JP6829102B2 - Toner binder manufacturing method and toner manufacturing method - Google Patents

Description

The present invention relates to a method for producing a toner binder and a method for producing a toner. More specifically, the present invention relates to a method for producing a toner binder used for developing an electrostatic charge image or a magnetic latent image and a method for producing a toner in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copiers and laser printers has been rapidly increasing, and the demand for their performance is also increasing. Generally, in the electrophotographic method, a static charge image (latent image) is formed on a photoconductor, and then the latent image is developed with toner to form a toner image. After transferring the toner image onto a recording medium such as paper, it is fixed by a method such as heating.

From the viewpoint of energy saving such as reduction of energy consumption in the fixing process as well as promotion of miniaturization, high speed, and high image quality of the electrophotographic apparatus, improvement of low temperature fixability of toner is strongly required.
As a means for lowering the fixing temperature of the toner, a technique for lowering the glass transition point of the binder resin is generally used. However, if the glass transition point is set too low, powder agglutination (blocking) is likely to occur and the storage stability of the toner is lowered. Therefore, the lower limit of the glass transition point is practically 50 ° C. This glass transition point is a design point of the binder resin, and a method of lowering the glass transition point cannot obtain a toner that can be fixed at a lower temperature.

Further, as another means, the molecular weight is reduced. However, if the molecular weight is made too small, when the toner image is fixed by the thermal roll fixing method, the thermal roll and the molten toner come into direct contact at the time of fixing, but at this time, the toner transferred onto the thermal roll is next. There is a drawback that the so-called offset phenomenon, which stains the transferred transfer paper or the like, is likely to occur.

As a means for solving such a problem, for example, a toner (Patent Document 1) composed of a vinyl polymer appropriately crosslinked using a cross-linking agent and a molecular weight modifier, or a weight average molecular weight / number average molecular weight ratio. A toner having a wide molecular weight distribution so as to have a molecular weight distribution of 3.5 to 40 (Patent Document 2) has been proposed.
However, these toners have a wider fixable range, that is, a temperature range between the offset generation temperature and the lower limit temperature of fixing, as compared with the conventional uncrosslinked single resin having a narrow molecular weight distribution, but they are not yet sufficient.

On the other hand, toners using a reaction product of a mixture of polyester resins and isocyanate have been proposed (Patent Documents 3 to 10).
However, even if this method can prevent the offset phenomenon at high temperature to some extent, the lower limit temperature of fixing also rises at the same time, which makes low temperature fixing difficult, and the demand for high speed and energy saving has not been sufficiently met yet. ..

Special Publication No. 51-2334 Special Publication No. 55-6805 Japanese Unexamined Patent Publication No. 63-56659 Japanese Unexamined Patent Publication No. 1-154068 Japanese Unexamined Patent Publication No. 2-166464 Japanese Unexamined Patent Publication No. 2-308175 Japanese Unexamined Patent Publication No. 4-2112272 JP-A-11-28203 Japanese Unexamined Patent Publication No. 11-305481

The present invention provides a toner binder having excellent low-temperature fixability, glossiness and hot offset resistance, and excellent toner fluidity, heat storage stability, charge stability, pulverization property, image strength, bending resistance and document offset property. It is an object of the present invention to provide a manufacturing method and a manufacturing method of toner.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, it is a method for producing a toner binder containing a urethane-modified polyester resin (D) in which a polyester resin (A), a polyester resin (B) and a polyvalent isocyanate (C) are kneaded and reacted at 150 to 210 ° C. , A method for producing a toner binder in which the hydroxyl value OHV _A of the polyester resin (A) is 10 to 80 KOHmg / g and the hydroxyl value OHV _B of the polyester resin (B) is less than 10 KOHmg / g; the toner containing the toner binder It is a manufacturing method.

According to the present invention, a toner binder having excellent low temperature fixability, glossiness and hot offset resistance, and excellent toner fluidity, heat storage stability, charge stability, pulverization property, image strength, bending resistance and document offset property. It has become possible to provide toner.

