JP2018151629A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder and a toner excellent in charging characteristics (saturated charged amount, charge rising property and charge stability).SOLUTION: A toner binder contains a polyester resin (A) obtained by reaction of a polyol component (x) and a polycarboxylic acid component (y) as constituent materials, where (A) contains 80-100 mol% of an aromatic polycarboxylic acid component based on the total molar number of the polycarboxylic component (y) as the constituent material, contains 70-100 mol% of an aromatic dicarboxylic acid component (y1) having two carboxyl groups at a para position of the aromatic ring based on the total molar number of the polycarboxylic acid component (y), and satisfies the following relational expression (1): Q(60)=α×acid value+β. In the relational expression (1), Q(60)(μC/g) is a 60 seconds agitation charged amount; the acid value is an acid value of (A); α value is -1.0 to -0.8; and β value is -25 to -20.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder and a toner.

In recent years, with the rapid progress of digitization, colorization, combination, high speed, and high image quality of electrophotographic copiers and printers, more demands have been made on energy saving, high reliability, and environmental stability than ever before. Is growing.
The electrophotographic system includes a process composed of steps of charging, exposure, development, transfer, fixing, cleaning, and static elimination, and material technology represented by a photoreceptor and a developer (toner). Various improvements have been made to each process technology and material technology from the invention by Carlson to the present. The characteristics required for the toner are various, such as charging characteristics, powder characteristics, thermal characteristics, and color characteristics. In particular, charging characteristics that control toner movement are an important key technology in developing toners in order to cope with energy saving, high reliability, and environmental stability.
For example, in order to save energy, it is necessary to improve the charge rising property of the toner in order to obtain a desired toner charge amount by friction in a very short time. Further, for high reliability, stable toner charge amount control is required so that the toner charge amount at the development site always falls within the set range allowed in the process. Furthermore, under high humidity conditions, the toner charge amount decreases and the toner is developed on white areas, and when dried, the image quality density decreases due to overcharging. Therefore, there is a need to eliminate the change in toner charge amount due to environmental differences such as high temperature and high humidity in the winter and low temperature and low humidity in winter. In the toner industry, there is an urgent need to develop a high-quality toner whose charging characteristics are highly controlled.
The toner is composed of a toner binder, a pigment, a wax, a charge control agent (CCA), and an external additive. The toner binder is the main component of the toner and occupies 80 to 90% by weight. Since toner is generally charged by friction, how to control the surface property of the toner is important, and the toner binder, which is the main component of the toner, plays a significant role in charging characteristics.
As the toner binder, styrene resin, polyester resin, epoxy resin, or the like is used. In particular, due to the recent strong demand for energy saving, development of polyester resins that can be fixed at a lower temperature is active. A characteristic of polyester resins is that they have carboxylic acid groups and hydroxyl groups in the molecule, and these functional groups hydrogen bond in and between molecules, increasing the apparent molecular weight of the resin and preventing offset. , Improve the mechanical strength. The charging characteristics are faster and better than the styrene resin, but there are problems such as a large change in the charge amount in a high-temperature and high-humidity environment.

As a conventional technique, there are an acid value, an aromatic ring concentration, hygroscopicity, and the like as control factors for the charging characteristics (saturation charge amount, charge rising property and charge stability) of a polyester resin.
<Acid value>
The charge of the polyester resin is affected by the amount of acid groups (acid value) present in the molecule. In general, the higher the acid value, the higher the negative chargeability and the faster the rise of charge. However, in a high-temperature and high-humidity environment, the charge amount change of the polyester resin having a high acid value is large, and it is difficult to achieve both the charge amount and the charge amount change only by controlling the acid value.
<Aromatic ring concentration>
If the aromatic ring concentration in the polyester resin is increased, the charge amount is increased and the charge rising property is also improved. For example, Patent Document 1 defines the amounts of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, aromatic diol and aromatic dicarboxylic acid in order to improve the charge rising property and durability. Although the toner has been disclosed and the effect has been obtained, it is still not sufficient, and further improvement is desired.
Patent Document 2 also discloses a toner that defines an aromatic ring concentration, but it does not satisfy all of the saturation charge amount, charge rising property, and charge stability.
<Hygroscopicity>
If the hygroscopicity is high, the change in charge amount in a high temperature and high humidity environment becomes large. In order to improve the hygroscopicity, Patent Document 3 discloses a toner binder in which the number of terminal functional groups of a polyester resin is controlled by copolymerizing a monovalent carboxylic acid and / or a monovalent alcohol component. . Although some effect is obtained, further performance improvement is desired.
Patent Document 4 discloses a polyester in which an aromatic ring is introduced into a polyester terminal by polycondensation of an alcohol component containing a specific amount of a (poly) alkylene glycol monoaryl ether of a monovalent aromatic alcohol and an aromatic dicarboxylic acid. An example of hydrophobizing is disclosed, but although the charge rising property and charge stability are improved to some extent, the saturation charge amount is not sufficient.
It is a major issue in toner development to simultaneously satisfy all of the charging characteristics such as the saturation charge amount, the charge rising property, and the charging stability, and a solution is urgently required.

Japanese Patent Laid-Open No. 2006-33606 Japanese Patent Laying-Open No. 2006-80861 JP-A-6-263854 JP, 2006-218392, A

  An object of the present invention is to provide a toner binder excellent in charging characteristics (saturation charge amount, charge rising property and charge stability) and a toner containing the toner binder.

As a result of intensive investigations to solve these problems, the present inventors have reached the present invention.
That is, the present invention provides a toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) and a polycarboxylic acid component (y) as constituent raw materials, wherein (A) is a constituent raw material. As an aromatic polycarboxylic acid component based on the total number of moles of the polycarboxylic acid component (y) is contained in an amount of 80 to 100 mol%, and based on the total number of moles of the polycarboxylic acid component (y), A toner binder which is a polyester resin containing 70 to 100 mol% of an aromatic dicarboxylic acid component (y1) having two carboxyl groups and satisfying the following relational expression (1); containing the above toner binder and colorant Toner.
Q (60) = α × acid value + β (1)
[However, in the relational expression, the 60-second stirring charge amount Q (60) (μC / g) is obtained by comparing (A) with a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution (volume average particle size and number average). (Particle diameter ratio) A particle charged with Dv / Dn = 1.3 is a 60-second stirring charge amount by a blow-off method in an environment of a temperature of 23 ° C. and a humidity of 50%. Dn is the number average particle diameter (μm) of the particles. The acid value (mgKOH / g) is the acid value of (A). The α value is −1.0 to −0.8, and the β value is −25 to −20. ]
The present invention also provides
A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) and a polycarboxylic acid component (y) as constituent raw materials, wherein (A) is a polycarboxylic acid component as a constituent raw material 80 to 100 mol% of the aromatic polycarboxylic acid component based on the total number of moles of (y), and two carboxyl groups at the para position of the aromatic ring based on the total number of moles of the polycarboxylic acid component (y) The aromatic dicarboxylic acid component (y1) having a content of 70 mol% or more and less than 100 mol%, and the aromatic polycarboxylic acid component (y2) having 3 or more carboxyl groups is contained more than 0 mol% and 10 mol% or less. And a toner containing a toner binder, which is a polyester resin satisfying the following relational expression (1), and a colorant.
Q (60) = α × acid value + β (1)
[60 second stirring charge amount Q (60) (μC / g): (A) is a volume average particle size (Dv) of 5-8 μm and particle size distribution (ratio of volume average particle size to number average particle size) Dv /Dn=1.3 Particles with a temperature of 23 ° C. and a humidity of 50% are 60-second stirring charge amount by blow-off method. Dn is the number average particle diameter (μm) of the particles. The acid value (mgKOH / g) is the acid value of (A). The α value is −1.0 to −0.8, and the β value is −25 to −20. ]

