Polyester resin, its manufacturing method, and toner

Abstract

To provide a polyester resin having good wax dispersibility and a method for producing the polyester resin.SOLUTION: There is provided a polyester resin including: a constitutional part (A1) derived from an aliphatic hydrocarbon-based modifier (modifier A) having a melting point of 90°C or higher and having a functional group capable of reacting with an acid or an alcohol; and a constitutional part (B1) derived from an aliphatic hydrocarbon-based modifier (modifier B) having a melting point of 90°C or lower and having a functional group capable of reacting with an acid or an alcohol, wherein a mass ratio of the constitutional part (A1) to the constitutional part (B1) is in a range of 1:2 to 1:12.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyester resin having good wax dispersibility. [Background technology]

[0002] Polyester resins are widely used in a wide range of applications, including coating materials, adhesives, films, and electrophotographic toners. It has a wide range of uses and is blended with a variety of functional materials depending on the application. For example, when polyester resin is used as a binder resin for toner, it is necessary to add peelability. It is known that wax is blended into polyester resin to give it a smoother texture and sharper melting properties. It is being done. However, since polyester resin and wax are not compatible with each other, the wax component is not easily separated. Therefore, the wax dispersion in polyester resin has been Considerations are being made to improve the quality of life.

[0003] For example, Patent Document 1 discloses a method for polymerizing a polymer in the presence of a long-chain alkyl group having a specific functional group at the end. By using polyester resin with high light transmittance, it has good fixing performance and non-off property. It has good setting properties, image stability, and durability, and also has excellent color development that can be used for color printing. Patent Document 2 discloses a technique for providing a toner having good color reproducibility and color reproducibility. The present invention relates to a polyester resin containing a structural unit derived from oxidized polyolefin and an oxidized polyolefin. By using a binder resin composition for toner containing The technology for providing a toner having good setting properties, image stability, and durability is disclosed. Patent Document 3 discloses a polyester resin for toner obtained in the presence of a wax having a polar group. By using this, a toner with excellent hot offset resistance and charging properties can be provided. The technology is disclosed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-133391 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-158502 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-18032 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the methods described in Patent Documents 1 and 2, the particle size is larger than the toner particle size. Materials tend to remain in the resin, especially toners manufactured using methods that do not involve melt-kneading, such as chemical methods. In this case, the particles of the modifier itself become a cause of the problem. The polyester resin does not have sufficient dispersibility of wax.

[0006] Therefore, the present invention is a method for producing a polyester resin that does not leave any modifier particles of 10 μm or more in size at a stage before the melt-kneading process. The object of the present invention is to provide a steric resin. Another object of the present invention is to provide a polyester resin having good wax dispersibility. . [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A polycarboxylic acid-derived structural unit (C1) and a polyhydric alcohol-derived structural unit (D 1) and a fat having a melting point of 90°C or higher and a functional group capable of reacting with an acid or alcohol. A component (A1) derived from an aromatic hydrocarbon-based modifier (modifier A) and a component (A2) having a melting point of less than 90°C. and an aliphatic hydrocarbon-based modifier (modifier B) having a functional group capable of reacting with an acid or alcohol. ) and a constituent part (B1) derived from the constituent part (A1), and the mass of the constituent part (A1) and the constituent part (B1) Polyester resin, with a ratio 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] Modifier A is a substance having an acid or alcohol at one end of a linear alkyl group, and At least one ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol The polyester resin according to [1] or [2], comprising: [4] The amount of the constituent part (A1) is 0.2% by mass to 100% by mass of the polyester resin. The polyester resin according to any one of [1] to [3], wherein the content is in the range of 3% by mass. [5] The polyester according to any one of [1] to [4], wherein the melting point of the modifier B is 60°C or higher. Tere resin. [6] Modifier B is a substance having an acid or alcohol at one end of a linear alkyl group, and At least one ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol The polyester resin according to any one of [1] to [5], comprising: [7] The amount of the constituent part (B1) is 0.5% by mass to 100% by mass of the polyester resin. The polyester resin according to any one of [1] to [6], wherein the content is in the range of 8% by mass. [8] A toner using the polyester resin according to any one of [1] to [7]. [9] A monomer mixture containing a polycarboxylic acid and a polyhydric alcohol is mixed with a polymer having a melting point of 90°C or higher. There are aliphatic hydrocarbon-based modifiers with functional groups that can react with acids or alcohols (modifiers A) and a fat having a melting point of less than 90°C and a functional group capable of reacting with an acid or alcohol. A method for producing a polyester resin by polycondensation in the presence of an aromatic hydrocarbon modifier (modifier B). When the amount of modifier A added is 1, the amount of modifier B added is in the range of 1 to 6. 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. Construction method.

[11] Modifier A is a substance having an acid or alcohol at one end of a linear alkyl group, and At least one ester of a linear alkyl monocarboxylic acid and a linear alkyl monoalcohol The method for producing a polyester resin according to [9] or

[10] , comprising:

[12] The amount of modifier A added is 0.5 mass% of the resulting polyester resin (100 mass%). % to 5% by mass of the polyester resin according to any one of [9] to

[11] . Manufacturing method.

[13] The polymer according to any one of [9] to

[12] , wherein the melting point of the modifier B is 60°C or higher. A method for producing polyester resin.

[14] Modifier B is a substance having an acid or alcohol at one end of a linear alkyl group, linear Contains either an ester of an alkyl monocarboxylic acid and a linear alkyl monoalcohol The method for producing a polyester resin according to any one of [9] to

[13] .

[15] The amount of modifier B added is 0.5 mass% of the resulting polyester resin (100 mass%). % to 8 mass% of the polyester resin according to any one of [9] to

[14] . Manufacturing method.

[16] A component derived from a polycarboxylic acid (C1) and a component derived from a polyhydric alcohol ( D1) and the number of carbon atoms derived from modifier A (16 + 2n, n is at least one integer between 12 and 15) ) constituent parts (at least one of a12 to a15) and the modifiers A and B It has a carbon number (16 + 2m, m is an integer between 3 and 8) and a structural unit (ab3 to ab8). , In the chromatogram of m / z=87 in the reaction PyGC-MS measurement, ab4-derived The detection signal strength from ab8 is 0.01 or more and 0.05 or less when the detection signal strength of Polyester resin.