The method for producing a toner binder of the present invention contains a urethane-modified polyester resin (D) in which a polyester resin (A), a polyester resin (B), and a polyvalent isocyanate (C) are kneaded and reacted at 150 to 210 ° C. A method for producing a toner binder, wherein the hydroxyl value OHV _A of the polyester resin (A) is 10 to 80 KOHmg / g, and the hydroxyl value OHV _B of the polyester resin (B) is less than 10 KOHmg / g. Is.

Hereinafter, the polyester resin (A), the polyester resin (B), the polyhydric isocyanate (C), the urethane-modified polyester resin (D), and a method for producing the same will be sequentially described.

In producing the urethane-modified polyester resin (D) of the toner binder of the present invention, the hydroxyl value of the polyester resin (A) and the hydroxyl value of the polyester resin (B) have low-temperature fixability, heat-resistant storage stability, charge stability, and pulverizability. It is important from the viewpoint of.
Specifically, the hydroxyl value OHV _A of the polyester resin (A) of the present invention is 10~80KOHmg / g, preferably from 10~50KOHmg / g, more preferably 20~40KOHmg / g. If (A) exceeding 80 KOH mg / g is used, the charge stability and pulverizability may be deteriorated.

On the other hand, the hydroxyl value OHV _B of the polyester resin (B) of the present invention is less than 10 KOH mg / g, preferably less than 5 KOH mg / g, and more preferably less than 1 KOH mg / g.

The hydroxyl values of the polyester resin (A) and the polyester resin (B) can be measured by the method specified in JIS K0070.

The glass transition temperature (hereinafter, may be abbreviated as Tg) of the polyester resin (A) of the present invention is preferably 35 to 65 ° C, more preferably -30 to 35 ° C, and particularly preferably −20. ~ 15 ° C.
If the temperature is lower than −35 ° C., the heat-resistant storage stability may be deteriorated, and if the temperature exceeds 65 ° C., the low-temperature fixability may be deteriorated.

The glass transition temperature is measured by a differential scanning calorimetry device (DSC) by the method (DSC method) specified in ASTM D3418-82, and is a turning point showing the glass transition temperature (Tg) on the DSC chart. Can be confirmed. For example, it can be measured using DSC20 and SSC / 580 manufactured by Seiko Instruments Inc.

Specifically, 5 mg of the sample was placed in a container of the DSC device, heated at 20 ° C. per minute to a temperature about 30 ° C. higher than the end of the glass transition, and cooled at 60 ° C. per minute to a temperature about 50 ° C. lower than the glass transition temperature. After that, it is heated at 20 ° C. per minute to a temperature about 30 ° C. higher than that at the end of the glass transition.
From the above measurement, draw a graph of heat absorption and heat generation and temperature, and at the point where the straight line extending the baseline on the low temperature side of the graph to the high temperature side and the slope of the curve of the stepwise change part of the glass transition are maximized. The temperature at the intersection with the drawn tangent is the glass transition temperature.

The Tg of the polyester resin (B) of the present invention is 45 to 80 ° C, preferably 50 to 70 ° C, and more preferably 55 to 65 ° C.
If the temperature is lower than 45 ° C., the heat-resistant storage property may be deteriorated, and if the temperature exceeds 80 ° C., the low-temperature fixability may be deteriorated.

In producing the urethane-modified polyester resin (D) of the toner binder of the present invention, the weight ratio (A) / (B) of the polyester resin (A) to the polyester resin (B) is preferably 2/98 to 50/50. It is more preferably 5/95 to 40/60, further preferably 7/93 to 30/70, particularly preferably 9/91 to 20/80, and most preferably 10/90 to 18/82. If the weight ratio (A) / (B) is lower than 2/98, heat-resistant storage and image strength may deteriorate, and if the weight ratio (A) / (B) is higher than 50/50, crushability and glossiness may be deteriorated. Low temperature fixability may deteriorate.

The polyester resin (A) and the polyester resin (B) in the present invention are obtained by polycondensing one or more kinds of polyol components (x) and one or more kinds of polycarboxylic acid components (y). Examples of the polyol component (x) include a diol (x1) and a polyol (x2) having a valence of 3 to 8 or more.