  According to the present invention, it is possible to provide a toner binder excellent in charging characteristics (saturation charge amount, charge rising property and charge stability) and a toner containing the toner binder.

The present invention is described in detail below.
The polyester resin (A) used in the present invention is obtained by reacting (polycondensation) the polyol component (x) and the polycarboxylic acid component (y), and the total number of moles of the polycarboxylic acid component (y) as a constituent raw material. An aromatic dicarboxylic acid component containing 80 to 100 mol% of an aromatic polycarboxylic acid component and having two carboxyl groups in the para position of the aromatic ring based on the total number of moles of the polycarboxylic acid component (y) ( The other resin composition is not particularly limited as long as it contains 70 to 100 mol% of y1) and satisfies the following relational expression (1).
The polyester resin (A) used in the present invention is obtained by reacting (polycondensation) the polyol component (x) and the polycarboxylic acid component (y), and the total moles of the polycarboxylic acid component (y) as a constituent raw material. Aromatic dicarboxylic acid containing 80 to 100 mol% of aromatic polycarboxylic acid component based on the number and having two carboxyl groups in the para position of the aromatic ring based on the total number of moles of polycarboxylic acid component (y) The component (y1) is 70 mol% or more and less than 100 mol%, and the aromatic polycarboxylic acid component (y2) having 3 or more carboxyl groups is contained more than 0 mol% and 10 mol% or less, and the relational formula described later Other resin compositions are not particularly limited as long as (1) is satisfied.
Further, the polyester resin (A) may be one kind or a mixture of two or more kinds of polyester resins, for example, a combination of a linear polyester resin and a non-linear polyester resin.

Examples of the polyol component (x) include diols and 3 to 8 or more valent polyols, and examples of the polycarboxylic acid component (y) include dicarboxylic acids and 3 to 6 or more valent polycarboxylic acids. .
As the polyol component (x), the diol includes an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); (poly) oxy of the above alicyclic diol Rukylene [Alkylene group having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) or less polyoxyalkylene group is the same] Ether [Oxyalkylene unit (hereinafter abbreviated as AO unit) 1 to 30]; Divalent phenol [ And monocyclic dihydric phenols (for example, hydroquinone), polyoxyalkylene ethers of bisphenols (number of AO units: 2 to 30); and the like.
Examples of the polyol having 3 to 8 valences or more include 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin and trimethylolethane). , Trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol); saccharides and esterified products thereof such as sucrose and methylglucoside); (poly) oxyalkylene ethers (AO units) of the above aliphatic polyhydric alcohols 1 to 30); polyoxyalkylene ethers of trisphenols (such as trisphenol PA) (numbers of AO units 2 to 30); polys of novolak resins (such as phenol novolac and cresol novolac, average polymerization degree 3 to 60) Oxyalkylene ether Etc. (the number 2 to 30 of AO units) can be mentioned.

Polyoxyalkylene ethers of bisphenols are obtained by adding alkylene oxide (hereinafter abbreviated as AO) to bisphenols. Examples of bisphenols include those represented by the following general formula (1).
OH-Ar-X-Ar-OH (1)
[Wherein X is an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond, Ar is substituted with halogen or an alkyl group having 1 to 30 carbon atoms. Represents a good phenylene group. ]
Specifically, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2 , 2′-diethylbisphenol F, and two or more of these may be used in combination. As AO added to these bisphenols, those having 2 to 4 carbon atoms are preferable. Specifically, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2 , 3-, 1,3- or iso-butylene oxide, tetrahydrofuran (hereinafter referred to as THF) and a combination of two or more thereof. Of these, EO and / or PO are preferred. The added mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles.
Of the polyoxyalkylene ethers of bisphenols, EO and / or PO adducts of bisphenol A (average added mole number of 2 to 4, especially 2 to 3) are preferable from the viewpoint of toner fixing properties and charging characteristics. .

  Among the polyol components (x), those which are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance when used as a toner are alkylene glycols having 2 to 12 carbon atoms and polyoxyalkylene ethers (AO units) of bisphenols. 2 to 30), 3 to 8 or higher aliphatic polyhydric alcohols, and polyoxyalkylene ethers of novolac resins (2 to 30 AO units), which are more preferable from the viewpoint of storage stability. Are alkylene glycols having 2 to 10 carbon atoms, polyoxyalkylene ethers of bisphenols (number 2 to 5 of AO units), polyoxyalkylene ethers of novolac resins (number 2 to 30 of AO units), and particularly preferably , C 2-6 alkylene glycol, bisphenol A polyoxyalkylene An ether (number of AO units 2-5), and most preferably, ethylene glycol, propylene glycol, a polyoxyalkylene ether of bisphenol A (number of AO units 2-3).

  The polyol component (x) contains an aromatic diol of 70 mol% or more based on the total number of moles of the polyol component (x) from the viewpoint of chargeability (saturation charge amount, charge rising property, charge stability). The content is preferably 80 mol% or more, more preferably 90 mol% or more.

As the aromatic diol, a polyoxyalkylene ether having a bisphenol A structure is preferable, and not only charging characteristics are improved but also resin strength is increased and durability as a toner is also improved.
As the polyol component (x), one kind or two or more kinds of raw materials may be used in combination.

As polycarboxylic acid component (y), as dicarboxylic acid, C2-C50 alkane dicarboxylic acid (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, sebacic acid, etc.), C4-C50 Alkene dicarboxylic acids (alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid), C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) Acid and naphthalenedicarboxylic acid, etc.), vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid Copolymer) and the like.
Examples of the trivalent to hexavalent or higher polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid). Etc.), vinyl polymers of unsaturated carboxylic acids [Mn: 450 to 10,000] (styrene / maleic acid copolymers, styrene / acrylic acid copolymers, styrene / fumaric acid copolymers, etc.) and the like. It is done.
As the polycarboxylic acid component (y), anhydrides and lower alkyl (carbon number 1 to 4) esters (such as methyl ester, ethyl ester, and isopropyl ester) of these polycarboxylic acids may be used.