[17] Modifier A is a component of carbon number (16 + 2n, n is any integer between 0 and 15). The polyester resin according to

[16] , comprising (a0 to a15).

[18] Modifier B is a compound having a structure of carbon number (16 + 2p, where p is at least one integer between 3 and 5). The polyester resin according to

[16] , having a structural moiety (at least one of b3 to b5).

[19] The polyester resin according to

[0018] , wherein the modifier B does not have any constituent moieties derived from a carbon chain having more than 40 carbon atoms.

[20] A toner using the polyester resin according to any one of

[16] to

[19] . [Effects of the Invention]

[0008] According to the present invention, polyester resins are prepared in such a manner that no components of 10 μm or more remain before the melt-kneading step. It is possible to provide a resin that does not leave components of 10 μm or more in size at the stage before the melt-kneading process. By using polyester resin, defects caused by the particle size of the particles contained in polyester resin can be eliminated. It is possible to provide a toner with reduced particle size. Furthermore, according to the present invention, a polyester resin having good wax dispersibility can be provided. The polyester resin of this ink has good wax dispersibility, so it has low-temperature fixability and anti-blocking properties. Therefore, a toner with excellent properties can be provided. [Brief explanation of the drawings]

[0009] [Figure 1] Reaction PyGC-MS measurement results for polyester resin 1 at m / z=87. [Figure 2] Enlarged view of the reaction PyGC-MS measurement results for polyester resin 1 at m / z=87. [Figure 3] Reaction PyGC-MS measurement results for Modifier A at m / z=87. [Figure 4] PyGC-MS measurement results of the reaction of modifier B at m / z=87. [Figure 5] PyGC-MS measurement results of the reaction of modifier B at m / z=87. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Polyester resin> The polyester resin of the present invention comprises a polycarboxylic acid-derived constituent moiety (C1) and a polyhydric alcohol-derived constituent moiety (C2). The constituent part (D1) derived from alcohol and the melting point of the compound are 90°C or higher and can react with acid or alcohol. A constituent part (A1) derived from an aliphatic hydrocarbon-based modifier (modifier A) having a functional group capable of being used for the modification of carbon black. aliphatic carbonized polymers having a melting point of less than 90°C and functional groups capable of reacting with acids or alcohols; A component (B1) derived from a hydrogen-based reformer (reformer B), and a component (B2) derived from reformer A The mass ratio of the component (A1) to the component (B1) derived from the modifier B is in the range of 1:2 to 12. , polyester resin. The constituent moiety (C1) may be a polycarboxylic acid, an acid anhydride thereof, or a lower alkyl ester thereof. This also includes those derived from esters (hereinafter referred to as "equivalent raw materials"). The raw materials equivalent to these are collectively called "polycarboxylic acid raw materials." Similarly, the term "raw materials" includes equivalent raw materials.

[0011] <Polycarboxylic acid raw material> Polycarboxylic acid raw materials include dicarboxylic acids and tricarboxylic or higher carboxylic acids, as well as Equivalent raw materials include: Examples of dicarboxylic acid raw materials include terephthalic acid, isophthalic acid, and naphthalene. Isomers of dicarboxylic acids (specifically 1,4-, 1,5-, 1,6-, 1,7-, 2,5- Aromatic dicarboxylic acids such as 2,6-, 2,7-, 2,8-, and the like, and their equivalent raw materials; Succinic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, Aliphatic dicarboxylic acids such as sebacic acid and furandicarboxylic acid, and their equivalents are included. Examples of lower alkyl esters of terephthalic acid and isophthalic acid include terephthalic acid, Dimethyl terephthalate, Dimethyl isophthalate, Diethyl terephthalate, Diethyl isophthalate, Examples include dibutyl terephthalate and dibutyl isophthalate. Among these, as a dicarboxylic acid raw material, it is excellent in terms of handling properties and cost. In this respect, terephthalic acid, isophthalic acid, and adipic acid are preferred. These dicarboxylic acid raw materials may be used alone or in combination of two or more. It may also be used in combination with a trivalent or higher carboxylic acid raw material, which will be described later.

[0012] Examples of raw materials for trivalent or higher carboxylic acids 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 its equivalent raw materials. As a raw material for trivalent or higher carboxylic acids, tricarboxylic acid is preferred due to its ease of handling and cost. Mellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride are preferred. Particularly preferred is trimellitic acid and its anhydride.

[0013] <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, polyoxypropylene-(2.3)-2,2- Bis(4-hydroxyphenyl)propane, Polyoxypropylene(2.2)-polyoxy Diethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene Dipropylene(6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene Propylene (2.2)-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene Propylene-(2.4)-2,2-bis(4-hydroxyphenyl)propane, polyoxy Aromatics such as propylene(3.3)-2,2-bis(4-hydroxyphenyl)propane Alcohol, ethylene glycol, neopentyl glycol, propylene glycol, Xanediol, polyethylene glycol, 1,3-propanediol, 1,4-butane Diol, diethylene glycol, triethylene glycol, 1,4-cyclohexanediol Methanol, D-Isosorbide, L-Isosorbide, Isomannide, Erythritan, Examples include aliphatic alcohols such as 1,4-dihydroxy-2-butene. These may be used alone or in combination of two or more. It may be used in combination with the above alcohols.

[0014] Examples of trihydric or higher alcohols include sorbitol, 1,4-sorbitan, pentaerythritol, and the like. Erythritol, dipentaerythritol, tripentaerythritol, 1,2,4-bromo Tantriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2 ,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylol Examples of the hydroxypropyl methyl ether include dimethyl ether, ... Among these, trimethylolpropane and glycerol are preferred in terms of reactivity, ease of handling, and cost. Lycerin is preferred.