As the diol (x1), 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-Nonandiol, 1,10-decanediol, 1,12-dodecanediol, etc.);
Alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols with 6 to 36 carbon atoms (1,4-cyclohexane) Dimethanol and hydrogenated bisphenol A, etc.);
(Poly) oxyalkylene of the above alicyclic diol [The same applies to polyoxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) or less of the alkylene group] Ether [Oxyalkylene unit (hereinafter abbreviated as AO unit) (May be.) Numbers 1 to 30];
Divalent phenol [monocyclic divalent phenol (for example, hydroquinone), polyoxyalkylene ether of bisphenols (number of AO units 2 to 30); and the like.

The polyoxyalkylene ether of bisphenols is usually obtained by adding an alkylene oxide (hereinafter, may be 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 represents an alkylene group having 1-3 carbon atoms, -SO _2- , -O-, -S-, or a direct bond; Ar is substituted with a halogen atom or an alkyl group having 1 to 30 carbon atoms. Represents a phenylene group which may be. ]

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 these can be used in combination of two or more.

As the alkylene oxide added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, and specifically, ethylene oxide (hereinafter, may be abbreviated as EO) and propylene oxide (hereinafter, PO and the like). It may be abbreviated.), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran and a combination of two or more of these can be mentioned.
Of these, EO and / or PO are preferred. The number of moles of AO added is preferably 2 to 30 moles, more preferably 2 to 10 moles.
Among the polyoxyalkylene ethers of bisphenols, those preferable from the viewpoint of toner fixability are EO and / or PO adducts of bisphenol A (average number of moles added 2 to 4, particularly 2 to 3).

Examples of the 3- to 8-valent or higher valence polyol (x2) include 3- to 8-valent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and their intramolecular or intermolecular dehydrations. For example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol);
Sugars and their derivatives such as sucrose and methyl glucosides);
(Poly) oxyalkylene ether of the above aliphatic polyhydric alcohol (number of AO units 1 to 30);
Polyoxyalkylene ethers of trisphenols (trisphenol PA, etc.) (number of AO units 2 to 30);
Examples thereof include polyoxyalkylene ethers (number of AO units 2 to 30) of novolak resins (phenol novolac, cresol novolak, etc., average degree of polymerization 3 to 60).

Among these polyol components (x), those preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms and polyoxyalkylene ethers of bisphenols (number of AO units 2 to 2). 30) Aliphatic polyhydric alcohols of 3 to 8 or more valences, and polyoxyalkylene ethers of novolak resins (number of AO units 2 to 30).

From the viewpoint of storage stability, alkylene glycols having 2 to 10 carbon atoms, polyoxyalkylene ethers of bisphenols (number of AO units 2 to 5), and polyoxyalkylene ethers of novolak resin (number of AO units 2) are more preferable. ~ 30).
Particularly preferred are alkylene glycol having 2 to 6 carbon atoms and polyoxyalkylene ether of bisphenol A (number of AO units 2 to 5), and most preferably polyoxyalkylene ether of ethylene glycol, propylene glycol and bisphenol A (the number of AO units is 2 to 5). The number of AO units is 2-3).

Examples of the polycarboxylic acid component (y) include a dicarboxylic acid (y1) and / or a polycarboxylic acid (y2) having a value of 3 to 6 or more.

Examples of the dicarboxylic acid (y1) include alcandicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid and sebacic acid), and arcendicarboxylic acids having 4 to 50 carbon atoms (dodecenyl succinic acid). Alkenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, etc.), aromatic dicarboxylic acids with 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) ), Vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, by gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer, etc.), etc. Can be mentioned.

Examples of the polycarboxylic acid (y2) having a valence of 3 to 6 or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and aliphatic acids having 6 to 36 carbon atoms. Vinyl polymers of tricarboxylic acids (hexanetricarboxylic acids, etc.) and unsaturated carboxylic acids [Mn: 450-10,000] (styrene / maleic acid copolymers, styrene / acrylic acid copolymers, and styrene / fumaric acid copolymers) Coalescence, etc.) and the like.
As the polycarboxylic acid component (y), anhydrous or lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these polycarboxylic acids may be used, or these polycarboxylic acids may be used. It may be used in combination with a carboxylic acid.