  Among these polycarboxylic acid components (y), those preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance are alkanedicarboxylic acids having 2 to 50 carbon atoms, alkenedicarboxylic acids having 4 to 50 carbon atoms, carbon An aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aromatic polycarboxylic acid having 9 to 20 carbon atoms, and more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, and terephthalic acid from the viewpoint of storage stability. , Isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and combinations thereof, particularly preferably adipic acid, terephthalic acid, trimellitic acid and combinations thereof. These acid anhydrides and lower alkyl esters (for example, alkyl groups having 1 to 4 carbon atoms, for example) are also preferred.

  As the aromatic dicarboxylic acid component (y1), terephthalic acid and / or terephthalic acid alkyl ester having 1 to 4 carbon atoms in the alkyl group are preferable, and both the saturated charge amount, charge rising property and charging stability are good. Further, the resin strength is increased and the blocking resistance is improved.

The polycarboxylic acid component (y) contains 80 to 100 mol% of an aromatic polycarboxylic acid component based on the total number of moles of the polycarboxylic acid component (y) as a constituent raw material. If it is less than 80 mol%, the charging characteristics are not good.
Moreover, 70-100 mol% of aromatic dicarboxylic acid components (y1) which have two carboxyl groups in the para position of an aromatic ring based on the total number of moles of a polycarboxylic acid component (y) are contained. If it is less than 70 mol%, the charging characteristics are not good.
Alternatively, the aromatic dicarboxylic acid component (y1) having two carboxyl groups at the para position of the aromatic ring based on the total number of moles of the polycarboxylic acid component (y) is 70 mol% or more and less than 100 mol%, and 3 or more The aromatic polycarboxylic acid component (y2) having a carboxyl group of more than 0 mol% and not more than 10 mol% is contained. When (y1) is less than 70 mol%, the charging characteristics are not good, and when (y2) exceeds 10 mol%, it is difficult to achieve both hot offset resistance and low-temperature fixability.
The content of (y2) is preferably 0.1 to 9 mol%, more preferably 0.1 to 8 mol%.

Examples of the aromatic polycarboxylic acid component (y2) include trimellitic acid, pyromellitic acid, anhydrides of these acids, and alkyl esters having 1 to 4 carbon atoms in the alkyl group of these acids from the viewpoint of charging characteristics. preferable.
As the polycarboxylic acid component (y), one kind or two or more kinds of raw materials may be used in combination.

  In order to control the hygroscopicity of the polyester resin, the alcohol component may appropriately contain a monovalent monoalcohol, and the carboxylic acid component may appropriately contain a monovalent monocarboxylic acid.

Examples of monovalent monoalcohols include aliphatic monoalcohols and aromatic monoalcohols.
Examples of the aliphatic monoalcohol include chain saturated monoalcohol and chain unsaturated monoalcohol.

  Examples of the chain saturated monoalcohol include linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms (methanol, ethanol, 1-propanol, propyl alcohol, isopropyl alcohol, butanol, pentanol, 2-methyl-1- Butanol, 2,2-dimethyl-1-propanol, hexanol, 4-methyl-1-pentanol, 2,3-dimethyl-2-butanol, heptanol, 3-ethyl-3-pentanol, octanol, 2-ethyl- 1-hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol), and straight-chain or branched-chain saturated monomers having 1 to 30 carbon atoms Alcohol with 2 to 4 carbon atoms (EO, PO and BO) obtained by adding the (addition molar number of 1 to 20 mol), and the like.

  Examples of the chain unsaturated monoalcohol include linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (allyl alcohol, 2-buten-1-ol, 2-penten-1-ol, 2-hexene- 1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitolyl alcohol, oleyl alcohol and linoleyl alcohol Etc.), and those obtained by adding AO (EO, PO, and BO) having 2 to 4 carbon atoms to linear or branched chain-type unsaturated monoalcohol having 1 to 30 carbon atoms (addition mole number 1 to 20 moles), etc. Is mentioned.

  As the aromatic monoalcohol, aromatic monoalcohol having 6 to 30 carbon atoms (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.), and 6 to 30 carbon atoms. Examples include aromatic monoalcohols added with AO (EO, PO, and BO) having 2 to 4 carbon atoms (added mole number of 1 to 20 moles).

Examples of monovalent monocarboxylic acids include aliphatic monocarboxylic acids and aromatic monocarboxylic acids.
Examples of the aliphatic monocarboxylic acid include a chain saturated monocarboxylic acid, a chain unsaturated monocarboxylic acid, and an alicyclic monocarboxylic acid.
As the chain saturated monocarboxylic acid, a linear or branched chain saturated monocarboxylic acid having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthic acid, capryl) Acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid and lignoceric acid).
Examples of the chain unsaturated monocarboxylic acid include linear or branched chain unsaturated monocarboxylic acid having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, α-linolenic acid. Acid, γ-linolenic acid, eleostearic acid, 8,11-icosadienoic acid, 5,8,11-icosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, dihomo-γ- Linolenic acid, docosapentaenoic acid, elaidic acid, erucic acid, nervonic acid and the like).
Examples of the alicyclic monocarboxylic acid include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (such as cyclopropane carboxylic acid, cyclobutane carboxylic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, and cycloheptane carboxylic acid). .
Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms, specifically, benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, t-butyl benzoic acid, and cumic acid. , Naphthoic acid, biphenyl monocarboxylic acid and furic acid.
Of the monocarboxylic acids, aromatic monocarboxylic acids are preferable from the viewpoint of low-temperature fixability and wet heat storage stability, and benzoic acid, t-butylbenzoic acid and naphthoic acid are more preferable.

  The acid value of the polyester resin (A) used in the present invention is preferably 5 to 30 mgKOH / g, more preferably 6 to 25 mgKOH / g, and particularly preferably 7 to 20 mgKOH / g from the viewpoint of charge stability and hygroscopicity. It is.

  The hydroxyl value of the polyester resin (A) used in the present invention is preferably 0 to 60 mgKOH / g, more preferably 0 to 40 mgKOH / g, particularly preferably 0 to 30 mgKOH / g, most preferably from the viewpoint of offset resistance of the toner. Preferably it is 0-20 mgKOH / g.

  In addition, the acid value and hydroxyl value in this invention can be measured by the method prescribed | regulated to JISK0070 (1992 edition).

  The flow softening point (hereinafter abbreviated as Tm) of the polyester resin (A) used in the present invention is preferably from 80 to 160 ° C., more preferably from 85 to 150 ° C., particularly from the viewpoint of achieving both offset resistance and low-temperature fixability. Preferably it is 90-140 degreeC.