[0015] <Component parts derived from modifier A and component parts derived from 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. Polyester having a constituent part derived from modifier A and a constituent part derived from modifier B. To obtain the above, a polycarboxylic acid raw material and a polyhydric alcohol are reacted in the presence of modifiers A and B. The monomer mixture containing the modifier A and the polyvalent carbonyl in the presence of the modifier A may be polycondensed. Modifier A and Modifier B are obtained by polycondensation of a monomer mixture containing a carboxylic acid raw material and a polyhydric alcohol. The functional group of the modifier B that can react with an acid or alcohol is a polycarboxylic acid raw material. and condensation with polyhydric alcohol to form a constituent part derived from modifier A and a constituent part derived from modifier B. Aliphatic carbonization, i.e., moieties containing aliphatic hydrocarbon groups, are introduced into the polyester resin. The hydrogen group has high compatibility with wax components, and when introduced into polyester resin, it This can improve the dispersibility of the powder. In the present invention, a modifier A having a melting point of 90°C or higher and a modifier B having a melting point of less than 90°C are combined. By using them in combination, aliphatic hydrocarbon groups with different carbon chain lengths were introduced into the polyester resin. Therefore, it is thought that the wax dispersibility has been significantly improved. Or, even if it has only a component part derived from modifier B, it is possible to use a component part derived from modifier A or modifier B. Compared to the case where the component part is not included, the wax dispersibility is improved, but the By using both of the modifiers B, a significant effect can be obtained. Specifically, the polyester resin contains constituent parts derived from modifier A and constituent parts derived from modifier B. By having both of these properties, wax dispersibility is significantly improved, making it suitable as a binder resin for toner. When used, the low-temperature fixing property, blocking resistance, offset resistance, and anti-blocking property of the obtained toner are improved. The durability is extremely good.

[0016] <Modifier A> Modifier A has a melting point of 90°C or higher and has a functional group that can react with an acid or alcohol. It is an aliphatic hydrocarbon-based modifier. The functional group capable of reacting with an acid or alcohol is not particularly limited, but may be a carboxyl group. or its anhydride, hydroxyl group, ester group, glycidyl group, alkoxy group, isocyanate Among these, a carboxy group or its anhydride, a hydroxyl group, and an ester group are preferred. stomach. The melting point of the modifier A is 90°C or higher, preferably 95°C or higher and 120°C or lower, and more preferably 100°C or lower. The melting point of the modifier A is preferably 90°C or higher, and the wax content is more preferably 115°C or lower. In addition, by setting the melting point of Modifier A to 120°C or less, the properties of Modifier A can be improved. The reactivity of the functional group with the functional group at the polyester end increases, and the constituent parts derived from Modifier A are converted into the polyester. It can be effectively applied to ester resins. Modifier A is a substance having an acid or alcohol at one end of a linear alkyl group, esters of alkyl monocarboxylic acids and linear alkyl monoalcohols. It is preferable that the linear alkyl group has a functional group at one end thereof. The constituent parts derived from the modifier A can be bonded to the polyester resin terminals. This improves the compatibility between the constituent parts of Modifier A and the wax, and improves wax dispersion. Improve. In a structure having a functional group at the end of a linear alkyl group, the number of carbon atoms in the linear alkyl group is approximately When the carbon number is around 30, the melting point is around 90°C. The constituent parts derived from modifier A have a carbon number of 32 or more. For example, a structure containing a linear alkyl group having 36 to 70 carbon atoms is preferred. Preferred are structures containing alkyl groups and structures containing linear alkyl groups having 36 to 60 carbon atoms. .

[0017] The amount of the constituent parts derived from Modifier A is 0.2% by mass to 100% by mass of polyester resin. The range of 3% by mass is preferable. When the content is 0.2% by mass or more, the wax dispersibility is improved. In addition, by keeping the content at 3 mass % or less, the reactivity during resin production and the stability of the obtained resin are improved. The lower limit of the amount of the constituent parts derived from the modifier A is preferably 0.3 mass % or more. It is preferably 0.5 mass % or more, and particularly preferably 0.5 mass % or more. If the amount of the component derived from modifier A, which is a constituent part of the polyester resin, is within the above range, For example, the modifier A itself can be mixed with the polyester resin without being bonded to it. However, in the case of toners manufactured using a method that does not include a melt-kneading process, the particles of each component are If the particles are too large, problems may occur, so the particle size of each component in the mixture is less than 10 μm. It is preferable that

[0018] Modified material A includes Unisid 350, Unisid 425, Unisid 550, and Unisid Baker Hughes acid-terminated polyethylene wax such as BB-700; Unilin 42 5. Baker Hughes alcohol-terminated polyisocyanates such as Unilin 550 and Unilin 700 Ethylene wax: Westlake Chemical Company's Epolene E-10J, Epolene E- 14. Clariant Ricowax PED-822, Innospec Viscowax Oxidized polyethylene waxes such as 262; etc. can be used. These can be used alone or in combination. The above can be used in combination. For example, if Unicid 700 is used alone as modifier A, Also, Unisid 700 and Epolene E-10J are combined and used as modifier A. It is possible.

[0019] In this specification, among the constituent parts derived from the modifier A, those derived from the component with the carbon number (16 + 2n) are The structural portion derived from the carbon number 16 is expressed as an (n is an integer of 0 or more). is represented as a0, and the constituent part derived from carbon number 32 is represented as a8.

[0020] <Modifier B> Modifier B is a fat having a melting point of less than 90°C and a functional group that can react with acid or alcohol. It is an aliphatic hydrocarbon-based modifier. The functional group capable of reacting with an acid or alcohol is not particularly limited, but may be a carboxyl group. or its anhydride, hydroxyl group, glycidyl group, alkoxy group, isocyanate group, and ester group Among these, a carboxyl group or its anhydride, a hydroxyl group, and an ester group are preferred. I wish. The melting point of the modifier B is preferably 60°C or higher and lower than 90°C, and more preferably 65°C or higher and lower than 90°C. It is more preferable that the temperature is 70°C or higher and lower than 90°C, and it is even more preferable that the temperature is 60°C or higher. This improves wax dispersibility. Modifier B is a substance having an acid or alcohol at one end of a linear alkyl group, Preferably, the compound contains either 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, the end of the polyester resin can be modified. It is possible to bond the constituent parts derived from material B. The polyester resin is bonded to the end This improves the compatibility between the constituent parts of Modifier B and wax, improving wax dispersion. do. In order to make the melting point of modifier B less than 90°C, the constituent parts derived from modifier B must have a carbon number of 30 or less. The following structures containing straight-chain alkyl groups are preferred: For example, straight-chain alkyl groups having 28 to 18 carbon atoms: A structure containing an alkyl group or a structure containing a linear alkyl group having 28 to 20 carbon atoms is preferred. It's nice.

[0021] In this specification, among the constituent parts derived from the modifier B, those derived from the component with the carbon number (16+2p) are The structural part derived from the carbon number 16 is represented as bp (p is an integer of 0 or more). is denoted as b0, and the constituent part derived from carbon number 32 is denoted as b8.

