trimellitic acid and its anhydride are particularly preferred.

<Polyhydric alcohol>
The polyhydric alcohols include dihydric alcohols and trihydric or higher alcohols.
Examples of dihydric alcohols include polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(2.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, and polyoxypropylene-(2.3)-2,2-bis(4-hydroxyphenyl)propane.
aromatic alcohols such as bis(4-hydroxyphenyl)propane, polyoxypropylene(2.2)-polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2.4)-2,2-bis(4-hydroxyphenyl)propane, and polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, neopentyl glycol, propylene glycol, hexanediol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, D-isosorbide, L-isosorbide, isomannide, and erythritan;
Aliphatic alcohols such as 1,4-dihydroxy-2-butene are included.
These may be used alone or in combination of two or more thereof, and may also be used in combination with a trihydric or higher alcohol described below.

Examples of trihydric or higher alcohols include sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2
, 3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, glycerin, and the like.
Of these, trimethylolpropane and glycerin are preferred in terms of reactivity, ease of handling, and cost.

<Constituent parts derived from modifier A and constituent parts derived from modifier B>
The polyester resin of the present invention has a constituent moiety derived from modifier A and a constituent moiety derived from modifier B. To obtain a polyester having a constituent moiety derived from modifier A and a constituent moiety derived from modifier B, a monomer mixture containing a polycarboxylic acid raw material and a polyhydric alcohol is polycondensed in the presence of modifier A and modifier B. By polycondensing a monomer mixture containing a polycarboxylic acid raw material and a polyhydric alcohol in the presence of modifier A and modifier A, functional groups reactive with acid or alcohol possessed by modifier A and modifier B condense with the polycarboxylic acid raw material and the polyhydric alcohol, and a constituent moiety derived from modifier A and a constituent moiety derived from modifier B, i.e., a moiety containing an aliphatic hydrocarbon group, is introduced into the polyester resin. Aliphatic hydrocarbon groups are highly compatible with wax components, and their introduction into a polyester resin can improve the dispersibility of the wax.
In the present invention, by using a combination of modifier A having a melting point of 90°C or higher and modifier B having a melting point of less than 90°C, aliphatic hydrocarbon groups with different carbon chain lengths are introduced into the polyester resin, which is thought to have significantly improved wax dispersibility.
Or, even if only the constituent parts derived from modifier B are contained, the wax dispersibility is improved compared to when the constituent parts derived from modifier A or modifier B are not contained, but by using both modifier A and modifier B, a significant effect can be obtained.
Specifically, by having both constituent parts derived from modifier A and constituent parts derived from modifier B in the polyester resin, the wax dispersibility is significantly improved, and when used as a binder resin for toner, the resulting toner has extremely good low-temperature fixing properties, blocking resistance, offset resistance, and durability.

<Modifier A>
Modifier A is an aliphatic hydrocarbon-based modifier having a melting point of 90° C. or higher and having a functional group capable of reacting with an acid or alcohol.
The functional group capable of reacting with an acid or alcohol is not particularly limited, but examples thereof include a carboxy group or anhydride thereof, a hydroxyl group, an ester group, a glycidyl group, an alkoxy group, an isocyanate group, etc. Among these, a carboxy group or anhydride thereof, a hydroxyl group, and an ester group are preferred.
The melting point of modifier A is 90°C or higher, preferably 95°C or higher and 120°C or lower, and more preferably 100°C or higher and 115°C or lower. By making the melting point of modifier A 90°C or higher, wax dispersibility can be improved. Furthermore, by making the melting point of modifier A 120°C or lower, the reactivity between the functional groups of modifier A and the functional groups at the polyester terminals is increased, and constituent sites derived from modifier A can be effectively imparted to the polyester resin.
Modifier A preferably contains either a substance having an acid or alcohol at one end of a linear alkyl group, or an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. By having a functional group at one end of the linear alkyl group, a constituent moiety derived from modifier A can be bonded to the end of the polyester resin. By bonding to the end of the polyester resin, the compatibility of the constituent moiety derived from modifier A with the wax is improved, and wax dispersibility is improved.
In a structure having a functional group at the end of a linear alkyl group, the melting point is around 90°C when the number of carbon atoms in the linear alkyl group is approximately 30. The constituent portion derived from modifier A preferably has a structure containing a linear alkyl group having 32 or more carbon atoms. For example, a structure containing a linear alkyl group having 36 to 70 carbon atoms or a structure containing a linear alkyl group having 36 to 60 carbon atoms is preferred.

The amount of the constituent moiety derived from modifier A is preferably in the range of 0.2% to 3% by mass based on 100% by mass of the polyester resin. A content of 0.2% by mass or more improves wax dispersibility. Furthermore, a content of 3% by mass or less improves the reactivity during resin production and the storage stability of the resulting resin. The lower limit of the amount of the constituent moiety derived from modifier A is more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more.
As long as the amount of the component derived from modifier A that constitutes the polyester resin is within the above range, modifier A itself can be used as a mixture without being bonded to the polyester resin. However, in toners and the like produced by a manufacturing method that does not include a melt-kneading step, large particles of each component can cause problems, so it is preferable that the particle size of each mixed component be less than 10 μm.