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, alkendicarboxylic acids having 4 to 50 carbon atoms, and carbons. It is an aromatic dicarboxylic acid having a number of 8 to 20 and an aromatic polycarboxylic acid having 9 to 20 carbon atoms.
From the viewpoint of storage stability, adipic acid, alkenylsuccinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and a combination thereof are more preferable.
Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Anhydrides and lower alkyl esters of these acids are similarly preferred.

The reaction ratio of the polyol component (x) to 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. It is 5 / 1-1 / 1.3, particularly preferably 1.4 / 1-1 / 1.2.

Examples of the polyisocyanate (C) of the present invention include divalent diisocyanate (C2) and 3- to 8-valent polyisocyanate (C1).

Examples of the divalent diisocyanate (C2) include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4,4. -Trimethylhexamethylene diisocyanate and the like.

Examples of the alicyclic diisocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogen. Examples thereof include added toluene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.

Examples of the aromatic diisocyanate include phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate (MDI), and 4,4'-diphenylmethane diisocyanate, 4 , 4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate and the like.

Among the divalent diisocyanates (C2), those preferable from the viewpoint of cross-linking density are aromatic diisocyanates having 6 to 15, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms. Particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

The 3- to 8-valent polyisocyanate (C1) is not particularly limited as long as it is a compound having 3 to 8 isocyanate groups, but is triisocyanate, tetraisocyanate, isocyanurate (trivalent duranate TPA-100), biuret ( Examples thereof include compounds containing the chemical structure of trivalent duranate 24A-100). Further, a product obtained by synthesizing a 3- to 8-valent polyisocyanate (C1) or a polyisocyanate having a higher valence using a 1- to 3-valent isocyanate as a raw material can be used.

Examples of the triisocyanate include compounds represented by the following chemical formula (1).

[In the formula, R ₁ represents an alkyl group and R ₂ represents an alkylene group. ]

Examples of the tetraisocyanate include compounds represented by the following chemical formula (2).

[In the formula, R ₂ represents an alkylene group. ]

Examples of the compound having an isocyanurate structure include an isocyanurate trimer and an isocyanurate pentamer, and there are also isocyanurate tetramers and multimers of isocyanurate tetramers and 9 or more.
The isocyanurate trimer is a polyisocyanate composed of three molecules of a diisocyanate monomer and having an isocyanurate group, and examples thereof include compounds represented by the following chemical formula (3).

[In the formula, R represents a residue obtained by removing one isocyanate group from the diisocyanate monomer. ]

The isocyanurate pentamer is a polyisocyanate having an isocyanurate structure composed of 6 molecules of a diisocyanate monomer, and examples thereof include a compound represented by the following chemical formula (4).

[In the formula, -R represents a residue obtained by removing one isocyanate group from the diisocyanate monomer, and -R- represents a residue obtained by removing two isocyanate groups from the diisocyanate monomer. ]

The compound having a biuret structure is formed from a urea and an isocyanate group, and examples thereof include a compound represented by the following chemical formula (5).

[In the formula, R represents a residue obtained by removing one isocyanate group from the diisocyanate monomer. ]

Further, as the polyisocyanate (C) used for this purpose, a modified polyisocyanate (C3) can be used in addition to the divalent diisocyanate (C2) and the 3- to 8-valent polyisocyanate (C1).

Examples of the urethane-modified polyvalent isocyanate (C31) include urethane-modified products of diisocyanate (C2) and polyhydric alcohol.

Examples of the polyhydric alcohol include divalent alcohols having 1 to 20 carbon atoms, trihydric alcohols, tetravalent alcohols, pentavalent alcohols, hexahydric alcohols and the like. Of these, trimethylolpropane, which is a trihydric alcohol having 6 carbon atoms, is preferable.