[0022] The amount of the constituent parts derived from Modifier B is 0.5 to 100% by mass of polyester resin. The range of 8% by mass is preferable. When the content is 0.5% by mass or more, the wax dispersibility is improved. In addition, by keeping the content at 8 mass % or less, the reactivity during resin production and the preservation of the obtained resin are improved. The stability is improved. If the amount of the component derived from modifier B, which is a constituent part of the polyester resin, is within the above range, For example, the modifier B itself can be mixed with the polyester resin without being bonded to it. However, in the case of toners manufactured using a method that does not include a melt-kneading process, the particles of each component are If the particles are too large, problems may occur, so the particle size of each component in the mixture is less than 10 μm. It is preferable that

[0023] Modifier B includes myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, Fatty carboxylic acids such as lauryl alcohol, stearyl alcohol, behenyl alcohol Fatty alcohols such as kohl; rice wax, carnauba wax, candelilla wax Natural ester waxes such as WEP-2, WEP-3, WEP-4, WEP-5, Synthetic ester waxes such as WEP-6 manufactured by NOF Corporation can be used. Or you can use two or more types in combination. For example, rice wax and carnauba wax can be used. It can be used alone as Modifier B or in combination with Carnauba wax and Rice wax. It can be used as modifier B.

[0024] The polyester resin of the present invention contains a constituent part derived from modifier A and a constituent part derived from modifier B. The mass ratio of the constituent parts derived from modifier A to the constituent parts derived from modifier B is 1:2-12. When the mass of the component parts derived from modifier A is 1, the mass of the component parts derived from modifier B is 2 or more. This improves wax dispersibility. In addition, when the constituent parts derived from modifier A are set to 1, the By limiting the mass of the constituent parts derived from B to 12 or less, the storage stability of the polyester resin is good. This further improves wax dispersibility. When the component parts derived from modifier A are taken as 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.

[0025] <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, components with the same carbon number may exist in Modifier B and Modifier B. In such cases, mass spectrometry may be used. In this case, the peaks from modifier A and modifier B are added together to form one peak. In this specification, such a structural portion is referred to as a structural portion abm (m is 0 The constituent parts abm are derived from components with carbon numbers (16 + 2m). It is a component part.

[0026] The polyester resin of the present invention has an m / z value of 87 in the reactive PyGC-MS measurement described below. In the chromatogram of the component ab4, the detection signal intensity is set to 1. The detection signal intensity derived from ab8 is preferably 0.5 or less, and is preferably 0.01 to 0.05. By making the peak derived from ab8 0.01 or more, the wax component can be By setting the ratio to 0.05 or less, the reactivity during resin production and the stability of the resulting resin can be improved. The stability of the material is improved.

[0027] <Method of manufacturing polyester resin> Polyester resin is made from raw materials containing acid components, alcohol components, modifier A, modifier B, and catalysts. The solvent is placed in a reaction vessel, heated to a high temperature, and an esterification reaction or transesterification reaction is carried out. The water or alcohol produced in the reaction was removed, and then the pressure inside the reactor was gradually reduced to 150 Geo under pressure of 20 kPa or less, preferably 20 mmHg or less It can be produced by carrying out polycondensation while distilling off the alcohol component. The constituent parts derived from Modifier A are 0.2 to 3 mass% of 100 mass% polyester resin. To achieve this, the amount of Modifier A added must be 0.5 mass % of 100 mass % polyester resin. It is preferable that the content of the constituent portion derived from the modifier B is in the range of 5% by mass to 5% by mass. To contain the modifier B in the range of 0.5 to 8 mass% in 100 mass% of resin, the amount of modifier B added must be adjusted accordingly. It is preferable that the content of the polyester resin is in the range of 0.5 to 8% by mass relative to 100% by mass of the polyester resin. The value for 100% by mass of polyester resin is calculated by dividing the total amount of raw materials used by the esterification reaction or is the weight of water or alcohol released by the transesterification reaction and polycondensation reaction. Calculated values ​​were used.

[0028] <Catalyst> The catalyst used in the esterification reaction, transesterification reaction, and polycondensation is not particularly limited. For example, titanium alkoxide compounds having an alkoxy group, titanium carboxylates, carboxylates, etc. Titanium compounds such as titanyl phosphate, titanyl carboxylate, and titanium chelate compounds, Organic tin compounds such as butyltin oxide, inorganic tin compounds such as tin oxide and 2-ethylhexane tin compounds, and acetic acid Calcium, calcium acetate hydrate, zinc acetate, antimony trioxide, germanium dioxide Examples include: Examples of titanium alkoxide compounds having an alkoxy group include tetramethoxytitanium. Titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, titanium tetrapentoxide Examples include titanium nitrate, titanium nitrate, and titanium tetraoctoxide. Examples of the titanium carboxylate compound include titanium formate, titanium acetate, and titanium propionate. Titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, adipine Titanium sebacate, titanium hexanetricarboxylate, isooctane tricarboxylate Titanium phosphate, titanium octane tetracarboxylate, titanium decane tetracarboxylate, benzoin Titanium oxide, titanium phthalate, titanium terephthalate, titanium isophthalate, 1,3-naphthalate Titanium dicarboxylate, 4,4-biphenyldicarboxylate, 2,5-toluenedicarboxylate Titanium carboxylate, titanium anthracene dicarboxylate, titanium trimellitate, 2,4, 6-Naphthalenetricarboxylic acid titanium, Pyromellitic acid titanium, 2,3,4,6-naphthalenetricarboxylic acid titanium Titanium tetracarboxylate and the like. Among these, tetrabutoxytitanium is preferred. One of these may be used alone, or two of these may be used in combination. The above may be used in combination.

[0029] The reaction temperature for esterification, transesterification, and polycondensation reactions is 180 to 280°C. The higher the reaction temperature, the higher the productivity, and the lower the reaction temperature, the more likely it is that the polyester resin will decompose and the odor will be reduced. It is possible to suppress the by-production of volatile matter that causes odors, and TVOC (Total Volatility The polymerization temperature is 20 A temperature of 0°C or higher and 270°C or lower is more preferable.