Tm in the present invention can be measured by the following method.
<Tm measurement method>
Using a Koka flow tester {for example, CFT-500D manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a temperature rising rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent (flow value)” and “temperature”, and set the temperature corresponding to 1/2 of the maximum plunger descent Read from the graph and Tm is this value (temperature when half of the measurement sample flows out).

The glass transition temperature (hereinafter abbreviated as Tg) of the polyester resin (A) used in the present invention is preferably 40 to 80 ° C., more preferably 50 to 70 ° C., and particularly preferably from the viewpoint of blocking resistance and low-temperature fixability. 55-65 ° C.
In addition, Tg in this invention can be measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Instruments Co., Ltd. DSC20 and SSC / 580.

The peak top molecular weight (hereinafter sometimes referred to as Mp) of the THF-soluble component of the polyester resin (A) used in the present invention is 2,000 to 50, from the viewpoint of compatibility between toner durability and low-temperature fixability. 000 is preferable, and 4,000 to 20,000 is more preferable.
In addition, Mp means the molecular weight which shows the maximum peak height on the obtained chromatogram.

The molecular weight [Mp, Mn, weight average molecular weight (hereinafter referred to as Mw)] of the polyester resin in the present invention can be measured using GPC under the following conditions.
Apparatus (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSYRENE) [manufactured by Tosoh Corporation] 12 points (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190 , 000 355,000 1,090,000 2,890,000)
The molecular weight is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The SP value [solubility parameter: (cal / cm ³ ) ^1/2 ] of the polyester resin (A) of the present invention is preferably 9.5 to 11.5, more preferably 10.0 to 11.0. . When the SP value is in the above range, the charging characteristics, particularly the saturation charge amount, are good.
The SP value of the polyester resin in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"

  The hygroscopicity of the polyester resin (A) of the present invention is evaluated by the moisture content in (A) after storing (A) for 20 hours under the conditions of 40 ° C. and 90% relative humidity. Based on the weight of (A), it is preferably 10,000 ppm or less, more preferably 9500 ppm or less, and particularly preferably 9000 ppm or less.

  The water content (A) in the present invention is a value measured using a Karl Fischer moisture measuring device [for example, trade name: AQV-200 (manufactured by Hiranuma Sangyo)].

Temperature of the polyester resin (A) according to the present invention in which the volume average particle size (Dv) is 5 to 8 μm and the particle size distribution (ratio of volume average particle size to number average particle size) Dv / Dn = 1.3 The charge amount Q (60) (μC / g) for 60 seconds by the blow-off method in an environment of 23 ° C. and 50% humidity must satisfy the following relational expression (1) from the viewpoint of charging characteristics (saturation charge amount). There is. Dn is the number average particle diameter (μm) of the particles.
Q (60) = α × acid value + β (1)
[The acid value (mgKOH / g) is the acid value of (A), the α value is −1.0 to −0.8, and the β value is −25 to −20. ]

As for the α value, the absolute value of the α value can be increased by increasing the acid value, hydroxyl value and SP value of (A). In particular, increasing the acid value derived from the crosslinking agent has a great effect. On the other hand, the β value increases the content of the aromatic polycarboxylic acid constituting (A), the content of the aromatic dicarboxylic acid component (y1) having two carboxyl groups at the para position of the aromatic ring, and hygroscopicity. The absolute value of the β value can be increased by lowering. In particular, the effect of increasing the content of (y1) is great. The hygroscopicity can be adjusted by the number of terminal functional groups (= acid value + hydroxyl value) in (A). The number of terminal functional groups can be controlled by the equivalent ratio [OH] / [COOH] of hydroxyl group and carboxyl group and end-capping with monoalcohol or monocarboxylic acid. When the number of terminal functional groups is increased, the hygroscopicity is increased. Hygroscopicity is low.
When the relational expression (1) is not satisfied, for example, when the absolute amount of charging of the toner becomes small, the image quality may be deteriorated due to fogging due to toner scattering. On the other hand, when the absolute amount of toner charge increases, the image quality density may decrease due to overcharging. In any case, if the relational expression (1) is not satisfied, there is a high possibility that problems such as development failure and deterioration of transfer efficiency occur.

［６０秒撹拌帯電量Ｑ（６０）（μＣ／ｇ）は、（Ａ）を体積平均粒子径（Ｄｖ）が５〜８μｍかつ粒子径分布Ｄｖ／Ｄｎ＝１．３の粒子にしたものの温度２３℃、湿度５０％の環境内でブローオフ法による６０秒撹拌帯電量である。６００秒撹拌帯電量Ｑ（６００）（μＣ／ｇ）は、（Ａ）を体積平均粒子径（Ｄｖ）が５〜８μｍかつ粒子径分布Ｄｖ／Ｄｎ＝１．３の粒子にしたものの温度２３℃、湿度５０％の環境内でブローオフ法による６００秒撹拌帯電量である。］ The polyester resin (A) in the present invention is made into particles having a volume average particle diameter (Dv) of 5 to 8 μm and a particle diameter distribution Dv / Dn = 1.3, and is blown off in an environment of a temperature of 23 ° C. and a humidity of 50%. The 60-second stirring charge amount Q (60) (μC / g) and the 600-second stirring charge amount Q (600) (μC / g) are the changes in charge defined by the following relational expression (2) from the viewpoint of toner reliability. The amount (%) is preferably -20 to 20% (± 20% or less).

[60 second stirring charge amount Q (60) (μC / g) is a temperature of 23 obtained by converting (A) into particles having a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution Dv / Dn = 1.3. The charge amount is stirred for 60 seconds by blow-off method in an environment of 50 ° C. and humidity of 50%. 600 seconds stirring charge amount Q (600) (μC / g) is a temperature of 23 ° C. when (A) is a particle having a volume average particle diameter (Dv) of 5 to 8 μm and a particle diameter distribution Dv / Dn = 1.3. The charge amount is stirred for 600 seconds by the blow-off method in an environment with a humidity of 50%. ]

The content of the polyester resin (A) in the present invention is preferably 90% by weight or more, more preferably 95% by weight or more from the viewpoint of charging characteristics, based on the weight of the toner binder.
The toner binder of the present invention may contain, in addition to the polyester resin (A), other resins generally used as a toner binder as long as the properties are not impaired. Examples of other resins include polyester resins other than the polyester resin (A), vinyl resins having an Mw of 1,000 to 1,000,000, epoxy resins, and polyurethane resins. Other resins may be blended with (A) or partially reacted. The content of the other resin is preferably 10% by weight or less, more preferably 5% by weight or less, based on the weight of the toner binder.