Modifier A includes terminal acid-modified polyethylene waxes manufactured by Baker Hughes, such as Unicid 350, Unicid 425, Unicid 550, and Unicid 700; Unilin 42
5. Alcohol-terminated polyethylene waxes manufactured by Baker Hughes, such as Unilin 550 and Unilin 700; Epolene E-10J and Epolene E-
14, oxidized polyethylene waxes such as Clariant's Licowax PED-822 and Innospec's Viscowax 262; etc. can be used. These can be used alone or in combination of two or more. For example, Unicid 700 can be used alone as modifier A, or Unicid 700 can be used in combination with Epolene E-10J as modifier A.

In this specification, among the constituent parts derived from modifier A, the constituent parts derived from a component with a carbon number of (16 + 2n) are denoted as an (n is an integer of 0 or more). For example, the constituent part derived from a component with a carbon number of 16 is denoted as a0, and the constituent part derived from a component with a carbon number of 32 is denoted as a8.

<Modifier B>
Modifier B is an aliphatic hydrocarbon-based modifier having a melting point of less than 90° C. and a functional group capable of reacting with an acid or alcohol.
The functional group capable of reacting with an acid or alcohol is not particularly limited, but examples thereof include a carboxy group or anhydride thereof, a hydroxyl group, a glycidyl group, an alkoxy group, an isocyanate group, and an ester group. Of these, a carboxy group or anhydride thereof, a hydroxyl group, and an ester group are preferred.
The melting point of the modifier B is preferably 60° C. or higher and lower than 90° C., more preferably 65° C. or higher and lower than 90° C., and even more preferably 70° C. or higher and lower than 90° C. By making the melting point 60° C. or higher, wax dispersibility is improved.
Modifier B preferably contains either a substance having an acid or alcohol at one end of a linear alkyl group, or an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. By having a functional group at the end of the linear alkyl group, a component derived from modifier B can be bonded to the end of the polyester resin. By bonding to the end of the polyester resin, the compatibility of the component derived from modifier B with the wax is improved, and wax dispersibility is improved.
In order to make the melting point of the modifier B less than 90°C, the constituent portion derived from the modifier B must have a carbon number of 30 or less.
The following structures containing a linear alkyl group are preferred: For example, a structure containing a linear alkyl group having 28 to 18 carbon atoms, or a structure containing a linear alkyl group having 28 to 20 carbon atoms.

In this specification, among the constituent parts derived from modifier B, the constituent part derived from a component with a carbon number of (16 + 2p) is denoted as bp (p is an integer of 0 or more). For example, the constituent part derived from a component with a carbon number of 16 is denoted as b0, and the constituent part derived from a component with a carbon number of 32 is denoted as b8.

The amount of the constituent moiety derived from Modifier B is preferably in the range of 0.5% to 8% by mass based on 100% by mass of the polyester resin. A content of 0.5% by mass or more improves wax dispersibility. Furthermore, a content of 8% by mass or less improves reactivity during resin production and storage stability of the resulting resin.
As long as the amount of the component derived from modifier B that constitutes the polyester resin is within the above range, the modifier B itself can be mixed without being bonded to the polyester resin. However, in toners manufactured by a manufacturing method that does not include a melt-kneading step, if the particles of each component are large, problems may occur, so it is preferable that the particle size of each mixed component is less than 10 μm.

Modifier B includes aliphatic carboxylic acids such as myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid; aliphatic alcohols such as lauryl alcohol, stearyl alcohol, and behenyl alcohol; natural ester waxes such as rice wax, carnauba wax, and candelilla wax; WEP-2, WEP-3, WEP-4, WEP-5, and the like.
Synthetic ester waxes such as WEP-6 manufactured by NOF Corporation can be used. These can be used alone or in combination of two or more. For example, rice wax or carnauba wax can be used alone as modifier B, or a combination of carnauba wax and rice wax can be used as modifier B.

The polyester resin of the present invention contains a constituent part derived from modifier A and a constituent part derived from modifier B, and the mass ratio of the constituent part derived from modifier A to the constituent part derived from modifier B is 1:2-12.
Wax dispersibility is improved by making the mass of the constituent parts derived from modifier B 2 or more when the mass of the constituent parts derived from modifier A is 1. Furthermore, by making the mass of the constituent parts derived from modifier B 12 or less when the mass of the constituent parts derived from modifier A is 1, the storage stability of the polyester resin is improved and wax dispersibility is also improved.
When the mass of the component parts derived from modifier A is 1, the mass of the component parts derived from modifier B is 4 or more, 1
It is more preferable that the number is 0 or less, and further more preferable that the number is 5 or more and 8 or less.

<Constituent parts derived from both modifier A and modifier B>
When both Modifier A and Modifier B are used as raw materials for polyester resin, Modifier A
In some cases, a component with the same carbon number may exist in modifier A and modifier B. In such cases, in mass spectrometry, the peaks derived from modifier A and modifier B are added together and detected as a single peak. In this specification, such a constituent portion is referred to as a constituent portion abm (m is 0).
The constituent moieties abm are constituent moieties derived from a component having the carbon number (16+2m).