[0030] The method for producing a polyester resin of the present invention is a method for producing a polyester resin containing a polycarboxylic acid raw material and a polyhydric alcohol. A polyester resin is prepared by polycondensing a monomer mixture in the presence of the modifier A and the modifier B. In the presence of the modifier A and the modifier B, a polyvalent carboxylic acid raw material and By polycondensing a monomer mixture containing hydroxyl groups and polyhydric alcohols, hydrocarbons are formed at the molecular ends, etc. In addition, the polyester resin of the present invention can be obtained by When used as a binder resin for toner, the polyester resin of the present invention and the toner are It can significantly improve compatibility with the wax blended in, improving wax dispersibility. It is possible.

[0031] <Physical properties of polyester resin> The glass transition temperature (Tg) of the polyester resin of the present invention is preferably 40 to 85°C. The higher the glass transition temperature, the more improved the storage stability of the toner. The lower the temperature, the more the toner tends to improve in low-temperature fixability. The glass transition temperature of the polyester resin is determined as follows: The baseline on the low temperature side of the chart when measured using a calorimeter at a temperature rise rate of 5°C / min. The temperature at the intersection with the tangent of the endothermic curve near the glass transition temperature is determined and is taken as Tg.

[0032] The softening temperature (T4) of the polyester resin of the present invention is preferably 80 to 170°C, more preferably 85 to 170°C. The higher the softening temperature, the better the hot offset resistance. The lower the temperature, the more the fixability tends to improve. The softening temperature of the polyester resin can be measured using a flow tester.

[0033] The acid value of the polyester resin of the present invention is preferably 0.1 to 60 mgKOH / g, and more preferably 0.5 Up to 50 mgKOH / g is more preferable, and 1 mgKOH / g or more but less than 30 mgKOH / g is preferable. The higher the acid value, the more the productivity of the polyester resin tends to improve. The more the moisture resistance of the polyester resin improves, the easier it becomes to produce a toner that is less susceptible to the effects of the usage environment. There is a tendency for it to become less The acid value of polyester resin is the amount of water required to neutralize the carboxyl groups per 1 g of sample. The amount of potassium oxide expressed in milligrams, expressed in units of mgKOH / g.

[0034] <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 the 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, Inorganic fine powder, resin other than the polyester resin of the present invention (other binder resin), lubricant, etc. It may also contain a mixture.

[0035] Colorants include carbon black, nigrosine, aniline blue, and phthalocyanine blue. Blue, Phthalocyanine Green, Hansa Yellow, Rhodamine dyes and pigments, Chrome Yellow , quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, mono Examples include azo, disazo, and condensed azo dyes or pigments. They may be used alone or in combination of two or more. When the toner is used as a color toner, benzidine yellow is used as a yellow colorant. Examples of magenta colorants include monoazo dyes and pigments, and condensed azo dyes and pigments. Nacridone, rhodamine dyes and pigments, monoazo dyes and pigments, etc., are examples of cyan colorants and Examples include phthalocyanine blue. The content of the colorant is not particularly limited, but it is preferable to use a colorant containing a large amount of the toner in order to obtain excellent color tone, image density, and thermal properties. Therefore, the content is preferably 2 to 10% by mass in 100% by mass of the toner.

[0036] Charge control agents include quaternary ammonium salts and basic or electron-donating organic substances. Positively charged charge control agents; metal chelates, metal-containing dyes, acidic or electron-withdrawing organic Examples of charge control agents include negatively chargeable substances. When the toner is used as a color toner, the charge control agent is colorless or light-colored. Suitable charge control agents are those that have little color disturbance to the ink. Metal salts and complexes of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, etc. amide compounds, phenol compounds, naphthol compounds, etc. Charge control of vinyl polymers with vinyl groups, acrylic acid groups, methacrylic acid groups, and sulfonic acid groups It may also be used as a drug. The content of the charge control agent is preferably 0.5 to 5% by mass in 100% by mass of the toner. If the content of the control agent is 0.5% by mass or more, the amount of charge of the toner tends to be at a sufficient level. If the content is 5 mass % or less, the decrease in the charge amount due to aggregation of the charge control agent tends to be suppressed. .

[0037] As for the wax, carnauba wax was used in consideration of the toner's releasability, storage stability, fixation, color development, etc. Wax, rice wax, beeswax, polypropylene wax, polyethylene wax , synthetic ester wax, paraffin wax, fatty acid amide, silicone wax These may be used alone or in combination of two or more. That's fine. 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 since it affects the above-mentioned toner performance, The wax content is preferably 0.3 to 15% by mass in 100% by mass. The upper limit of the wax content is preferably 2% by mass or more, and more preferably 2% by mass or more. The value is more preferably 13% by mass or less, particularly preferably 12% by mass or less. The polyester resin of the present invention has excellent wax dispersibility, so waxes that can be blended It is now possible to increase the types and amounts of inks used, resulting in higher performance in fixing properties and offset resistance than ever before. Therefore, a toner having good storage stability can be provided.

[0038] Additives such as flow modifiers include fine powders of silica, alumina, titania, etc. Superpolymer: magnetite, ferrite, cerium oxide, strontium titanate, conductive titanium Examples include inorganic fine powders such as nia; resistance regulators such as styrene resins and acrylic resins; and lubricants. These are used as internal or external additives. The content of these additives is preferably 0.05 to 10% by mass in 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 is sufficient. When the content is 10% by mass or less, the image stability of the toner tends to be good. do.

[0039] Other binder resins include, for example, polyester resins other than those of the present invention, styrene resins, etc. These include olefin resins, cyclic olefin resins, and epoxy resins. Alternatively, two or more of them may be used in combination. When other binder resins are used, the polyester resin of the present invention is contained in 100% by mass of the total binder resins. It is preferable to use 20% by mass or more of steric resin.

[0040] The toner of the present invention may be used in any of magnetic one-component developers, non-magnetic one-component developers, and two-component developers. It can also be used as a pigment.

[0041] When the toner of the present invention is used as a magnetic one-component developer, the toner contains a magnetic material. Examples of magnetic materials include ferrite, magnetite, and ferromagnetic materials containing iron, cobalt, nickel, etc. Ferromagnetic alloys; they do not contain compounds or ferromagnetic elements, but can be made ferromagnetic by appropriate heat treatment. Alloys that become like this (e.g. manganese-copper-aluminum, manganese-copper-tin, etc.) Examples of suitable alloys include the so-called Heusler alloy containing chromium and copper, and chromium dioxide. The content of the magnetic material is not particularly limited, but it has a large effect on the grindability of the toner. The content of the magnetic material is preferably 3 to 70% by mass in 100% by mass of the toner. The amount of charge on the toner tends to be at a sufficient level, and if it is 70% by mass or less, the toner can be fixed. The upper limit of the content of the magnetic material is preferably 60% by mass or less. It is preferable, and 50 mass % or less is particularly preferable.