The polyester resin (A) in the present invention can be produced in the same manner as a known polyester production method. For example, the reaction temperature of the polyol component (x) and the polycarboxylic acid component (y) is preferably 150 to 280 ° C., more preferably 170 to 260 ° C., particularly preferably in an inert gas (nitrogen gas or the like) atmosphere. Can be carried out by reacting at 180 to 240 ° C, most preferably 200 to 230 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, Japanese Patent Application Laid-Open No. 2006-243715. Catalysts described in the publication [titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolaminate), and intramolecular polycondensates thereof], and catalyst described in JP2007-11307A (Titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), zinc acetate and the like. Among these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the polyol component (x) and the polycarboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 5/1 to 1 / 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

  Examples of the method for producing the fine particles of the polyester resin (A) of the present invention include a known pulverization method. For example, by first roughly pulverizing with a lab mill or the like, then finely pulverizing using a jet mill pulverizer or the like, and further classifying, the volume average particle size (Dv) is preferably 5 to 8 μm and the particle size distribution Dv / Dn. = 1.3 can be produced as particles. The volume average particle diameter (Dv) and the number average particle diameter (Dn) can be measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

The charge amount Q in the present invention can be measured by the following blow-off method.
A magnet is attached to the lower part of the container of the roll mill, which is a mag roll, and an agitation device comprising a sealed container that can be agitated while applying a load to the magnetic carrier in the container by the magnetic force of the magnet is prepared. 0.25 g of the resin fine particles (A) and 5 g of the magnetic carrier are put into the sealed container of the stirring device, and left to stand for 1 hour or more in an atmosphere at a temperature of 23 ° C. and a humidity of 50%, and then set in the stirring device. And stirred for 60 seconds at a rotation speed of 280 rpm. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device in which a 20 μm stainless wire mesh was set, and the charge amount of the remaining iron powder was measured under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. The charge amount of the resin particles is calculated by an ordinary method, and this is defined as Q (60). Moreover, what made the said stirring time 600 seconds is set to Q (600).

  The toner of the present invention contains the toner binder of the present invention and a colorant.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, or nickel or a compound such as magnetite, hematite, or ferrite) can also be included as a colorant.

  In addition to the toner binder and the colorant, the toner of the present invention may contain one or more additives selected from the group consisting of a release agent, a charge control agent, a fluidizing agent, and the like.

As the mold release agent, those having a melting point of 50 to 170 ° C. are preferable, and polyolefin wax, natural wax, Fischer-Tropsch wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Can be mentioned.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modified products of olefin (co) polymers [eg maleic acid and its esterified products (maleic anhydride)] Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), and olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [ Alkyl (meth) acrylate (alkyl having 1 to 18 carbon atoms) Copolymers of ester and alkyl maleate (C1-18 alkyl) esters, etc.] and the like.

Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
The Fischer-Tropsch wax includes petroleum-based Fischer-Tropsch wax (Paraflint H1, Paraflint H1N4, Paraflint C105, etc. manufactured by Schumann-Sazol), natural gas Fischer-Tropsch wax (FT100, manufactured by Shell MDS, etc.), and these Fischer-Tropsch waxes And purified by a method such as fractional crystallization [Nippon Seiwa Co., Ltd. MDP-7000 and MDP-7010] and the like.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol.
Examples of the fatty acid having 30 to 50 carbon atoms include triacontanoic acid.

  Charge control agents include nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole ring-containing compounds, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine Examples include dyes, salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

The content of each component constituting the toner of the present invention is as follows.
The content of the toner binder in the toner of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly preferably 45 to 92% by weight based on the weight of the toner.
The content of the colorant in the toner of the present invention is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the toner. %.
The content of the release agent in the toner of the present invention is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight based on the weight of the toner. .
The content of the charge control agent in the toner of the present invention is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7.5% based on the weight of the toner. % By weight.
The content of the fluidizing agent in the toner of the present invention is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0.1 to 4% by weight based on the weight of the toner. .
The total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight based on the weight of the toner.
When the composition ratio of the toner is in the above range, a toner having good charging characteristics can be easily obtained.

  Examples of the method for producing the toner of the present invention include a known kneading and pulverizing method. For example, after dry blending the components constituting the above toner excluding the fluidizing agent, melt-kneading, then coarsely pulverized, finally finely divided using a jet mill pulverizer, etc., and further classified, After the volume average particle diameter (D50) is preferably 5 to 20 μm, it can be produced by mixing a fluidizing agent. The particle size (D50) can be measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

  The toner of the present invention is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as necessary to form an electrical latent image. Used as a developer. When the total weight of [toner / carrier particles] is 100, the weight ratio [toner / carrier particles] of the toner and carrier particles is preferably [1/99 to 100/0]. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner of the present invention is fixed on a support (paper, polyester film, etc., preferably paper) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Example 1> [Toner binder (TB-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 210 parts by weight (32.6 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 547 parts by weight (Sanyo Chemical Industries Himer BP-3P) 547 parts by weight (76.2 mol%), 214 parts by weight (70 mol%) terephthalic acid, 92 parts by weight (30 mol%) isophthalic acid, titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added and reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off generated water. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 4 hours, and when the acid value became 15, it picked out and obtained the toner binder (TB-1) containing a polyester resin (A-1).
The acid value of the polyester resin (A-1) was 15, Tg was 57 ° C., Tm was 99 ° C., and the peak top molecular weight Mp was 6200.

<Example 2> [Toner binder (TB-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 174 parts by weight (27.2 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), bisphenol A · PO 3 mol 584 parts by weight (Sanyo Kasei Kogyo Himer BP-3P) 584 parts by weight (81.7 mol%), 244 parts by weight terephthalic acid (80 mol%), 2.5 weight titanium dihydroxybis (triethanolamate) as a condensation catalyst The reaction was conducted while distilling off the generated water while raising the temperature to 230 ° C. under a reduced pressure of 0.5 to 2.5 kPa, and when the acid value became less than 2, 61 parts by weight of isophthalic acid was added. (20 mol%) was added, and the mixture was further reacted for 4 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 15, the polyester resin (A-2) was contained. To obtain toner binder (TB-2).
The acid value of the polyester resin (A-2) was 13, Tg was 55 ° C., Tm was 95 ° C., and the peak top molecular weight Mp was 6100.

<Example 3> [Toner binder (TB-3)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 139 parts by weight (21.8 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 621 parts by weight (Sanyo Chemical Industries Himer BP-3P) 621 parts by weight (87.1 mol%), terephthalic acid 304 parts by weight (100 mol%), titanium dihydroxybis (triethanolaminate) 2.5 parts by weight as a condensation catalyst The reaction was carried out for 4 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Further, the reaction was carried out for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and when the acid value became less than 15, the toner binder (TB-3) containing the polyester resin (A-3) was obtained. .
The acid value of the polyester resin (A-3) was 10, Tg was 59 ° C., Tm was 100 ° C., and the peak top molecular weight Mp was 5900.