The polyester resin of the present invention has an m/z of 87 in reactive PyGC-MS measurement described below.
In the chromatogram of Fig. 1, the detection signal intensity from component ab8 is preferably 0.5 or less, and more preferably 0.01 or more and 0.05 or less, when the detection signal intensity from component ab4 is taken as 1. By making the peak from ab8 0.01 or more, the wax dispersibility becomes good, and by making it 0.05 or less, the reactivity during resin production and the storage stability of the obtained resin become good.

<Method of producing polyester resin>
The polyester resin is prepared by placing raw materials including an acid component, an alcohol component, modifier A, modifier B, and a catalyst into a reactor, heating the reactor to raise the temperature, causing an esterification reaction or an ester exchange reaction, removing the water or alcohol produced by the reaction, and then gradually reducing the pressure inside the reactor to 150°C.
The polycondensation can be carried out while distilling off the diol component under a pressure of not more than 20 kPa (2 mmHg), preferably not more than 2 kPa (15 mmHg).
To contain constituent parts derived from modifier A in the range of 0.2% by mass to 3% by mass relative to 100% by mass of polyester resin, it is preferable to set the amount of modifier A added in the range of 0.5% by mass to 5% by mass relative to 100% by mass of polyester resin. To contain constituent parts derived from modifier B in the range of 0.5% by mass to 8% by mass relative to 100% by mass of polyester resin, it is preferable to set the amount of modifier B added in the range of 0.5% by mass to 8% by mass relative to 100% by mass of polyester resin.
The value for 100% by mass of polyester resin was calculated by subtracting the weight of water or alcohol removed by the esterification reaction or transesterification reaction and polycondensation reaction from the total amount of raw materials charged.

<Catalyst>
The catalyst used in the esterification reaction, transesterification reaction, and polycondensation is not particularly limited, and examples thereof include titanium compounds such as titanium alkoxide compounds having an alkoxy group, titanium carboxylate, titanyl carboxylate, titanyl carboxylate salts, and titanium chelate compounds; organic tin compounds such as dibutyltin oxide; inorganic tin compounds such as tin oxide and 2-ethylhexanetin; calcium acetate, calcium acetate hydrate, zinc acetate, antimony trioxide, and germanium dioxide.
Examples of titanium alkoxide compounds having an alkoxy group include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium, and tetraoctoxytitanium.
Examples of the titanium carboxylate compound include titanium formate, titanium acetate, titanium propionate, titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, titanium isooctanetricarboxylate, titanium octanetetracarboxylate, titanium decanetetracarboxylate, titanium benzoate, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalenedicarboxylate, titanium 4,4-biphenyldicarboxylate, titanium 2,5-toluenedicarboxylate, titanium anthracenedicarboxylate, titanium trimellitate, and titanium 2,4,
Examples include titanium 6-naphthalenetricarboxylate, titanium pyromelliticate, and titanium 2,3,4,6-naphthalenetetracarboxylate.
Among these, tetrabutoxytitanium is preferred. One of these may be used alone, or two or more of these may be used in combination.

The reaction temperature for the esterification reaction, transesterification reaction, and polycondensation reaction is preferably 180 to 280°C. The higher the reaction temperature, the higher the productivity, while the lower the reaction temperature, the more effectively it is possible to suppress the decomposition of polyester resin and the by-production of volatile matter that causes odor, and to reduce TVOC (Total Volatile Organic Compounds).
The polymerization temperature is 20
A temperature of 0°C or higher and 270°C or lower is more preferable.

The method for producing a polyester resin of the present invention is a method for producing a polyester resin in which a monomer mixture containing a polycarboxylic acid raw material and a polyhydric alcohol is polycondensed in the presence of modifier A and modifier B. By polycondensing a monomer mixture containing a polycarboxylic acid raw material and a polyhydric alcohol in the presence of modifier A and modifier B, a polyester resin having hydrocarbon groups at molecular ends, etc. can be obtained. Furthermore, when the polyester resin of the present invention is used as a binder resin for toner, the compatibility of the polyester resin of the present invention with wax blended during toner production can be significantly improved, and the wax dispersibility can be improved.

<Physical properties of polyester resin>
The glass transition temperature (Tg) of the polyester resin of the present invention is preferably 40 to 85°C.
A temperature of 5 to 75° C. is more preferable. The higher the glass transition temperature, the more improved the storage stability of the toner, and the lower the glass transition temperature, the more improved the low-temperature fixability of the toner.
The glass transition temperature of a polyester resin is determined as follows: That is, the glass transition temperature is determined by measuring the low-temperature baseline of a chart measured at a temperature rise rate of 5°C/min using a differential scanning calorimeter.
The temperature at the intersection with the tangent of the endothermic curve near the glass transition temperature is determined and is taken as Tg.

The softening temperature (T4) of the polyester resin of the present invention is preferably 80 to 170°C, more preferably 85 to 170°C.
A softening temperature of 160° C. is more preferable. The higher the softening temperature, the better the hot offset resistance becomes, and the lower the softening temperature, the better the low-temperature fixability tends to be.
The softening temperature of the polyester resin can be measured using a flow tester.

The acid value of the polyester resin of the present invention is preferably 0.1 to 60 mgKOH/g, and more preferably 0.5
The higher the acid value, the more likely it is that the productivity of the polyester resin will improve, while the lower the acid value, the more likely it is that the moisture resistance of the polyester resin will improve, making it easier to produce a toner that is less susceptible to the effects of the usage environment.
The acid value of a polyester resin is the amount of potassium hydroxide required to neutralize the carboxyl groups per 1 g of sample, expressed in milligrams, and is expressed in mgKOH/g.

