JP6983696B2 - Toner binder and toner - Google Patents

Description

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

In recent years, with the rapid progress of digitization, colorization, compounding, high speed, and high image quality of electrophotographic copiers and printers, further demands for energy saving, high reliability, and environmental stability have been made more than ever. Is increasing.
The electrophotographic method comprises a process consisting of each step of charging, exposure, development, transfer, fixing, cleaning, and static elimination, and material technology represented by a photoconductor 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 toner are diverse, such as charging characteristics, powder characteristics, thermal characteristics, and color characteristics. Above all, the charging characteristic that controls the movement of toner is an important key technology for energy saving, high reliability, and environmental stability in toner development.
For example, as an energy-saving measure, it is necessary to improve the charge rising property of the toner in order to obtain a desired toner charge amount by friction for a very short time. Further, as a measure for high reliability, stable control of the toner charge amount is required so that the toner charge amount in the developed portion always falls within the set range allowed in the process. Furthermore, under high humidity conditions, the amount of toner charge decreases and the toner develops on the white background, and when it dries, the image quality density decreases due to overcharging. It is required to eliminate changes in the amount of toner charged due to environmental differences such as high temperature and high humidity and low temperature and low humidity in winter. In the toner industry, there is an urgent need to develop high-quality toners whose charging characteristics are highly controlled.
The toner is composed of a toner binder, a pigment, a wax, a charge control agent (CCA: Charge Control Agent), and an external additive. The toner binder is the main component of toner and occupies 80 to 90% of the 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 large role in the charging characteristics.
As the toner binder, a styrene resin, a polyester resin, an epoxy resin, or the like is used. Above all, due to the strong demand for energy saving in recent years, the development of polyester resin that can be fixed at a lower temperature is active. A characteristic of polyester resin is that it has a carboxylic acid group and a hydroxyl group in the molecule, and these functional groups form hydrogen bonds in the molecule and between the molecules, increasing the apparent molecular weight of the resin and resistance to offset. , Improves mechanical strength. As for the charging characteristics, the charging rising property is faster and better than that of the styrene resin, but there are problems such as a large change in the charging amount in a high temperature and high humidity environment, and it is necessary to study.

As a prior art, control factors for the charge characteristics (saturated charge amount, charge rise property and charge stability) of the polyester resin include acid value, aromatic ring concentration and hygroscopicity.
<Acid value>
The charge of the polyester resin is affected by the amount of acid groups (acid value) present in the molecule. Generally, the higher the acid value, the higher the negative charge property, and the faster the charge rises. However, in a high temperature and high humidity environment, the change in the charge amount 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>
As the concentration of the aromatic ring in the polyester resin increases, the amount of charge increases and the charge rising property also improves. For example, Patent Document 1 defines the amounts of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, aromatic diols and aromatic dicarboxylic acids in order to improve charge rise and durability. Although the toner has been disclosed and the effect has been obtained, it cannot be said that it is sufficient, and further improvement is desired.
Patent Document 2 also discloses a toner that defines an aromatic ring concentration, but cannot satisfy all of the saturated charge amount, charge rising property, and charge stability.
<Hygroscopicity>
If the hygroscopicity is high, the change in the amount of charge in a high temperature and high humidity environment becomes large. In order to improve 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 monohydric alcohol component. .. Although some effects have been obtained, further performance improvement is desired.
In Patent Document 4, an aromatic ring is introduced into the polyester terminal by polycondensing an aromatic dicarboxylic acid with an alcohol component containing a specific amount of (poly) alkylene glycol monoaryl ether as a monovalent aromatic alcohol. Although an example of making the above hydrophobic is disclosed, the charge rising property and the charge stability are improved to some extent, but the saturated charge amount is not sufficient.
It is a big issue in toner development to simultaneously achieve both saturated charge amount, charge rise property and charge stability, which are charge characteristics, and a solution is urgently required.

Japanese Unexamined Patent Publication No. 2016-33606 Japanese Unexamined Patent Publication No. 2016-80861 Japanese Unexamined Patent Publication No. 6-263854 Japanese Unexamined Patent Publication No. 2016-218392