<Example 4> [Toner binder (TB-4)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 212 parts by weight (32.7 mol%) of bisphenol A · PO 2 mol adduct (Hymar BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 3 553 parts by weight of an adduct (Hymer BP-3P manufactured by Sanyo Chemical Industries) (76.2 mol%), 278 parts by weight of terephthalic acid (90 mol%), 22 parts of fumaric acid (10 mol%), titanium dihydroxybis as a condensation catalyst (Triethanolaminate) 2.5 parts by weight was added and reacted at 230 ° C. in a nitrogen stream while distilling off the generated water. Further, the reaction was carried out for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and when the acid value became less than 15, the toner binder (TB-4) containing the polyester resin (A-4) was obtained. .
The acid value of the polyester resin (A-4) was 10, Tg was 55 ° C., Tm was 96 ° C., and the peak top molecular weight Mp was 5800.

<Example 5> [Toner binder (TB-5)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 34 parts by weight (5.4 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 3 1. Adduct (Sanyo Chemical Industries Hymer BP-3P) 719 parts by weight (102.4 mol%), terephthalic acid 239 parts by weight (77.7 mol%), titanium dihydroxybis (triethanolamate) as a condensation catalyst 5 parts by weight was added and reacted while distilling off generated water while raising the temperature to 230 ° C. under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 2, isophthalic acid 60 Part by weight (19.4 mol%) and trimellitic anhydride 10 parts by weight (2.9 mol%) are added, and further reacted under reduced pressure of 0.5 to 2.5 kPa for 4 hours. became Removed at the point to obtain toner binder (TB-5) containing a polyester resin (A-5).
The acid value of the polyester resin (A-5) was 10, Tg was 61 ° C., Tm was 110 ° C., and the peak top molecular weight Mp was 11000.

<Example 6> [Toner binder (TB-6)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 757 parts by weight (118.4 mol%) of bisphenol A / PO3 mol adduct (Sanyo Chemical Industries, Hymer BP-3P), 218 parts of terephthalic acid ( 73 mol%), isophthalic acid 55 parts by weight (18.3 mol%), trimellitic anhydride 30 parts by weight (8.8 mol%), and titanium dihydroxybis (triethanolaminate) 2.5 parts by weight as a condensation catalyst The reaction was carried out for 4 hours at 230 ° C. under a nitrogen stream while distilling off the water produced. Furthermore, the mixture was reacted for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value became less than 15, to obtain a toner binder (TB-6) containing a polyester resin (A-6). .
The acid value of the polyester resin (A-6) was 9, Tg was 60 ° C., Tm was 120 ° C., and the peak top molecular weight Mp was 12000.

<Example 7> [Toner binder (TB-7)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 69 parts by weight (11.8 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 3 Adduct (Sanyo Chemical Industries Hymer BP-3P) 697 parts by weight (106.5 mol%), terephthalic acid 222 parts by weight (73 mol%), isophthalic acid 28 parts by weight (9.1 mol%), fumaric acid 19 Part by weight (9.1 mol%), trimellitic anhydride 30 parts by weight (8.8 mol%), and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added, and a nitrogen stream at 230 ° C. Below, it was made to react for 4 hours, distilling off the water to produce | generate. Further, the mixture was reacted for 4 hours under reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value became less than 15, to obtain a toner binder (TB-7) containing a polyester resin (A-7). .
The acid value of the polyester resin (A-7) was 10, Tg was 64 ° C., Tm was 130 ° C., and the peak top molecular weight Mp was 11700.

<Example 8> [Toner binder (TB-8)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 140 parts by weight (23.7 mol%) of bisphenol A · PO 2 mol adduct (Sanyo Kasei Kogyo Himer BP-2P), bisphenol A · PO 3 mol 626 parts (94.7 mol%) of adduct (Hymer BP-3P manufactured by Sanyo Chemical Industries), 226 parts by weight (73 mol%) of terephthalic acid, 39 parts by weight (18.3 mol%) of fumaric acid, trimellitic anhydride 31 parts by weight (8.8 mol%) of acid and 2.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst were added for 4 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Reacted. Further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa for 4 hours. When the acid value reached 15, the toner was taken out to obtain a toner binder (TB-8) containing a polyester resin (A-8).
The acid value of the polyester resin (A-8) was 15, Tg was 62 ° C., Tm was 138 ° C., and the peak top molecular weight Mp was 10600.

<Example 9> [Toner binder (TB-9)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 761 parts by weight (118.4 mol%) of bisphenol A / PO3 mole adduct (Sanyo Kasei Kogyo Himer BP-3P), 2219 parts by weight of terephthalic acid (74.6 mol%), isophthalic acid 55 parts by weight (18.7 mol%), pyromellitic anhydride 26 parts by weight (6.7 mol%), titanium dihydroxybis (triethanolamate) as a condensation catalyst 5 parts by weight was added and reacted for 4 hours at 230 ° C. under a nitrogen stream while distilling off the water produced. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 4 hours, and when the acid value became 10, it took out and obtained the toner binder (TB-9) containing a polyester resin (A-9).
The acid value of the polyester resin (A-9) was 10, Tg was 61 ° C., Tm was 119 ° C., and the peak top molecular weight Mp was 10700.

<Example 10> [Toner binder (TB-10)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 624 parts by weight (94.8 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 78 parts by weight (10.5 mol%) of adduct (Sanyo Chemical Industries Hymer BP-3P), 225 parts by weight of terephthalic acid (71.5 mol%), 101 parts by weight of dodecenyl succinic anhydride (20.0 mol%) , 31 parts by weight of trimellitic anhydride (8.5 mol%), 2.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst, and distilling off the water produced at 230 ° C. under a nitrogen stream The reaction was continued for 4 hours. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 4 hours, and when the acid value became 10, it took out and obtained the toner binder (TB-10) containing a polyester resin (A-10).
The acid value of the polyester resin (A-10) was 10, Tg was 59 ° C., Tm was 120 ° C., and the peak top molecular weight Mp was 9800.

<Example 11> [Toner binder (TB-11)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 726 parts by weight (106.5 mol%) of bisphenol A / PO 3 mol adduct (Sanyo Kasei Kogyo Himer BP-3P), 232 parts by weight of terephthalic acid (73.0 mol%), isophthalic acid 58 parts by weight (18.3 mol%), trimellitic anhydride 32 parts by weight (8.8 mol%), titanium dihydroxybis (triethanolaminate) as a condensation catalyst 5 parts by weight was added and reacted for 4 hours at 230 ° C. under a nitrogen stream while distilling off the water produced. Further, 15 parts by weight of 1,2-propylene glycol (11.8 mol%) was added and reacted for 1 hour, and then reacted for 1 hour under reduced pressure of 0.5 to 2.5 kPa, so that the acid value became 11. The toner binder (TB-11) containing the polyester resin (A-11) was obtained by taking out at the time.
The acid value of the polyester resin (A-11) was 11, Tg was 60 ° C., Tm was 117 ° C., and the peak top molecular weight Mp was 10200.