<Binder resin for toner>
The polyester resin of the present invention can be suitably used as a binder resin for toner. The toner of the present invention is a toner using the polyester resin of the present invention as a binder resin for toner. The content of the polyester resin of the present invention in 100% by mass of the toner of the present invention is 20 to 9
0% by mass is preferred.
The toner of the present invention may further contain, as required, a colorant, a charge control agent, a wax, a flow modifier,
The polyester resin may contain additives such as inorganic fine powder, resins other than the polyester resin of the present invention (other binder resins), lubricants, and the like.

Examples of colorants include carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes or pigments, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, and condensed azo dyes or pigments, etc. These may be used alone or in combination of two or more.
When the toner is used as a color toner, examples of yellow colorants include benzidine yellow, monoazo dyes and pigments, and condensed azo dyes and pigments; examples of magenta colorants include quinacridone, rhodamine dyes and pigments, and monoazo dyes and pigments; and examples of cyan colorants include phthalocyanine blue.
The content of the colorant is not particularly limited, but is preferably 2 to 10% by mass relative to 100% by mass of the toner in terms of providing excellent color tone, image density, and thermal properties of the toner.

Examples of the charge control agent include positively charged charge control agents such as quaternary ammonium salts and basic or electron-donating organic substances; and negatively charged charge control agents such as metal chelates, metal-containing dyes, and acidic or electron-withdrawing organic substances.
When the toner is used as a color toner, a charge control agent that is colorless or light in color and that does not adversely affect the color tone of the toner is suitable, and examples of such charge control agents include metal salts of salicylic acid or alkyl salicylic acid with chromium, zinc, aluminum, etc., metal complexes, amide compounds, phenol compounds, naphthol compounds, etc. Furthermore, styrene-based, acrylic acid-based, methacrylic acid-based, and vinyl polymers having sulfonic acid groups may also be used as charge control agents.
The content of the charge control agent is preferably 0.5 to 5% by mass relative to 100% by mass of the toner. If the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be at a sufficient level, and if the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent tends to be suppressed.

The wax may be appropriately selected from carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, silicone wax, etc., taking into consideration the releasability, storage stability, fixability, color development, etc. of the toner. These may be used alone or in combination of two or more.
The melting point of the wax may be appropriately determined in consideration of the above-mentioned toner properties.
The wax content is not particularly limited, but is preferably 0.3 to 15% by mass relative to 100% by mass of the toner, since it affects the above-mentioned toner performance. The lower limit of the wax content is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit of the wax content is more preferably 13% by mass or less, and particularly preferably 12% by mass or less.
Since the polyester resin of the present invention has extremely good wax dispersibility, it is possible to increase the types and amounts of wax that can be blended, and to provide a toner having higher performance in fixing property, offset resistance, and storage stability than conventional toners.

Examples of additives such as flow modifiers include flow improvers such as fine powders of silica, alumina, and titania; inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania; resistance adjusters such as styrene resins and acrylic resins; and lubricants, which are used as internal or external additives.
The content of these additives is preferably 0.05 to 10% by mass relative to 100% by mass of the toner. If the content of these additives is 0.05% by mass or more, the effect of improving the performance of the toner tends to be sufficient, and if it is 10% by mass or less, the image stability of the toner tends to be good.

Examples of other binder resins include polyester resins other than those of the present invention, styrene-based resins, cyclic olefin resins, epoxy resins, etc. These may be used alone or in combination of two or more.
When other binder resins are used, it is preferable to use 20% by mass or more of the polyester resin of the present invention in 100% by mass of all binder resins.

The toner of the present invention can be used as any of magnetic one-component developers, non-magnetic one-component developers, and two-component developers.

When the toner of the present invention is used as a magnetic one-component developer, the toner contains a magnetic material, such as ferromagnetic alloys containing ferrite, magnetite, iron, cobalt, nickel, etc., and alloys that do not contain compounds or ferromagnetic elements but become ferromagnetic by appropriate heat treatment (e.g., so-called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum and manganese-copper-tin, chromium dioxide, etc.).
The content of the magnetic material is not particularly limited, but since it has a significant effect on the grindability of the toner, it is preferably 3 to 70% by mass relative to 100% by mass of the toner. If the content of the magnetic material is 3% by mass or more, the toner tends to have a sufficient level of charge, and if it is 70% by mass or less, the toner tends to have good fixability and grindability. The upper limit of the content of the magnetic material is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

When the toner of the present invention is used as a two-component developer, the toner of the present invention is used in combination with a carrier.
Examples of the carrier include magnetic substances such as iron powder, magnetite powder, and ferrite powder, and those coated with a resin on the surface thereof, magnetic carriers, etc. Examples of the coating resin for the resin-coated carrier include styrene-based resins, acrylic-based resins, styrene-acrylic copolymer-based resins, silicone-based resins, modified silicone-based resins, fluorine-based resins,
and mixtures of these resins.
The amount of carrier used is preferably 500 to 3,000 parts by mass relative to 100 parts by mass of toner. If the amount of carrier used is 500 parts by mass or more, fogging and the like tend to be less likely to occur, and if it is 3,000 parts by mass or less, the density of the fixed image tends to be sufficient.