[0042] 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. It is used in this way. The carrier may be, for example, a magnetic substance such as iron powder, magnetite powder, or ferrite powder; Examples include magnetic carriers and those with a resin coating on the surface. Examples of the coating resin for the carrier include styrene resin, acrylic resin, styrene resin, and Acrylic copolymer resin, silicone resin, modified silicone resin, fluorine resin, and mixtures of these resins. The amount of the carrier used is preferably 500 to 3,000 parts by mass relative to 100 parts by mass of the toner. If the amount of carrier used is 500 parts by mass or more, fogging and other problems tend to be less likely to occur. If the amount is 3000 parts by mass or less, the density of the fixed image tends to be sufficient.

[0043] The method for producing the toner of the present invention is not particularly limited. After mixing the fat and the above-mentioned compound, the mixture is melt-kneaded in a twin-screw extruder or the like, and then crushed into coarse, fine, or fine powder. A method of producing the product by classifying the product and, if necessary, adding inorganic particles to the outside (pulverization method); The clear polyester resin and compound are dissolved and dispersed in a solvent, granulated in an aqueous medium, and then The solvent is removed, washed, and dried to obtain toner particles, which are then optionally treated with external addition of inorganic particles. and a method of producing the polyester resin of the present invention by emulsifying the polyester resin in water and mixing it with a finely divided blend. Both are aggregated and fused in water to form granules, which are then washed and dried to obtain toner particles. Examples of such a method include a manufacturing method in which inorganic particles are externally added (chemical method).

[0044] 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 If the average particle size of the toner is 3 μm or more, productivity is good. On the other hand, if the average particle size of the toner is 15 μm or less, high-quality images can be formed stably. do. [Example]

[0045] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. It is not something that is done. The polyester resins shown in the examples were evaluated as follows.

[0046] [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- 60"), the baseline and endothermic curve of the chart at a heating rate of 5℃ / min The measurement was made from the intersection point with the tangent of the line. The measurement sample was weighed out in an aluminum pan at 10 mg ± 0.5 mg. After melting for 10 minutes at 100°C, which is above the glass transition temperature, the sample was rapidly cooled using dry ice. The sample was used.

[0047] <Measurement of softening temperature (T4)> The softening temperature of polyester resin was measured using a flow tester (Shimadzu Corporation, CFT-500 D"), a 1mmφ×10mm nozzle, a load of 294N, and a temperature rise rate of 3℃ / min The temperature was measured when half of a 1.0 g resin sample flowed out under a constant rate of temperature increase. was taken as the softening temperature.

[0048] <Acid value measurement> The acid value of the polyester resin was measured as follows. Approximately 0.2 g of the measurement sample was accurately weighed into a side-arm Erlenmeyer flask (a(g)), and Add 20 mL of colander, heat in a nitrogen atmosphere at 230°C for 15 minutes, and measure the sample size. After cooling to room temperature, add 20 mL of chloroform and a few drops of cresol red solution. was added and titrated with 0.02N KOH solution (titration amount = b (mL), the strength of the KOH solution A blank measurement was carried out in the same way (titer = c (mL)), and the acid value was calculated according to the following formula: Calculated. Acid value (mgKOH / g)={(bc)×0.02×56.11×p} / a

[0049] <Content of constituent parts derived from modifier A and constituent parts derived from modifier B> Components derived from modifier A and components derived from modifier B bonded to polyester resin The content of each of these was measured as follows. Pre-measurement processing Each polyester resin was dissolved in chloroform and the insoluble matter was removed. When no polyester resin is used (polyester resin 20 described later), there is no insoluble matter, and the insoluble matter is mainly polyester. This is due to modifiers A and B being mixed with the polyester resin without bonding. The chloroform was removed from the obtained chloroform solution, and the dried solution was used for each analysis. Modified materials A and B were also subjected to the respective measurements as they were.

[0050] ·NMR measurement Measurement was performed under the following conditions, and the composition was calculated using the integral value of the spectrum. The constituent parts of the resin derived from modifier A and modifier B are not classified by compound but by The total amount of components derived from Modifier A and Modifier B was calculated. [NMR measurement conditions] Equipment JEOL ECS-400 Magnet JMTC-400 / 54 / SS Observation frequency 1 H 400MHz 13 C 100MHz Solvent Polyester resin: deuterated chloroform Modifier A, Modifier B: DMSO-d6 Temperature Polyester resin: 35℃ Modifier A, Modifier B: 120℃ Polyester resin: 1 H 1000 times, 13 C 1024 times Modifier A, Modifier B: 1 H 64 times, 13 C 1024 times

[0051] Reaction PyGC-MS measurement The measurements were carried out in the following manner. Step 1. Calculate the sum of the peak areas in the chromatogram of m / z=87 for each modifier itself. The "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. It means "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. Mix equal amounts of rice wax, a type of modifier B, and other modifiers A and B. The blend was measured, and the representative peaks of each modifier were measured in the mass spectrum at m / z = 87. The peak area of ​​each modifier was calculated using the peak area and the area ratio obtained in step 2. The area ratio of each modifier was calculated when the wax was set to 1. Step 4. In the chromatogram of the sample m / z=87, identify the representative peaks of each modifier. Using the area and the area ratio obtained in step 2, calculate the sum of the peak areas derived from each modifier in the sample. Using the area ratio of the sum calculated and the same weight of the modifier calculated in step 3, calculate the modifier. The weight ratio was calculated. Step 5: Using the weight ratio of the modifiers obtained in step 4 and the molecular weight of each modifier, calculate the molar ratio of the modifiers. Calculated.

[0052] [Reaction PyGC-MS measurement conditions] Equipment: Agilent Technology GC / MS 7890 / 5975 Lontia Labs PY-3030D Double Shot Pyrolyzer Column: Frontier Labs Ultra-Alloy +5 (30m x 0.25mm) ID 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℃ Quadrupole temperature 150℃ Scan resin 20~500amu Thermal decomposition temperature 400℃ Interface temperature 300℃ Reaction reagent: 25% TMAH-methanol solution The total amount (molar ratio) of modifier to resin determined by NMR and reaction PyGC-MS The molar ratio of the modifier in the sample is used to calculate the content of the modifier relative to the resin in the sample. did.