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

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention is a toner binder containing a polyester resin (A) formed by reacting a polyol component (x) with a polycarboxylic acid component (y) as a constituent raw material, wherein (A) is the constituent raw material. 80 to 100 mol% of the aromatic polycarboxylic acid component is contained based on the total number of moles of the polycarboxylic acid component (y), and the para-position of the aromatic ring is based on the total number of moles of the polycarboxylic acid component (y). A toner binder that 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 formula (1); contains the above-mentioned toner binder and colorant. It is a toner.
Q (60) = α × acid value + β (1)
[However, in the relational expression, the 60-second stirring charge amount Q (60) (μC / g) is (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 size ratio) The particle size is Dv / Dn = 1.3, and the amount of charge is stirred for 60 seconds by the blow-off method in an environment where the temperature is 23 ° C. and the humidity is 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. ]
Further, the present invention
A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) with a polycarboxylic acid component (y) as a constituent raw material, wherein (A) is a polycarboxylic acid component as a constituent raw material. Contains 80 to 100 mol% of 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 polycarboxylic acid component (y). Contains 70 mol% or more and less than 100 mol% of the aromatic dicarboxylic acid component (y1), and more than 0 mol% and 10 mol% or less of the aromatic polycarboxylic acid component (y2) having 3 or more carboxyl groups. It is a toner containing a toner binder and a colorant, which are polyester resins satisfying the following relational expression (1).
Q (60) = α × acid value + β (1)
[60 seconds stirring charge amount Q (60) (μC / g) is (A) with a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution (ratio of volume average particle size to number average particle size) Dv. It is a 60-second stirring charge amount by the blow-off method in an environment where the particles are made into particles of / Dn = 1.3 and have 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. ]

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a toner binder having excellent charging characteristics (saturated charging amount, charging rising property and charging stability) and a toner containing a toner binder.

Hereinafter, the present invention will be described in detail.
The polyester resin (A) used in the present invention is obtained by reacting (hypercondensing) a polyol component (x) with a polycarboxylic acid component (y) to obtain the total number of moles of the polycarboxylic acid component (y) as a constituent raw material. Based on this, an aromatic dicarboxylic acid component containing 80 to 100 mol% of an aromatic polycarboxylic acid component and having two carboxyl groups at the paraposition 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 relational expression (1) described later.
Further, the polyester resin (A) used in the present invention is obtained by reacting (hypercondensing) the polyol component (x) with the polycarboxylic acid component (y), and is the total molar of the polycarboxylic acid component (y) as a constituent raw material. An aromatic dicarboxylic acid containing 80 to 100 mol% of an aromatic polycarboxylic acid component based on the number and 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). A relational expression described later in which the component (y1) is contained in an amount 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 in an amount of more than 0 mol% and 10 mol% or less. As long as (1) is satisfied, other resin compositions are not particularly limited.
Further, the polyester resin (A) may be of one type, may be a mixture of two or more types of polyester resins, and may be, 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-valent or higher polyols, and examples of the polycarboxylic acid component (y) include dicarboxylic acids and 3- to 6-valent or higher polycarboxylic acids. ..
As the polyol component (x), the diol is an alkylene glycol having 2-36 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.); alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, etc.) , Polypropylene glycol and polytetramethylene ether glycol, etc.); Alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); The same applies to polyoxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) or less.] Ether [Number of oxyalkylene units (hereinafter abbreviated as AO units) 1 to 30]; Divalent phenol [single ring Examples thereof include divalent phenol (for example, hydroquinone), polyoxyalkylene ether of bisphenols (number of AO units 2 to 30); and the like.
Examples of the 3- to 8-valent or higher polyols include 3- to 8-valent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alcan polyols and their intramolecular or intermolecular dehydrations such as glycerin and trimethylolethane. , Trimethylol propane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol); saccharides and esterified products thereof such as sucrose and methyl glucoside); (poly) oxyalkylene ether (AO unit) of the above aliphatic polyhydric alcohol. 1 to 30); Polyoxyalkylene ethers of trisphenols (Trisphenol PA, etc.) (Number of AO units 2 to 30); Poly of novolak resin (phenol novolak, cresol novolak, etc., average polymerization degree 3 to 60) Examples thereof include oxyalkylene ether (number of AO units 2 to 30).

The polyoxyalkylene ether of bisphenols is obtained by adding an 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)
[In the formula, X is substituted with an alkylene group having 1 to 3 carbon atoms, -SO _2- , -O-, -S-, or a direct bond, and Ar is substituted with a 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, which can be used in combination of two or more. The AO added to these bisphenols preferably has 2 to 4 carbon atoms, and 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 number of moles of AO added is preferably 2 to 30 mol, more preferably 2 to 10 mol.
Among the polyoxyalkylene ethers of bisphenols, those preferable from the viewpoint of the fixing property and charging characteristics of the toner are EO and / or PO adducts of bisphenol A (average number of added moles 2 to 4, especially 2 to 3). ..

Among the polyol components (x), those 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. Nos. 2 to 30), tri-8-valent or higher aliphatic polyhydric alcohols, and novolak resin polyoxyalkylene ethers (number of AO units 2 to 30), which are more preferable from the viewpoint of storage stability. Is an alkylene glycol having 2 to 10 carbon atoms, a polyoxyalkylene ether of bisphenols (number of AO units 2 to 5), and a polyoxyalkylene ether of novolak resin (number of AO units 2 to 30), and is particularly preferable. , 2-6 carbon atoms, bisphenol A polyoxyalkylene ether (2-5 AO units), most preferably ethylene glycol, propylene glycol, bisphenol A polyoxyalkylene ether (AO units). The number 2 to 3).