The method for producing the toner of the present invention is not particularly limited. After mixing the polyester resin of the present invention with the above-mentioned compound, the mixture is melt-kneaded in a twin-screw extruder or the like, and then crushed, finely crushed, and then crushed.
Examples of the method include a production method in which classification is performed and, if necessary, external addition of inorganic particles is performed (pulverization method); a production method in which the polyester resin of the present invention and a blend are dissolved and dispersed in a solvent, granulated in an aqueous medium, the solvent is removed, washed, and dried to obtain toner particles, and if necessary, external addition of inorganic particles is performed; and a production method in which the polyester resin of the present invention is emulsified in water, and then aggregated and fused together with the finely granulated blend in water to obtain toner particles, which are then granulated, washed, and dried to obtain toner particles, and if necessary, external addition of inorganic particles is performed (chemical method).

The average particle size of the toner of the present invention is not particularly limited, but is preferably 3 to 15 μm, and more preferably 5 to 1
When the average particle diameter of the toner is 3 μm or more, productivity is good. On the other hand, when the average particle diameter of the toner is 15 μm or less, high quality images can be stably formed.

The present invention will be specifically described below with reference to examples, although the present invention is not limited to the following examples.
The polyester resins shown in the examples were evaluated as follows.

[Measurement and Evaluation]
<Measurement of Glass Transition Temperature (Tg)>
The glass transition temperature of the polyester resin was measured using a differential scanning calorimeter (Shimadzu Corporation, "DSC-
The measurement was performed using a 10 mg ± 0.5 mg sample weighed into an aluminum pan, melted at 100°C (a temperature above the glass transition temperature) for 10 minutes, and then rapidly cooled using dry ice.

<Measurement of Softening Temperature (T4)>
The softening temperature of the polyester resin was measured using a flow tester (Shimadzu Corporation, CFT-500
Using a thermocouple (D"), a 1 mmφ×10 mm nozzle was used, a load of 294 N was applied, and the temperature was raised at a uniform rate of 3° C./min. The temperature at which half of 1.0 g of the resin sample flowed out was measured, and this was taken as the softening temperature.

<Measurement of Acid Value>
The acid value of the polyester resin was measured as follows.
Approximately 0.2 g of a measurement sample was accurately weighed into a sidearm Erlenmeyer flask (a(g)), 20 mL of benzyl alcohol was added, and the mixture was heated in a nitrogen atmosphere using a heater at 230°C for 15 minutes to dissolve the measurement sample. After cooling to room temperature, 20 mL of chloroform and a few drops of cresol red solution were added, and the mixture was titrated with a 0.02N KOH solution (titer = b(mL), titer of the KOH solution = p). A blank measurement was performed in the same manner (titer = c(mL)), and the acid value was calculated according to the following formula.
Acid value (mgKOH/g) = {(b-c) x 0.02 x 56.11 x p}/a

<Contents of constituent parts derived from modifier A and constituent parts derived from modifier B>
The contents of the constituent parts derived from modifier A and the constituent parts derived from modifier B bonded to the polyester resin were measured as follows.
Pretreatment before measurement: Each polyester resin was dissolved in chloroform and insoluble matter was removed.
When no modifier is used (polyester resin 20 described later), there is no insoluble matter, and the insoluble matter is mainly derived from modifiers A and B that are mixed without bonding with the polyester resin.
The chloroform solution was dried and solidified after removing chloroform, and the resulting solution was subjected to each analysis. Modifiers A and B themselves were also subjected to each measurement as they were.

NMR measurement was performed under the following conditions, and the composition was calculated using the integral value of the spectrum. Note that for each constituent portion derived from modifier A and modifier B in the polyester resin, the total amount of the constituent portions derived from modifier A and modifier B was calculated, rather than for each compound. [NMR measurement conditions]
Equipment JEOL ECS-400
Magnet JMTC-400/54/SS
Observation frequency ^1H 400MHz ^13C 100MHz
Solvent Polyester resin: deuterated chloroform
Modifier A, Modifier B: DMSO-d6
Temperature Polyester resin: 35°C
Modifier A, Modifier B: 120°C
Accumulated number of times Polyester resin: ^1H 1000 times, ^13C 1024 times
Modifier A, Modifier B: ¹ H 64 times, ¹³ C 1024 times

Reaction PyGC-MS Measurement Measurement was carried out according to the following procedure.
Step 1. The sum of the peak areas in the chromatogram of m/z = 87 of each modifier itself was calculated. Note that "peak" refers to the signal detected by the detector, and "high peak" refers to the signal detected by the detector.
This means that the detected signal is strong. Also, "detected signal strength" means "detected signal strength."
Step 2. Select a representative peak in the chromatogram of m/z=87 for each modifier.
The ratio of the representative peak area to the sum of the peak areas was calculated.
Step 3. Rice wax, a type of modifier B, was blended in equal weights with the other modifiers A and B and measured. In the mass spectrum at m/z = 87, the sum of the peak areas of each modifier was calculated using the representative peak area of each modifier and the area ratio determined in Step 2, and the area ratio of each modifier was calculated when rice wax was set to 1.
Step 4. In the chromatogram of the sample at m/z = 87, the sum of the peak areas derived from each modifier in the sample was calculated using the representative peak area of each modifier and the area ratio determined in Step 2, and the weight ratio of the modifier was calculated using the calculated sum area and the area ratio to the same weight of modifier determined in Step 3.
Step 5. The molar ratio of the modifiers was calculated using the weight ratio of the modifiers obtained in Step 4 and the molecular weight of each modifier.