[0053] <Detection signal intensity from component ab8 when the detection signal intensity from component ab4 is set to 1 > In the chromatogram of m / z=87 in the reaction PyGC-MS measurement, RT=2 The detected signal strength from the baseline of 5.9 (indicating ab4) and RT=31.0 (ab The detected signal intensity of ab4 was measured from the baseline (shown in Fig. 8), and the detected signal intensity of ab4 was set as 1. The detected signal intensity of ab8 was calculated.

[0054] <Components in resin larger than 10 μm> 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 examined under a microscope. The number of components larger than 10 μm in any 100 μm square was counted. These are components derived from modifier A or modifier B. <Wax dispersibility> The formulations shown in Tables 5, 6, and 7 were polyester resin, modifier A, modifier B, and Fischer-Tropsch wax SX80 manufactured by Nippon Seiro Co., Ltd. was used in the dry blend. After mixing, the mixture was put into a twin-screw extruder (Ikegai PCM-29) with the barrel temperature set at 120°C. The sample pieces were kneaded in a press set at the softening temperature of the resin, and plate-shaped samples were taken. The film was then heat-pressed in a press to a thickness of 50 μm, and observed under a microscope at 500x magnification. The particle size of the wax particles within a 0 μm square was checked and evaluated according to the following criteria. S: Particles cannot be identified A: Particles smaller than 0.5 μm can be barely seen B: Particles of 0.5 μm or more and less than 1 μm can be confirmed C: Particles larger than 1 μm and smaller than 3 μm are observed, and dispersibility is somewhat poor. D: Particles between 3 μm and 5 μm in size are visible, and dispersibility is poor. E: Particles larger than 5 μm are observed, and dispersibility is significantly poor

[0055] [Examples 1 to 14, Comparative Examples 1 to 6] The materials used to prepare the polyester resins of the present invention and comparative polyester resins were The raw materials are shown in Tables 1 and 2. The mass % in Table 1 is the mass after the esterification reaction and polycondensation reaction. The total mass of the polyester resin obtained was calculated from the raw materials, and the total mass (calculated value) was multiplied by 10 This is the value when set to 0%.

[0056] [Table 1]

[0057] [Table 2]

[0058] Details of the abbreviations and names in Tables 1 and 2 are as follows: Diol A: Propylene oxide derivative of bisphenol A (PO2.3 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℃ Unilin 700: Baker Hughes, linear polyethylene with one terminal alcohol, melting point 100.3℃ Unilin 1000: Baker Hughes, linear polyethylene with one terminal alcohol, melting point 107.9℃ Epolene E-10J: Westlake Chemical Company, oxidized polyethylene, melting point 100 .9℃ Carnauba wax: Toyo Adre, 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

[0059] <Production of Polyester (PES) Resin 1> 82 mol parts of terephthalic acid and 13 mol parts of isophthalic acid per 100 mol parts of total acid components 5 parts by mole of trimellitic anhydride, 35 parts by mole of diol A, 1 part by mole of diol B, ethyl acetate 80 parts by mole of polyethylene glycol, 2% by mass of Uniside 700 as modifier A, Material B is 2% by mass of carnauba wax and 2% by mass of rice wax, and titanium is used as a catalyst. 500 ppm of tetrabutoxide based on the total acid components was added to the reaction vessel equipped with the 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 started to increase. The temperature was then heated to 265°C, and the esterification reaction was carried out while maintaining this temperature. After the distillation of water from the reaction system has stopped and the esterification reaction has finished, the temperature in the reaction system is lowered and the reaction mixture is heated for 2 The temperature was kept at 40°C, and the pressure inside the reaction vessel was reduced over approximately 40 minutes until the vacuum reached 133 Pa. The polycondensation reaction was carried out while distilling off the polyhydric alcohol. As the reaction progresses, the viscosity of the reaction system increases, and as the viscosity increases, the degree of vacuum increases, and the flow of the stirring blades The condensation reaction was carried out until the torque reached a value indicating the desired softening temperature. At the indicated time, the stirring was stopped, the reaction system was returned to atmospheric pressure, and the reactants were pressurized with nitrogen to transfer the reaction mixture to the reaction vessel. The mixture was taken out (discharged) from the flask to obtain Polyester Resin 1.

[0060] <Production of Polyester (PES) Resins 2 to 20> In the same manner as in polyester resin 1, raw materials having the composition shown in Tables 1 and 2 were used. Polyester resins 2 to 20 were obtained.

[0061] Resin compositions of polyester resins 1 to 20 and glass transition of the obtained polyester resins Measurement results of temperature Tg (℃), softening temperature T4 (℃), acid value AV (mgKOH / g) and resin evaluation The results of the value (components of 10 μm or more in the resin) are shown in Tables 3 and 4. The resin evaluations in Tables 3 and 4 were carried out by measuring small pieces of polyester resin at the softening temperature of the resin, as described above. Heat press to form a 50 μm film, observe under a microscope, and measure the thickness of the film within 10 μm or less within any 100 μm square. The number of components above was confirmed. Polyester resins 15 to 17, which used only Modifier A, were 10 It was confirmed that components larger than 1 μm were present. On the other hand, polyester resins 1 to 14 using both modifier A and modifier B, or only modifier B In polyester resins 18 and 19, no components larger than 10 μm were observed. .

[0062] [Table 3]

[0063] [Table 4]

[0064] Next, the wax dispersibility of the obtained polyester resin was evaluated. The formulations shown in Tables 6 and 7 were polyester resin, modifier A, modifier B, and wax ( Fischer-Tropsch wax SX80 (manufactured by Nippon Seiro Co., Ltd.) was mixed by dry blending. After that, the mixture was kneaded in a twin-screw extruder (Ikegai PCM-29) with the barrel temperature set to 120°C. A small piece of the sample was placed in a press set at the softening temperature of the resin. The film was then heat-pressed to a thickness of 50 μm and observed under a microscope at 500x magnification. The particle size of the wax particles in the container was checked and evaluated according to the following criteria. The longest distance was taken as the particle size, and if the particle was spherical, the diameter was taken as the particle size. S: Particles cannot be identified A: Particles smaller than 0.5 μm can be barely seen B: Particles of 0.5 μm or more and less than 1 μm can be confirmed C: Particles larger than 1 μm and smaller than 3 μm are observed, and dispersibility is somewhat poor. D: Particles between 3 μm and 5 μm in size are visible, and dispersibility is poor. E: Particles larger than 5 μm are observed, and dispersibility is significantly poor The types and amounts of resins and waxes used in the evaluation and the evaluation results are shown in Tables 5 to 7. vinegar.