The polyol component (x) may contain 70 mol% or more of aromatic diol based on the total number of moles of the polyol component (x) from the viewpoint of chargeability (saturated charge amount, charge rising property, charge stability). It is more preferable to contain 80 mol% or more, and further preferably 90 mol% or more.

As the aromatic diol, a polyoxyalkylene ether having a bisphenol A structure is preferable, and not only the charging characteristics are improved, but also the resin strength is increased and the 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 the polycarboxylic acid component (y), the dicarboxylic acid is an alkandicarboxylic acid having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, lepargic acid and sebacic acid) and having 4 to 50 carbon atoms. Arkendicarboxylic acid (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, etc.), aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, etc.) Acids and naphthalenedicarboxylic acids, etc.), vinyl polymers of unsaturated carboxylic acids [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid) Copolymers, etc.) and the like.
Examples of the tricarboxylic acid having a valence of 3 to 6 or more include an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and an aliphatic tricarboxylic acid having 6 to 36 carbon atoms (hexanetricarboxylic 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. Be done.
As the polycarboxylic acid component (y), an anhydride or a lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) 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 an arcandicarboxylic acid having 2 to 50 carbon atoms, an arcendicarboxylic acid having 4 to 50 carbon atoms, and carbon. It is an aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aromatic polycarboxylic acid having 9 to 20 carbon atoms, and more preferably adipinic 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 their combined use, and particularly preferably adipic acid, terephthalic acid, trimellitic acid and their combined use. Anhydrides and lower alkyl (eg, alkyl groups having 1 to 4 carbon atoms) esters of these acids are also preferred.

As the aromatic dicarboxylic acid component (y1), terephthalic acid and / or a terephthalic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and both the saturated charge amount, the charge rising property and the charge 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 as a constituent raw material based on the total number of moles of the polycarboxylic acid component (y). If it is less than 80 mol%, the charging characteristics are not good.
Further, it contains 70 to 100 mol% of an 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). If it is less than 70 mol%, the charging characteristics are not good.
Alternatively, 70 mol% or more and less than 100 mol%, and 3 or more of 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). Contains an aromatic polycarboxylic acid component (y2) having a carboxyl group of more than 0 mol% and 10 mol% or less. If (y1) is less than 70 mol%, the charging characteristics are not good, and if (y2) is more than 10 mol%, it is difficult to achieve both hot offset resistance and low temperature fixing property.
The content of (y2) is preferably 0.1 to 9 mol%, more preferably 0.1 to 8 mol%.

The aromatic polycarboxylic acid component (y2) includes trimellitic acid, pyromellitic acid, anhydrates of these acids, and alkyl esters having an alkyl group of 1 to 4 in 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, a monovalent monoalcohol may be appropriately contained in the alcohol component, and a monovalent monocarboxylic acid may be appropriately contained in the carboxylic acid component.

Examples of the monohydric monoalcohol include aliphatic monoalcohols and aromatic monoalcohols.
Examples of the aliphatic monoalcohol include chain-type saturated monoalcohols and chain-type unsaturated monoalcohols.

As the chain saturated monoalcohol, a 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, heptonol, 3-ethyl-3-pentanol, octanol, 2-ethyl- 1-hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and linear or branched chain saturated mono with 1 to 30 carbon atoms. Examples thereof include alcohols to which AO (EO, PO and BO) having 2 to 4 carbon atoms is added (additional moles 1 to 20 mol) and the like.

As the chain unsaturated monoalcohol, a linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (allyl alcohol, 2-butene-1-ol, 2-penten-1-ol, 2-hexene- 1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decene-1-ol, 2-dodecenol, palmitrail alcohol, oleyl alcohol and linoleil alcohol Etc.), and a linear or branched chain unsaturated monoalcohol having 1 to 30 carbon atoms to which AO (EO, PO and BO) having 2 to 4 carbon atoms is added (additional molar number of 1 to 20 mol), etc. Can be mentioned.

The aromatic monoalcohols include aromatic monoalcohols having 6 to 30 carbon atoms (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.) and 6 to 30 carbon atoms. Examples thereof include those obtained by adding AO (EO, PO and BO) having 2 to 4 carbon atoms to an aromatic monoalcohol (additional molar number of 1 to 20 mol).