<Example 12> [Toner binder (TB-12)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 757 parts by weight (118.4 mol%) of bisphenol A / PO3 mole adduct (Hymer BP-3P manufactured by Sanyo Chemical Industries), 109 parts by weight of terephthalic acid (36.5 mol%), 127 parts by weight (36.5 mol%) of dimethyl terephthalic acid, 55 parts by weight of isophthalic acid (18.3 mol%), 31 parts by weight of trimellitic anhydride (8.8 mol%), As a condensation catalyst, 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) was added and reacted at 230 ° C. in a nitrogen stream for 4 hours while distilling off generated water. Further, the mixture was reacted for 4 hours under reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 11, to obtain a toner binder (TB-12) containing a polyester resin (A-12).
The acid value of the polyester resin (A-12) was 10, Tg was 60 ° C., Tm was 118 ° C., and the peak top molecular weight Mp was 10500.

<Comparative Example 1> [Toner Binder (RTB-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 281 parts by weight (43.1 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 471 parts by weight (Hymer BP-3P manufactured by Sanyo Chemical Industries, Ltd.), 31 parts by weight (10 mol%) terephthalic acid, 279 parts by weight (90 mol%) isophthalic acid, titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added and reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off generated water. Further, the reaction was carried out for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and when the acid value became less than 15, it was taken out to obtain a toner binder (RTB-1) containing a polyester resin (RA-1). .
The acid value of the polyester resin (RA-1) was 13, Tg was 57 ° C., Tm was 99 ° C., and the peak top molecular weight Mp was 6200.

<Comparative Example 2> [Toner Binder (RTB-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 209 parts by weight (32.3 mol%) of bisphenol A · PO 2 mol adduct (Sanyo Kasei Kogyo Himer BP-2P), bisphenol A · PO 3 mol 546 parts by weight (Sanyo Kasei Kogyo Himer BP-3P) 546 parts by weight (75.5 mol%), 154 parts by weight (50 mol%) terephthalic acid, 154 parts by weight (50 mol%) isophthalic acid, titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added and reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off generated water. Furthermore, the reaction was carried out for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and the toner was taken out when the acid value was less than 15 to obtain a toner binder (RTB-2) containing a polyester resin (RA-2). .
The acid value of the polyester resin (RA-2) was 10, Tg was 58 ° C., Tm was 100 ° C., and the peak top molecular weight Mp was 6500.

<Comparative Example 3> [Toner Binder (RTB-3)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 130 parts by weight (18.6 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO Additive (Sanyo Chemical Industries Hymer BP-3P) 581 parts by weight (74.2 mol%), trimethylolpropane 23 parts by weight (8.4 mol%), terephthalic acid 33 parts by weight (10 mol%), isophthalic acid 300 parts by weight (90 mol%) and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 230 ° C. for 4 hours while distilling off the generated water under a nitrogen stream. . Furthermore, the reaction was carried out for 4 hours under a reduced pressure of 0.5 to 2.5 kPa, and when the acid value became less than 15, it was taken out to obtain a toner binder (RTB-3) containing a polyester resin (RA-3). .
The acid value of the polyester resin (RA-3) was 9, Tg was 61 ° C., Tm was 118 ° C., and the peak top molecular weight Mp was 10500.

<Comparative Example 4> [Toner Binder (RTB-4)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 300 parts by weight (40.7 mol%) of bisphenol A · PO 2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), bisphenol A · PO 3 mol 428 parts by weight (51.8 mol%) of adduct (Hymer BP-3P manufactured by Sanyo Chemical Industries), 24 parts by weight (8.3 mol%) of trimethylolpropane, 25 parts by weight of terephthalic acid (7 mol%), isophthalic acid 221 parts by weight (63 mol%), 74 parts by weight of fumaric acid (30 mol%), and 2.5 parts by weight of titanium dihydroxybis (triethanolamate) as a condensation catalyst are produced at 230 ° C. in a nitrogen stream. The reaction was carried out for 4 hours while distilling off water. Further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, the toner binder (RTB-4) containing the polyester resin (RA-4) was obtained. .
The acid value of the polyester resin (RA-4) was 10, Tg was 60 ° C., Tm was 120 ° C., and the peak top molecular weight Mp was 11000.

<Comparative Example 5> [Toner Binder (RTB-5)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 126 parts by weight (16.8 mol%) of bisphenol A · PO2 mol adduct (Hymer BP-2P manufactured by Sanyo Chemical Industries), 3 mol of bisphenol A · PO 564 parts by weight (Sanyo Chemical Industries Himer BP-3P), 564 parts by weight (67.3 mol%), 24 parts by weight (8.4 mol%) trimethylolpropane, 36 parts by weight (10 mol%) terephthalic acid, isophthalic acid 321 parts by weight (90 mol%) and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 230 ° C. for 4 hours while distilling off the generated water under a nitrogen stream. . Further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, the toner binder (RTB-5) containing the polyester resin (RA-5) was obtained. .
The acid value of the polyester resin (RA-5) was 20, Tg was 59 ° C., Tm was 119 ° C., and the peak top molecular weight Mp was 10800.

実施例及び比較例で得られたトナーバインダーについて、組成及び物性を表１に示す。

Table 1 shows the composition and physical properties of the toner binders obtained in Examples and Comparative Examples.

<Examples 13 to 25 and Comparative Examples 6 to 10>
Using the polyester resins (A-1) to (A-12) obtained in the above production examples and the polyester resins (RA-1) to (RA-5) obtained in the comparative production examples, a toner binder (T- 1) to (T-13) and toner binders (RTB-1) to (RTB-5) were blended according to the blending ratio (parts by weight) in Table 2 (carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation]], Polyolefin wax (Biscol 550P manufactured by Sanyo Chemical Industries, Ltd., charge control agent T-77 [Hodogaya Chemical Co., Ltd.]) was used to form a toner by the following method.
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.], the mixture was kneaded at 150 ° C. using a Laboplast mill MODEL4M150 [manufactured by Toyo Seiki Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and the particle size D50 is 8 μm toner particles were obtained. Next, 100 parts by weight of toner particles and 0.5 parts by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) are mixed in a sample mill, and the toners (T-1) to (T-13) of the present invention are compared. Toners (RT-1) to (RT-5) were obtained.

  With respect to the toners obtained in the examples and comparative examples, the saturation charge amount, charge rising property, charge stability, blocking resistance, low-temperature fixability and hot offset resistance were evaluated by the following methods. The evaluation results are shown in Table 2.