[Reaction PyGC-MS measurement conditions]
Apparatus: Agilent Technology GC/MS 7890/5975; Frontier Labs PY-3030D double-shot pyrolyzer column; Frontier Labs Ultra-Alloy +5 (30 m x 0.25 mm)
I. D. Film thickness 0.25μm)
Column temperature: 40°C (1 min) → 10°C/min → 300°C (5 m
in)
Inlet temperature 300℃
Interface 300℃
Carrier gas: He (flow rate 1 ml/min)
Split ratio 50:1
Ionization method EI
Ionization source temperature: 230°C
Quadrupole temperature 150℃
Scan resin 20-500 amu
Thermal decomposition temperature 400℃
Interface temperature: 300°C
Reaction reagent: 25% TMAH-methanol solution The content of modifier relative to resin in the sample was calculated using the total amount (molar ratio) of modifier relative to resin determined by NMR and the molar ratio of modifier in the sample determined by reaction PyGC-MS.

<Detection signal intensity from component ab8 when detection signal intensity from component ab4 is set to 1>
In the chromatogram of m/z=87 in the reaction PyGC-MS measurement, R.T=2
The detected signal strength from the baseline was 5.9 (indicating ab4) and R.T = 31.0 (indicating ab
The detection signal intensity of ab8 was calculated by measuring the detection signal intensity of ab4 (representing ab8) from the baseline.

<Components in resin with a particle size of 10 μm or more>
A small piece of polyester resin was heat-pressed at the softening temperature of the resin to form a 50 μm film, which was then observed under a microscope to count the number of components of 10 μm or more in any 100 μm square.
These are components derived from modifier A or modifier B.
<Wax dispersibility>
The polyester resin, modifier A, modifier B, and wax (Fischer-Tropsch Wax SX80 manufactured by Nippon Seiro Co., Ltd.) were dry-blended according to the formulations shown in Tables 5, 6, and 7, and then kneaded in a twin-screw extruder (PCM-29 manufactured by Ikegai Corporation) with the barrel temperature set to 120°C, and plate-shaped samples were obtained. Small pieces of the samples were hot-pressed in a press set to the softening temperature of the resin to form 50 μm films, which were then observed under a microscope at 500x magnification.
The particle size of wax particles within a 0 μm square was confirmed and evaluated according to the following criteria.
S: No particles can be seen. A: Particles smaller than 0.5 μm can be barely seen. B: Particles of 0.5 μm or more and smaller than 1 μm can be seen. C: Particles of 1 μm or more and smaller than 3 μm can be seen, with slightly poor dispersibility. D: Particles of 3 μm or more and smaller than 5 μm can be seen, with poor dispersibility. E: Particles of 5 μm or more can be seen, with significantly poor dispersibility.

[Examples 1 to 14, Comparative Examples 1 to 6]
The raw materials used to prepare the polyester resin of the present invention and the comparative polyester resin are shown in Tables 1 and 2. The mass % in Table 1 is calculated from the raw materials to obtain the total mass of the polyester resin obtained after the esterification reaction and the polycondensation reaction, and the total mass (calculated value) is multiplied by 10
This is the numerical value when the value is set to 0%.

Details of the abbreviations and names in Tables 1 and 2 are as follows:
Diol A: Propylene oxide derivative of bisphenol A (PO 2.3 mole adduct)
Diol B: Ethylene oxide derivative of bisphenol A (EO 2.2 mole adduct)
Unicid 700: Baker Hughes, linear polyethylene with one terminal carboxylic acid, melting point 110.5°C
Unilin 700: Baker Hughes, linear polyethylene with one terminal alcohol, melting point
100.3℃
Unilin 1000: Baker Hughes, linear polyethylene with one alcohol terminal, melting point 107.9°C
Epolene E-10J: manufactured by Westlake Chemical Co., oxidized polyethylene, melting point 100
．9℃
Carnauba wax: Toyo Adle Co., Ltd., natural ester, melting point 85.3°C
Rice wax: Manufactured by Boso Oil & Fat Co., Ltd., natural ester, melting point 81.5°C
WEP-3: NOF Corporation, synthetic ester, melting point 73.2°C