Examples of monovalent monocarboxylic acids include aliphatic monocarboxylic acids and aromatic monocarboxylic acids.
Examples of the aliphatic monocarboxylic acid include a chain-type saturated monocarboxylic acid, a chain-type unsaturated monocarboxylic acid, and an alicyclic monocarboxylic acid.
Chain-type saturated monocarboxylic acids include linear or branched chain-type saturated monocarboxylic acids having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthic acid, and capryl. Acids, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, margaric acid, stearic acid, tubercrostearic acid, arachidic acid, behenic acid, lignoseric acid, etc.) and the like.
Chain-unsaturated monocarboxylic acids include linear or branched chain-unsaturated monocarboxylic acids with 3 to 30 carbon atoms (acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, buxenic acid, linolenic acid, α-linolenic acid). Acid, γ-linolenic acid, eleostearic acid, 8,11-icosadienoic acid, 5,8,11-icosatrienic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, dihomo-γ- Linolenic acid, docosapentaenoic acid, ellagic acid, erucic acid, nervonic acid, etc.) and the like.
Examples of the alicyclic monocarboxylic acid include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, etc.). ..
Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms, and specific examples thereof include benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, t-butyl benzoic acid and cumnic acid. , Naftoeic acid, biphenylmonocarboxylic acid, floric acid and the like.
Among the monocarboxylic acids, aromatic monocarboxylic acids are preferable from the viewpoint of low-temperature fixing property and moisture-resistant 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. 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, and particularly preferably 0 to 30 mgKOH / g, from the viewpoint of toner offset resistance. It is preferably 0 to 20 mgKOH / g.

The acid value and the hydroxyl value in the present invention can be measured by the method specified in JIS K0070 (1992 edition).

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

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

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 50 to 70 ° C. from the viewpoint of blocking resistance and low temperature fixability. It is 55 to 65 ° C.
The Tg in the present invention can be measured by the method specified in ASTM D3418-82 (DSC method) using DSC20 and SSC / 580 manufactured by Seiko Instruments.

The peak top molecular weight of the THF-soluble component of the polyester resin (A) used in the present invention (hereinafter, may be referred to as Mp) is 2,000 to 50, from the viewpoint of achieving both toner durability and low-temperature fixability. 000 is preferable, and more preferably 4,000 to 20,000.
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.
Equipment (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE) [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 the polyester resin in THF and filtering the insoluble matter with a glass filter to obtain a sample solution.

The SP value [solability 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 saturated charging 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. (Pages 147 to 154)"

The hygroscopicity of the polyester resin (A) of the present invention is evaluated by the water content in (A) after storing (A) at 40 ° C. and a relative humidity of 90% for 20 hours. Based on the weight of (A), it is preferably 10000 ppm or less, more preferably 9500 ppm or less, and particularly preferably 9000 ppm or less.

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

The temperature of the polyester resin (A) in the present invention having a volume average particle diameter (Dv) of 5 to 8 μm and a particle size distribution (ratio of volume average particle diameter to number average particle diameter) Dv / Dn = 1.3. The 60-second stirring charge amount Q (60) (μC / g) by the blow-off method in an environment of 23 ° C. and 50% humidity needs to satisfy the following relational expression (1) from the viewpoint of charge 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, the hydroxyl value and the SP value of (A). In particular, the effect is great when the acid value derived from the cross-linking agent is increased. 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 the hygroscopicity. The absolute value of 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) of (A). The number of terminal functional groups can be controlled by the equivalent ratio of hydroxyl group to carboxyl group [OH] / [COOH] and the terminal blockade with monoalcohol or monocarboxylic acid. Moisture absorption is low.
If the relational expression (1) is not satisfied, for example, if the absolute amount of charge of the toner becomes small, fog may occur due to toner scattering, and the image quality may deteriorate. On the contrary, when the absolute amount of charge of the toner becomes large, 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 will 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 of Dv / Dn = 1.3, and is blown off in an environment with 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 charge changes defined by the following relational expression (2) from the viewpoint of toner reliability. The amount (%) is preferably -20 to 20% (± 20% or less).

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

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, based on the weight of the toner binder, from the viewpoint of charging characteristics.
In addition to the polyester resin (A), the toner binder of the present invention may contain other resins generally used as a toner binder as long as the characteristics are not impaired. Examples of other resins include polyester resins other than the polyester resin (A), vinyl resins having an Mw of 10 to 1,000,000, epoxy resins, and polyurethane resins. The other resin 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) in an inert gas (nitrogen gas or the like) atmosphere is preferably 150 to 280 ° C, more preferably 170 to 260 ° C, and particularly preferably. 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 if necessary. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts [eg, titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715. Catalysts described in JP-A [Titanium dihydroxybis (triethanol aminate), titanium monohydroxytris (triethanol aminate), and their intramolecular polycondensates, etc.], and catalysts described in JP-A-2007-11307. (Titanium tributoxyterephthalate, titaniumtriisopropoxyterephthalate, titaniumdiisopropoxyditerephthalate, etc.)], zirconium-containing catalysts (eg, zirconyl acetate), zinc acetate, and the like. Of 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. It is 5 / 1-1 / 1.3, particularly preferably 1.4 / 1-1 / 1.2.