<Saturation charge amount>
0.25 g of toner and 5 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) are put in a sealed container for mag rolls, and the container is conditioned for 1 hour or more in an atmosphere at a temperature of 23 ° C. and a humidity of 50%. Was set in a mag roll stirring device and stirred at 280 rpm × 60 seconds to prepare a sample. Next, a sample was taken out from the container, and the charge amount Q (60) (μC / g) of the toner was measured. This was used as an index of the saturation charge amount.
For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used.
[Criteria]
○: 30 μC / g or more Δ: 25 to less than 30 μC / g ×: less than 25 μC / g

<Charge rise characteristics>
In the measurement of the saturation charge amount, except that the stirring time was changed to 30 seconds, the toner charge amount measured by performing the same operation was set to Q (30) (μC / g), and this initial charge amount was determined as the charge rising property. It was used as an index.
[Criteria]
○: 20 μC / g or more Δ: Less than 15-20 μC / g ×: Less than 15 μC / g

<Charging stability>
In the measurement of the saturation charge amount, the same operation was performed except that the humidity control condition was changed from (1) a temperature of 23 ° C. and a humidity of 50% to (2) a temperature of 40 ° C. and a humidity of 85%. μC / g) was measured.
The ratio [Q (40 ° C., 85%) / Q (23 ° C., 50%)] of the charge amount under the humidity control condition (2) and the charge amount under the humidity control condition (1) is calculated and charged It was used as an index of stability.
[Criteria]
○: 0.5 or more Δ: 0.3 or more and less than 0.5 ×: less than 0.3

<Heat resistant storage stability>
The above toner was allowed to stand in an atmosphere of 45 ° C. for 24 hours, the degree of blocking was judged visually, and the heat resistant storage stability was evaluated according to the following criteria.
[Criteria]
○: Blocking has not occurred.
Δ: Blocking occurs in part.
X: Blocking has occurred throughout.

<Low temperature fixability>
An unfixed image developed using a commercial printer (HP laser printer) using the toner described above was evaluated using a commercial copying machine (AR5030; manufactured by Sharp).
After the fixed image was rubbed with a pad, the fixing roll temperature was decreased in increments of 5 ° C. until the residual ratio of the image density measured with a Macbeth reflection densitometer RD-191 (manufactured by Macbeth) was less than 70%. The lowest fixing roll temperature at which the residual ratio of image density is 70% or more was determined as the lowest fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

<Hot offset resistance>
Fixation was evaluated in the same manner as the above-described evaluation method for low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature was increased in increments of 5 ° C., and the fixing roll temperature at which hot offset occurred was defined as the hot offset generation temperature. In order to protect the fixing machine used for the measurement, the evaluation was performed up to 190 ° C., and “> 190 ° C.” was given when no hot offset occurred. The higher the hot offset generation temperature, the better the hot offset resistance.

  The toner binder and toner of the present invention are excellent in charging characteristics (saturation charge amount, charge rising property, charging stability) and excellent in blocking resistance, low-temperature fixing property and hot offset resistance. It can be suitably used as an electrostatic image developing toner and toner binder for use in electrophotography, electrostatic recording, electrostatic printing and the like.

Claims (10)

A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) and a polycarboxylic acid component (y) as constituent raw materials, wherein (A) is a polycarboxylic acid component as a constituent raw material 80 to 100 mol% of the aromatic polycarboxylic acid component based on the total number of moles of (y), and two carboxyl groups at the para position of the aromatic ring based on the total number of moles of the polycarboxylic acid component (y) A toner binder, which is a polyester resin containing 70 to 100 mol% of an aromatic dicarboxylic acid component (y1) having the following formula (1):
Q (60) = α × acid value + β (1)
[60 second stirring charge amount Q (60) (μC / g): (A) is a volume average particle size (Dv) of 5-8 μm and particle size distribution (ratio of volume average particle size to number average particle size) Dv /Dn=1.3 Particles with a temperature of 23 ° C. and a humidity of 50% are 60-second stirring charge amount by blow-off method. Dn is the number average particle diameter (μm) of the particles. The acid value (mgKOH / g) is the acid value of (A). The α value is −1.0 to −0.8, and the β value is −25 to −20. ] A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) and a polycarboxylic acid component (y) as constituent raw materials, wherein (A) is a polycarboxylic acid component as a constituent raw material 80 to 100 mol% of the aromatic polycarboxylic acid component based on the total number of moles of (y), and two carboxyl groups at the para position of the aromatic ring based on the total number of moles of the polycarboxylic acid component (y) The aromatic dicarboxylic acid component (y1) having a content of 70 mol% or more and less than 100 mol%, and the aromatic polycarboxylic acid component (y2) having 3 or more carboxyl groups is contained more than 0 mol% and 10 mol% or less. And a toner binder which is a polyester resin satisfying the following relational expression (1).
Q (60) = α × acid value + β (1)
[60 second stirring charge amount Q (60) (μC / g): (A) is a volume average particle size (Dv) of 5-8 μm and particle size distribution (ratio of volume average particle size to number average particle size) Dv /Dn=1.3 Particles with a temperature of 23 ° C. and a humidity of 50% are 60-second stirring charge amount by blow-off method. Dn is the number average particle diameter (μm) of the particles. The acid value (mgKOH / g) is the acid value of (A). The α value is −1.0 to −0.8, and the β value is −25 to −20. ]   The aromatic polycarboxylic acid component (y2) is at least selected from the group consisting of trimellitic acid, pyromellitic acid, anhydrides of these acids, and alkyl esters in which the alkyl group of these acids has 1 to 4 carbon atoms. The toner binder according to claim 2, which is one type. The toner binder according to claim 1, wherein the polyester resin (A) has a charge variation (%) defined by the following relational expression (2) of −20 to 20%.

[60 second stirring charge amount Q (60) (μC / g) is a temperature of 23 obtained by converting (A) into particles having a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution Dv / Dn = 1.3. The charge amount is stirred for 60 seconds by blow-off method in an environment of 50 ° C. and humidity of 50%. 600 seconds stirring charge amount Q (600) (μC / g) is a temperature of 23 ° C. when (A) is a particle having a volume average particle diameter (Dv) of 5 to 8 μm and a particle diameter distribution Dv / Dn = 1.3. The charge amount is stirred for 600 seconds by the blow-off method in an environment with a humidity of 50%. ]   The toner binder according to claim 1, wherein the polyester resin (A) contains 70 to 100 mol% of an aromatic diol component as a constituent raw material based on the total number of moles of the polyol component (x).   The toner binder according to any one of claims 1 to 5, wherein the aromatic dicarboxylic acid component (y1) is terephthalic acid and / or terephthalic acid alkyl ester having 1 to 5 carbon atoms in the alkyl group.   The toner binder according to any one of claims 1 to 6, wherein the flow softening point of the polyester resin (A) is 80 to 160 ° C.   The toner binder according to claim 1, wherein the glass transition temperature of the polyester resin (A) is 40 to 80 ° C.   The toner binder according to any one of claims 1 to 8, wherein the peak top molecular weight of the tetrahydrofuran-soluble component of the polyester resin (A) in the gel permeation chromatography is 2000 to 50000.   A toner comprising the toner binder according to claim 1 and a colorant.