<Production of Polyester (PES) Resin 1>
For 100 mol parts of the total acid components, 82 mol parts of terephthalic acid, 13 mol parts of isophthalic acid, 5 mol parts of trimellitic anhydride, 35 mol parts of diol A, 1 mol part of diol B, 80 mol parts of ethylene glycol, 2 mass% of Uniside 700 as modifier A, 2 mass% of carnauba wax and 2 mass% of rice wax as modifier B, and 500 ppm of titanium tetrabutoxide as a catalyst relative to the total acid components were charged into a reaction vessel equipped with a distillation column. The amounts of modifier A and modifier B charged were determined based on the amount of polyester resin to be obtained.
This is an internal number relative to 0% by mass.
Next, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, and the temperature was raised until the temperature in the reaction system reached 265°C. The esterification reaction was carried out by maintaining this temperature. After the distillation of water from the reaction system ceased and the esterification reaction was completed, the temperature in the reaction system was lowered to 265°C.
The temperature was kept at 40° C., and the pressure inside the reaction vessel was reduced over about 40 minutes to a vacuum degree of 133 Pa, and a polycondensation reaction was carried out while distilling off the polyhydric alcohol from the reaction system.
The viscosity of the reaction system increased with the reaction, and the degree of vacuum was increased as the viscosity increased, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating the desired softening temperature. Then, when the predetermined torque was reached, the stirring was stopped, the reaction system was returned to normal pressure, and pressurized with nitrogen, and the reaction product was removed (discharged) from the reaction vessel, thereby obtaining polyester resin 1.

<Production of Polyester (PES) Resins 2 to 20>
Polyester resins 2 to 20 were obtained in the same manner as in the production of polyester resin 1, using raw materials having the compositions shown in Tables 1 and 2.

The resin compositions of polyester resins 1 to 20, as well as the measurement results of the glass transition temperature Tg (°C), softening temperature T4 (°C), and acid value AV (mgKOH/g) of the obtained polyester resins, and the results of resin evaluation (components in the resin with a size of 10 μm or more) are shown in Tables 3 and 4.
As described above, the resin evaluations in Tables 3 and 4 were carried out by heat pressing small pieces of polyester resin at the softening temperature of the resin to form a 50 μm film, which was then observed under a microscope to count the number of components of 10 μm or more within an arbitrary 100 μm square.
It was confirmed that components of 1 μm or larger were present.
On the other hand, in polyester resins 1 to 14 in which modifier A and modifier B were used in combination, or in polyester resins 18 and 19 in which modifier B alone was used, no components of 10 μm or larger were found.

Next, the wax dispersibility was evaluated using the obtained polyester resin. The polyester resin, modifier A, modifier B, and wax (
After dry blending, the wax was kneaded in a twin-screw extruder (PCM-29 manufactured by Ikegai Corporation) with the barrel temperature set to 120°C, and a plate-shaped sample was obtained. A small piece of the sample was hot-pressed in a press set to the softening temperature of the resin to form a 50 μm film, which was then observed under a microscope at 500x magnification. The particle size of wax particles within any 50 μm square was confirmed and evaluated according to the following criteria. The particle size of the particles was determined as the longest distance of the particle, and if the particle was spherical, the diameter was used.
S: No particles were observed A: Particles less than 0.5 μm were barely observed B: Particles 0.5 μm or larger but less than 1 μm were observed C: Particles 1 μm or larger but less than 3 μm were observed, with slightly poor dispersibility D: Particles 3 μm or larger but less than 5 μm were observed, with poor dispersibility E: Particles 5 μm or larger were observed, with significantly poor dispersibility The types and amounts of resins and waxes used in the evaluation, and the evaluation results, are shown in Tables 5 to 7.

The wax dispersibility evaluation result for Example 1, in which polyester resin 1 was used, was S, and for Example 2, in which polyester resin 1 and a polyester resin other than the present invention were used in a ratio of 1:1, was also S. For Example 3, in which polyester resin 1 and a polyester resin other than the present invention were used in a ratio of 1:2, it was B.
In Examples 4 to 14, the wax dispersion evaluation results were all B or higher.

In Comparative Example 1, which used polyester resin 13 in which the mass ratio of modifier B to modifier A was 13, the wax dispersion particle diameter was 1 to 2 μm, and the wax dispersibility was inferior to when the polyester resin of the present invention was used. Also, in Comparative Example 2, which used polyester resin 14 in which the mass ratio of modifier B to modifier A was 1.7, the wax dispersion particle diameter was 1 to 2 μm, and the wax dispersibility was inferior to when the polyester resin of the present invention was used.
In Comparative Examples 3 and 4, which used polyester resins 18 and 19 prepared using only modifier B without modifier A, the wax dispersion evaluation results were C and D, and the wax dispersion was significantly inferior to that of Example 1.
In Comparative Example 5, unused polyester resin 20 was used for both Modifier A and Modifier B, and in Comparative Example 6, the same Modifier A and Modifier B as those added during polymerization of Polyester Resin 1 were blended into Polyester Resin 20 in the same amounts during kneading. In both cases, wax dispersibility was poor.

Next, the reaction PyGC-MS measurement results for polyester resin 1 at m/z = 87 are shown in Figure 1, and an enlarged view in the vertical direction of Figure 1 is shown in Figure 2. As examples of modifiers A and B, the reaction PyGC-MS measurement results for modifier A (Unicid 700) used in polyester resin 1 at m/z = 87 are shown in Figure 3, the reaction PyGC-MS measurement results for modifier B (carnauba wax) at m/z = 87 are shown in Figure 4, and the reaction PyGC-MS measurement results for modifier B (rice wax) at m/z = 87 are shown in Figure 5.