Examples of the method for producing fine particles of the polyester resin (A) of the present invention include known pulverization methods. For example, first, the particles are roughly pulverized with a lab mill or the like, then finely divided using a jet mill pulverizer or the like, and further classified to have a volume average particle size (Dv) of preferably 5 to 8 μm and a particle size distribution Dv / Dn. It can be produced as particles of = 1.3. 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 maglor, and a stirring device consisting of a closed container capable of stirring 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 of the above (A) are put into the closed container of the stirring device, allowed to stand in an atmosphere of a temperature of 23 ° C. and a humidity of 50% for 1 hour or more, and then set in a stirring device. The mixture is stirred at a rotation speed of 280 rpm for 60 seconds. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device set with a 20 μm stainless wire mesh, and the charge of the residual 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 a conventional method, and this is defined as Q (60). Further, the value obtained by setting the stirring time to 600 seconds is defined as Q (600).

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

As the colorant, all dyes, pigments and the like used as colorants for toner can be used. Specifically, Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Paranitroaniline Red, Truisin 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. Alternatively, two or more types can be mixed and used. Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also 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 mold release agent, a charge control agent, a fluidizing agent, and the like.

The release agent preferably has a melting point of 50 to 170 ° C., and contains polyolefin wax, natural wax, Fishertroph wax, fatty alcohols having 30 to 50 carbon atoms, fatty acids having 30 to 50 carbon atoms, and mixtures thereof. Can be mentioned.
As the polyolefin wax, a (co) polymer of an olefin (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and a mixture thereof) [(co) polymerization is obtained. And heat-reduced molded polyolefins], oxides of oxygen and / or ozone of (co) polymers of olefins, maleic acid modified products of (co) polymers of olefins [eg, maleic acid and its esterifieds (maleic anhydride). , Monomethyl maleate, monobutyl maleate and dimethyl maleate, etc.)], and olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [ Examples thereof include a copolymer with an alkyl (meth) acrylate (1 to 18 carbon atoms of an alkyl) ester and an alkyl maleate (1 to 18 carbon atoms of an alkyl) ester, etc.].

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

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

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

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% by weight, based on the weight of the toner. It is% 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 the 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, it is possible to easily obtain a toner having good charging characteristics.

Examples of the method for producing the toner of the present invention include known kneading and pulverizing methods. For example, the components constituting the above toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally finely divided using a jet mill pulverizer or the like, and further classified. It can be produced by mixing fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm and then mixing them with 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 a resin (acrylic resin, silicone resin, etc.) as needed, and an electrical latent image is obtained. It is used as a developer for. When the total weight of the [toner / carrier particles] is 100, the weight ratio [toner / carrier particles] between the toner and the carrier particles is preferably [1/99 to 100/0]. Further, instead of the carrier particles, it can be rubbed with a member such as a charged blade to form an electrical latent image.

The toner of the present invention is fixed to a support (paper, polyester film, etc., preferably paper) by a copying machine, a printer, or the like to be used as a recording material. As a method for fixing to the support, a known heat 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. Examples 1, 8, 13 and 20 are Reference Examples 1, 2, 3 and 4, respectively.