[0065] [Table 5]

[0066] [Table 6]

[0067] [Table 7]

[0068] In Example 1 using polyester resin 1, the wax dispersibility evaluation result was S. In addition, polyester resin other than that of the present invention was used in a ratio of 1:1 to 1 polyester resin. In Example 2, the result was S. In Example 3, the ester resin was used in a ratio of 1:2, which was B. In Examples 4 to 14, the wax dispersion evaluation results were all B or higher.

[0069] Comparison using polyester resin 13, where the mass ratio of modifier B is 13 when modifier A is 1. In Example 1, the dispersed particle diameter of wax is 1 to 2 μm, and the polyester resin of the present invention is used. In addition, the mass ratio of Modifier B to Modifier A was 1. Comparative Example 2, which used polyester resin 14 of 1.7, had a wax dispersed particle diameter of 1 to 2 μm. The wax dispersibility was inferior to that when the polyester resin of the present invention was used. Polyester resins 18 and 19 were prepared using only modifier B without using modifier A. In Comparative Examples 3 and 4, the wax dispersion evaluation results were C and D, respectively, and the wax dispersion was better than that of Example 1. was significantly inferior. In Comparative Example 5, unused polyester resin 20 was used for both Modifier A and Modifier B. In Example 6, the same modifiers A and B were added in the same amounts during polymerization of polyester resin 1. These waxes are blended into the polyester resin 20 during kneading so that the wax becomes The dispersibility was poor.

[0070] Next, the PyGC-MS measurement results for polyester resin 1 at m / z=87 are shown in Figure 1. 1, an enlarged view in the vertical axis direction of FIG. 1 is shown in FIG. 2. In addition, as an example of modifier A and modifier B, , and the m / z=87 of the modifier A (Unicid 700) used in polyester resin 1 The reaction PyGC-MS measurement results are shown in Figure 3. The PyGC-MS measurement results for the reaction in Fig. 4 are shown. The PyGC-MS measurement results for the reaction are shown in Figure 5.

[0071] The strongest detected signal is from the 24 carbon atom component (ab4 in Figure 1). The peaks are due to the carbon chain with 24 carbon atoms contained in modifier A and the carbon chain with 2 carbon atoms contained in modifier B. The detected signal is due to the carbon chain of 4. Also, the structure of 32 carbon atoms is observed very weakly. The detection signal derived from the component part (peak ab8 in Figure 1) was detected from the modified material A and modified material B. The detection signal is due to the carbon chain containing 32 carbon atoms. It can be seen that a peak originating from the constituent part of the carbon number 40 is detected. Considering the results, this peak is the detection signal due to the carbon number 40 contained in the modifier A (Fig. 2, a12 peak).

[0072] In polyester resin 1, in which modifier A and modifier B were introduced in the composition shown in Table 3, Compared with the detection signal from the prime number 32 component, the detection signal from the carbon number 24 component The signal was observed to be more than twice as strong.

Claims

1. A polyester resin having 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 A having a melting point of 90°C or higher and a functional group capable of reacting with an acid or an alcohol, and a constituent moiety (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 an alcohol, wherein the mass ratio of constituent moiety (A1) to constituent moiety (B1) is in the range of 1:2 to 12.

2. 2. The polyester resin according to claim 1, wherein the melting point of the modifier A is 120°C or less.

3. 3. The polyester resin according to claim 1, wherein the modifier A comprises 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 claims 1 to 3, wherein the amount of the constituent moiety (A1) is in the range of 0.2 mass% to 3 mass% based on 100 mass% of the polyester resin.

5. 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.

6. The modifier B comprises 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 5.

7. The polyester resin according to any one of claims 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 claims 1 to 7.

9. A method for producing a polyester resin, comprising polycondensing a monomer mixture containing a polycarboxylic acid and a polyhydric alcohol 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 an 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 an alcohol, wherein the amount of modifier B added is in the range of 1 to 6 relative to the amount of modifier A added.

10. The method for producing a polyester resin according to claim 9, wherein the melting point of the modifier A is 120°C or lower.

11. 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.

12. The method for producing a polyester resin according to any one of claims 9 to 11, wherein the amount of the 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.

13. 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.

14. The method for producing a polyester resin according to any one of claims 9 to 13, wherein 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.

15. The method for producing a polyester resin according to any one of claims 9 to 14, wherein the amount of the modifier B added is in the range of 0.5% by mass to 8% by mass based on 100% by mass of the polyester resin.

16. The composition comprises a polycarboxylic acid-derived constituent moiety (C1), a polyhydric alcohol-derived constituent moiety (D1), a constituent moiety an (where n is the same as n in the aliphatic hydrocarbon-based modifier A-derived carbon number of 16 + 2n, where n is at least one integer from 12 to 15), a melting point of 90°C or higher, and a functional group capable of reacting with an acid or alcohol, and a constituent moiety abm (where m is the same as m in the aliphatic hydrocarbon-based modifier A-derived carbon number of 16 + 2n, where n is at least one integer from 12 to 15), a melting point of less than 90°C, and a functional group capable of reacting with an acid or alcohol, and a carbon number of 16 + 2m (where m is an integer from 3 to 8), abm (where m is the same as m in the aliphatic hydrocarbon-based modifier A-derived carbon number of 16 + 2m, where m is an integer from 3 to 8), abm (where m is the same as m in the aliphatic hydrocarbon-based modifier B-derived carbon number of 16 + 2m, where m is an integer from ab3 to ab8), a 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 claim 16, wherein the modifier A includes constituent parts (a0 to a15) having a carbon number (16 + 2n, n is an integer from 0 to 15).

18. The polyester resin according to claim 16, wherein the modifier B has a constituent portion (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. The polyester resin according to claim 18, wherein the modifier B does not have a constituent moiety derived from a carbon chain having more than 40 carbon atoms.

20. A toner using the polyester resin according to any one of claims 16 to 19.

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