The most strongly observed detection signal (peak ab4 in Figure 1) derived from the constituent part with 24 carbon atoms is the carbon chain with 24 carbon atoms contained in modifier A and the carbon chain with 24 carbon atoms contained in modifier B.
The detection signal is due to the carbon chain with carbon number 4. Furthermore, the very weakly observed detection signal (peak ab8 in Figure 1) due to the constituent part with 32 carbon atoms is due to the carbon chain with 32 carbon atoms contained in Modifier A and Modifier B. Figure 2 shows that a peak due to the constituent part with 40 carbon atoms is detected in Polyester Resin 1. Considering the measurement results in Figures 3 to 5, this peak is thought to be the detection signal (peak a12 in Figure 2) due to the carbon number 40 contained in Modifier A.

In polyester resin 1 in which modifier A and modifier B were introduced in the composition shown in Table 3, the detection signal derived from the constituent part having 24 carbon atoms was observed to be more than twice as strong as the detection signal derived from the constituent part having 32 carbon atoms.

Claims (20)

A polyester resin comprising a constituent part (C1) derived from a polycarboxylic acid, a constituent part (D1) derived from a polyhydric alcohol, a constituent part (A1) derived from an aliphatic hydrocarbon-based modifier A having a melting point of 90°C or higher and a functional group capable of reacting with an acid or alcohol, and a constituent part (B1) derived from an aliphatic hydrocarbon-based modifier B having a melting point of less than 90°C and a functional group capable of reacting with an acid or alcohol, wherein the mass ratio of constituent part (A1) to constituent part (B1) is in the range of 1:2 to 12. The polyester resin according to claim 1, wherein the melting point of the modifier A is 120°C or lower. The polyester resin according to claim 1 or 2, wherein the modifier A includes at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. The polyester resin according to any one of claims 1 to 3, wherein the amount of the constituent moiety (A1) is in the range of 0.2% by mass to 3% by mass based on 100% by mass of the polyester resin. The polyester resin according to any one of claims 1 to 4, wherein the melting point of the modifier B is 60°C or higher. The polyester resin according to any one of claims 1 to 5, wherein the modifier B includes at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. The polyester resin according to any one of claims 1 to 6, wherein the amount of the constituent part (B1) is in the range of 0.5% by mass to 8% by mass based on 100% by mass of the polyester resin. A toner using the polyester resin described in any one of claims 1 to 7. A method for producing polyester resins in which a monomer mixture containing a polycarboxylic acid and a polyhydric alcohol is polycondensed in the presence of an aliphatic hydrocarbon-based modifier A having a melting point of 90°C or higher and a functional group capable of reacting with an acid or alcohol, and an aliphatic hydrocarbon-based modifier B having a melting point of less than 90°C and a functional group capable of reacting with an acid or alcohol, wherein the amount of modifier B added is in the range of 1 to 6 relative to the amount of modifier A added. The method for producing a polyester resin according to claim 9, wherein the melting point of the modifier A is 120°C or lower. The method for producing a polyester resin according to claim 9 or 10, wherein the modifier A includes at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. The method for producing a polyester resin according to any one of claims 9 to 11, wherein the amount of modifier A added is in the range of 0.5% by mass to 5% by mass based on 100% by mass of the polyester resin. The method for producing a polyester resin according to any one of claims 9 to 12, wherein the melting point of the modifier B is 60°C or higher. The method for producing a polyester resin according to any one of claims 9 to 13, wherein the modifier B includes at least one of a substance having an acid or alcohol at one end of a linear alkyl group, and an ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol. The method for producing a polyester resin according to any one of claims 9 to 14, wherein the amount of modifier B added is in the range of 0.5% to 8% by mass based on 100% by mass of the polyester resin. The modifier has a constituent moiety (C1) derived from a polycarboxylic acid, a constituent moiety (D1) derived from a polyhydric alcohol, a constituent moiety an having a carbon number (16 + 2n, n is at least one integer of 12 to 15) derived from an aliphatic hydrocarbon-based modifier A having a melting point of 90°C or higher and a functional group capable of reacting with an acid or an alcohol ( n is the same as n in the carbon number 16 + 2n derived from the aliphatic hydrocarbon-based modifier A, and an is at least one of a12 to a15), and a constituent moiety abm having a carbon number (16 + 2m, m is an integer of 3 to 8) derived from the modifier A and an aliphatic hydrocarbon-based modifier B having a melting point of less than 90°C and a functional group capable of reacting with an acid or an alcohol (m is the same as m in the carbon number 16 + 2m derived from the aliphatic hydrocarbon-based modifier A and the aliphatic hydrocarbon-based modifier B, and abm is ab3 to ab8),
A polyester resin in which the detection signal intensity derived from ab8 is 0.01 or more and 0.05 or less when the detection signal intensity derived from ab4 is taken as 1 in a chromatogram at m/z=87 in reaction PyGC-MS measurement. The polyester resin described in claim 16, wherein the modifier A includes constituent moieties (a0 to a15) with a carbon number (16 + 2n, where n is an integer from 0 to 15). The polyester resin described in claim 16, wherein the modifier B has a structural portion (at least one of b3 to b5) with a carbon number (16 + 2p, where p is at least one integer from 3 to 5). The polyester resin described in claim 18, wherein the modifier B does not have any structural moieties derived from a carbon chain having more than 40 carbon atoms. A toner using the polyester resin described in any one of claims 16 to 19.