<Example 1> [Toner binder (TB-1)]
210 parts by weight (32.6 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo Co., Ltd.), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Adduct (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 547 parts by weight (76.2 mol%), terephthalic acid 214 parts by weight (70 mol%), isophthalic acid 92 parts by weight (30 mol%), titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 15, it was taken out to obtain a 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)]
174 parts by weight (27.2 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), bisphenol A / PO 3 mol in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 584 parts by weight (81.7 mol%), terephthalic acid 244 parts by weight (80 mol%), 2.5 weights of titanium dihydroxybis (triethanolaminate) as a condensation catalyst The reaction was carried out 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 under a reduced pressure of 0.5 to 2.5 kPa for 4 hours. When the acid value became less than 15, it was taken out and a toner binder containing a polyester resin (A-2) (A-2). TB-2) was obtained.
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)]
139 parts by weight (21.8 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Adduct (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 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 part was put in and reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out to obtain a toner binder (TB-3) containing a polyester resin (A-3). ..
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)]
212 parts by weight (32.7 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Adduct (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 553 parts by weight (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 2.5 parts by weight of (triethanolaminate) was added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out to obtain a toner binder (TB-4) containing a polyester resin (A-4). ..
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)]
34 parts by weight (5.4 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), bisphenol A / PO 3 mol in a reaction vessel equipped with a cooling tube, agitator and a nitrogen introduction tube. Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 719 parts by weight (102.4 mol%), 239 parts by weight of terephthalic acid (77.7 mol%), titanium dihydroxybis (triethanolaminate) as a condensation catalyst 2. Add 5 parts by weight and react while distilling off the generated water while raising the temperature to 230 ° C. under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes less than 2, isophthalic acid 60 Add 10 parts by weight (19.4 mol%) and 10 parts by weight (2.9 mol%) of trimellitic anhydride and further react under reduced pressure of 0.5 to 2.5 kPa for 4 hours to reduce the acid value to less than 15. When it became, it was taken out to obtain a 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)]
757 parts by weight (118.4 mol%) of bisphenol A / PO 3 mol addition (Heimer BP-3P manufactured by Sanyo Kasei Kogyo), 218 parts of terephthalic acid (118.4 mol%) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. 73 mol%), 55 parts by weight of isophthalic acid (18.3 mol%), 30 parts by weight of trimellitic anhydride (8.8 mol%), 2.5 parts by weight of titanium dihydroxybis (triethanol aminate) as a condensation catalyst. Was put in and reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out 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 (Heimer BP-2P manufactured by Sanyo Kasei Kogyo Co., Ltd.), 3 mol of bisphenol A / PO Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 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 Add 2.5 parts by weight (9.1 mol%), 30 parts by weight (8.8 mol%) of trimellitic anhydride, and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, and nitrogen flow at 230 ° C. Underneath, the reaction was carried out for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out 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)]
140 parts by weight (23.7 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 626 parts by weight (94.7 mol%), terephthalic acid 226 parts by weight (73 mol%), fumaric acid 39 parts by weight (18.3 mol%), trimellitic anhydride Add 31 parts by weight (8.8 mol%) of acid and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, and distill off the generated water at 230 ° C. for 4 hours. It was reacted. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 15, it 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)]
761 parts by weight (118.4 mol%) of bisphenol A / PO 3 mol addition (Heimer BP-3P manufactured by Sanyo Kasei Kogyo), 2219 parts by weight of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. (74.6 mol%), 55 parts by weight (18.7 mol%) of isophthalic acid, 26 parts by weight (6.7 mol%) of pyromellitic anhydride, titanium dihydroxybis (triethanolaminate) as a condensation catalyst 2. Five parts by weight were added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 10, it was taken out to obtain a 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)]
624 parts by weight (94.8 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 78 parts by weight (10.5 mol%), 225 parts by weight of terephthalic acid (71.5 mol%), 101 parts by weight of dodecenyl anhydride succinic acid (20.0 mol%) , 31 parts by weight (8.5 mol%) of trimellitic anhydride and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, and distill off the generated water at 230 ° C. under a nitrogen stream. While reacting for 4 hours. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 10, it was taken out to obtain a 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)]
726 parts by weight (106.5 mol%) of bisphenol A / PO 3 mol addition (Heimer BP-3P manufactured by Sanyo Kasei Kogyo), 232 parts by weight of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. (73.0 mol%), 58 parts by weight (18.3 mol%) of isophthalic acid, 32 parts by weight (8.8 mol%) of trimellitic anhydride, titanium dihydroxybis (triethanol aminate) as a condensation catalyst 2. Five parts by weight were added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, 15 parts by weight (11.8 mol%) of 1,2-propylene glycol was added and reacted for 1 hour, and then reacted under a reduced pressure of 0.5 to 2.5 kPa for 1 hour, and the acid value became 11. At this point, it was taken out to obtain a toner binder (TB-11) containing a polyester resin (A-11).
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)]
757 parts by weight (118.4 mol%) of bisphenol A / PO 3 mol addition (Heimer BP-3P manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 109 parts by weight of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. (36.5 mol%), 127 parts by weight (36.5 mol%) of dimethylterephthalic acid, 55 parts by weight (18.3 mol%) of isophthalic acid, 31 parts by weight (8.8 mol%) of trimellitic anhydride, 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) was added as a condensation catalyst, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 11, it was taken out 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)]
281 parts by weight (43.1 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), bisphenol A / PO 3 mol in a reaction vessel equipped with a cooling tube, agitator and a nitrogen introduction tube. Adduct (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 471 parts by weight (64.7 mol%), terephthalic acid 31 parts by weight (10 mol%), isophthalic acid 279 parts by weight (90 mol%), titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, 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)]
209 parts by weight (32.3 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Adduct (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 546 parts by weight (75.5 mol%), 154 parts by weight of terephthalic acid (50 mol%), 154 parts by weight of isophthalic acid (50 mol%), titanium dihydroxy as a condensation catalyst 2.5 parts by weight of bis (triethanolaminate) was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out 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 tube, a stirrer and a nitrogen introduction tube, 130 parts by weight (18.6 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo Co., Ltd.), 3 mol of bisphenol A / PO Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 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) were added as a condensation catalyst, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. .. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, 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 (Heimer BP-2P manufactured by Sanyo Kasei Kogyo Co., Ltd.), 3 mol of bisphenol A / PO Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 428 parts by weight (51.8 mol%), trimethylolpropane 24 parts by weight (8.3 mol%), terephthalic acid 25 parts by weight (7 mol%), isophthalic acid 221 parts by weight (63 mol%), 74 parts by weight (30 mol%) of fumaric acid, and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst are added, and the mixture is produced at 230 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off the water. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out to obtain a toner binder (RTB-4) containing a polyester resin (RA-4). ..
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)]
126 parts by weight (16.8 mol%) of bisphenol A / PO 2 mol adduct (Heimer BP-2P manufactured by Sanyo Kasei Kogyo), 3 mol of bisphenol A / PO in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Additives (Heimer BP-3P manufactured by Sanyo Kasei Kogyo) 564 parts by weight (67.3 mol%), trimethylol propane 24 parts by weight (8.4 mol%), terephthalic acid 36 parts by weight (10 mol%), isophthalic acid 321 parts by weight (90 mol%) and 2.5 parts by weight of titanium dihydroxybis (triethanolaminate) were added as a condensation catalyst, and the reaction was carried out at 230 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. .. Further, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value became less than 15, it was taken out to obtain a toner binder (RTB-5) containing a polyester resin (RA-5). ..
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, Comparative Examples 6 to 10>
Using the polyester resins (A-1) to (A-12) obtained in the above production example and the polyester resins (RA-1) to (RA-5) obtained in the comparative production example, the toner binder (T-) was used. 1)-(T-13) and toner binders (RTB-1)-(RTB-5) are blended according to the blending ratio (part by weight) in Table 2 (Carbon Black MA-100 [manufactured by Mitsubishi Chemical Corporation], Polyester wax [Viscol 550P manufactured by Sanyo Kasei Kogyo Co., Ltd.], charge control agent T-77 [Hodoya Kagaku Co., Ltd.]) was used to make toner by the following method.
First, the mixture was premixed using a Henschel mixer [FM10B manufactured by Nippon Coke Industries Co., Ltd.] and then kneaded at 150 ° C. with Labplast Mill MODEL4M150 [manufactured by Toyo Seiki Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Industries Co., Ltd.], the particles are classified by an air flow classifier [MDS-I manufactured by Nippon Pneumatic Industries Co., Ltd.], and the particle size D50 is determined. 8 μm toner particles were obtained. Then, 0.5 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) was mixed with 100 parts by weight of the toner particles by a sample mill, and the toners (T-1) to (T-13) of the present invention were compared. Toners (RT-1) to (RT-5) for use were obtained.

The toners obtained in Examples and Comparative Examples were evaluated for saturation charge amount, charge rise property, charge stability, blocking resistance, low temperature fixability and hot offset resistance by the following methods. The evaluation results are shown in Table 2.

<Saturated charge amount>
Place 0.25 g of toner and 5 g of ferrite carrier (F-150, manufactured by Powdertech) in a closed container for maglor, and after adjusting the humidity for 1 hour or more in an atmosphere with a temperature of 23 ° C and a humidity of 50%, the container. Was set in a maglor stirrer and stirred at 280 rpm for 60 seconds to prepare a sample. Next, the sample was taken out from the container, the charge amount Q (60) (μC / g) of the toner was measured, and this was used as an index of the saturated charge amount.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
[criterion]
◯: 30 μC / g or more Δ: 25 to less than 30 μC / g ×: less than 25 μC / g

<Charging rising property>
In the measurement of the saturated charge amount, the charge amount of the toner measured by performing the same operation is set to Q (30) (μC / g) except that the stirring time is changed to 30 seconds, and this initial charge amount is the charge rise property. It was used as an index.
[criterion]
◯: 20 μC / g or more Δ15 to less than 20 μC / g ×: less than 15 μC / g

<Charging stability>
In the measurement of the saturated charge amount, the same operation was performed except that the humidity control conditions were changed from (1) temperature 23 ° C. and humidity 50% to (2) temperature 40 ° C. and humidity 85%. μC / g) was measured.
Calculate the ratio [Q (40 ° C, 85%) / Q (23 ° C, 50%)] between the charge amount under the humidity control condition (2) and the charge amount under the humidity control condition (1), and charge this. It was used as an index of stability.
[criterion]
◯: 0.5 or more Δ: 0.3 or more and less than 0.5 ×: less than 0.3

<Heat-resistant storage>
The above toner was allowed to stand in an atmosphere of 45 ° C. for 24 hours, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following judgment criteria.
[criterion]
◯: No blocking has occurred.
Δ: Blocking has occurred in a part.
X: Blocking has occurred in the whole.

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

<Hot offset resistance>
The fixing was evaluated in the same manner as the above-mentioned evaluation method of low temperature fixing property, and the presence or absence of hot offset to the fixed image was visually evaluated. The fixing roll temperature was raised in increments of 5 ° C., and the fixing roll temperature at which the hot offset occurred was defined as the hot offset generation temperature. In addition, in order to protect the fixing machine used for measurement, the evaluation was carried out up to 190 ° C, and the one in which hot offset did not occur was set as "> 190 ° C". 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 (saturated charge amount, charge rising property, charge stability), and are also excellent in blocking resistance, low temperature fixing property and hot offset resistance. It can be suitably used as a toner for static charge image development and a toner binder used for electrophotographic, electrostatic recording, electrostatic printing and the like.

Claims (10)

A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) with a polycarboxylic acid component (y) as a constituent raw material, wherein (A) is a polycarboxylic acid component as a constituent raw material. Contains 80 to 100 mol% of 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). aromatic dicarboxylic acid component (y1) containing 70 to 100 mol% with, and Ri polyester resin der satisfying the following relational expression (1),
The polyol component (x) contains an aromatic diol component, and the aromatic diol is a propylene oxide adduct of bisphenol A.
A toner binder in which the acid value of the polyester resin (A) is 5 to 13 mgKOH / g and the hydroxyl value of the polyester resin (A) is 14 to 36 mgKOH / g.
Q (60) = α × acid value + β (1)
[60 seconds stirring charge amount Q (60) (μC / g) is (A) with a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution (ratio of volume average particle size to number average particle size) Dv. It is a 60-second stirring charge amount by the blow-off method in an environment where the particles are made into particles of / Dn = 1.3 and have 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. ] A toner binder containing a polyester resin (A) obtained by reacting a polyol component (x) with a polycarboxylic acid component (y) as a constituent raw material, wherein (A) is a polycarboxylic acid component as a constituent raw material. Contains 80 to 100 mol% of 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 polycarboxylic acid component (y). Contains 70 mol% or more and less than 100 mol% of the aromatic dicarboxylic acid component (y1), and more than 0 mol% and 10 mol% or less of the aromatic polycarboxylic acid component (y2) having 3 or more carboxyl groups. and Ri polyester resin der satisfying the following relation (1),
The polyol component (x) contains an aromatic diol component, and the aromatic diol is a propylene oxide adduct of bisphenol A.
A toner binder in which the acid value of the polyester resin (A) is 5 to 13 mgKOH / g and the hydroxyl value of the polyester resin (A) is 14 to 36 mgKOH / g.
Q (60) = α × acid value + β (1)
[60 seconds stirring charge amount Q (60) (μC / g) is (A) with a volume average particle size (Dv) of 5 to 8 μm and a particle size distribution (ratio of volume average particle size to number average particle size) Dv. It is a 60-second stirring charge amount by the blow-off method in an environment where the particles are made into particles of / Dn = 1.3 and have 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. ] At least the aromatic polycarboxylic acid component (y2) is selected from the group consisting of trimellitic acid, pyromellitic acid, anhydrides of these acids and alkyl esters having an alkyl group of these acids having 1 to 4 carbon atoms. The toner binder according to claim 2, which is one type. Polyester resin (A) is charged variation to be defined by the following equation (2) (%) is -20 to 20% a toner binder according to any one of claims 1 to 3.

[The 60-second stirring charge amount Q (60) (μC / g) is the temperature 23 of (A) having a volume average particle diameter (Dv) of 5 to 8 μm and a particle diameter distribution Dv / Dn = 1.3. It is a 60-second stirring charge amount by the blow-off method in an environment of ° C. and humidity of 50%. The 600-second stirring charge amount Q (600) (μC / g) is a particle having a volume average particle diameter (Dv) of 5 to 8 μm and a particle diameter distribution Dv / Dn = 1.3, and the temperature is 23 ° C. It is a stirring charge amount for 600 seconds by the blow-off method in an environment of 50% humidity. ] Polyester resin (A), the toner binder according to any one of claims 1 to 4, containing 70 to 100 mole% of aromatic diol component based on the total moles of the polyol component as a raw material (x). Aromatic dicarboxylic acid component (y1) The toner binder according to any one of claims 1 to 5 carbon atoms of the terephthalic acid and / or alkyl groups are terephthalic acid alkyl ester is 1-5. Toner binder according to any one of claims 1 to 6 flow softening point of 80 to 160 ° C. of the polyester resin (A). Toner binder according to any one of claims 1 to 7 the glass transition temperature of the polyester resin (A) is 40 to 80 ° C.. Gel permeation chromatography in the polyester resin (A) in tetrahydrofuran-soluble matter of the toner binder according to any one of claims 1 to 8 peak top molecular weight of 2,000 to 50,000 of. Toner containing a colorant and a toner binder according to any one of claims 1-9.