The urethane-modified polyvalent isocyanate (C31) is preferably an adduct-type modified product of the above-mentioned trimethylolpropane and hexamethylene diisocyanate. (Product name: Duranate AE700-100 (manufactured by Asahi Kasei Chemicals))

Examples of the biuret-modified polyvalent isocyanate (C32) include a biuret-modified product of a diisocyanate mixture (C2) and water. Of these, Duranate 24A-100 (manufactured by Asahi Kasei Chemicals), which is a trimer of hexamethylene diisocyanate, is preferable.

Examples of the allophanate-modified polyvalent isocyanate (C33) include an allophanate-modified form of diisocyanate (C2). Of these, Duranate A201H (manufactured by Asahi Kasei Chemicals), which is a dimer of hexamethylene diisocyanate, is preferable.

Among the above multi-valent isocyanates (C), 3- to 8-valent polyisocyanates (C1) are preferable from the viewpoint of low temperature fixability, offset resistance, and heat storage stability.
Further, among the 3- to 8-valent polyisocyanates (C1), the polyisocyanate (C11) containing the chemical structure of isocyanurate and biuret is further preferable.

In the present invention, each polyester resin can be produced in the same manner as a normal polyester production method.
For example, the reaction can be carried out in an atmosphere of an inert gas (nitrogen gas or the like) at a reaction temperature of preferably 150 to 280 ° C., more preferably 160 to 250 ° C., and particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of the reaction rate of the polycondensation reaction.

At this time, an esterification catalyst can be used if necessary.
Further, a stabilizer may be added for the purpose of obtaining polyester polymerization stability. Examples of the stabilizer include hydroquinone, methylhydroquinone, hindered phenol compounds and the like.

The toner binder of the present invention contains a urethane-modified polyester resin (D), and the urethane-modified polyester resin (D) contains a polyester resin (A), a polyester resin (B), and a polyhydric isocyanate (C), 150. It is obtained by kneading and reacting at ~ 210 ° C.
The kneading method is not particularly limited as long as it is a method of kneading the polyester resin (A), the polyester resin (B), and the polyvalent isocyanate (C), but for example, the polyester resin (A) and the polyester resin (B). May be kneaded and melted and then the polyhydric isocyanate (C) is added and kneaded, or the polyester resin (A) and the polyvalent isocyanate (C) are kneaded and melted and then the polyester resin (B). May be added and kneaded, or the polyester resin (B) and the polyhydric isocyanate (C) may be kneaded and melted, and then the polyester resin (A) may be added and kneaded. Further, if necessary, it may be melted and then kneaded, or two or more of them may be mixed and then kneaded. The polyester resin (A), the polyester resin (B), and the multivalent isocyanate (C) may be kneaded at the same time.

In the urethane-modified polyester resin (D) obtained by the above method, the polyhydric isocyanate (C) acts as a cross-linking agent and reacts with the melt of the polyester resin (A) and / or the polyester resin (B) to carry out a cross-linking reaction. Is effective, so that the hot offset resistance and heat storage resistance of the toner are improved.

The method for performing this kneading is not particularly limited, and the kneading may be performed in a reaction vessel or may be heated by a twin-screw extruder for kneading.
For example, a mixture of polyester resin (A) and polyester resin (B) is injected into a twin-screw extruder at a constant rate, and at the same time, polyvalent isocyanate (C) is also injected at a constant rate, and kneaded and conveyed at a temperature of, for example, 150 ° C. There is a method of carrying out the reaction while charging the polyester resin (A) and the polyester resin (B) in a reaction vessel, heating them to a temperature at which they are in a solution state, and mixing them.

When a twin-screw extruder is used, the reaction raw materials, polyester resin (A) and polyester resin (B), which are charged or injected into the twin-screw extruder, are directly delivered to the extruder without being cooled from the resin reaction solution. It may be injected, or the resin once produced may be cooled and crushed and supplied to a twin-screw extruder.

In the present invention, the temperature at which the polyester resin (A), the polyester resin (B), and the polyhydric isocyanate (C) are kneaded and reacted is 150 to 210 ° C, preferably 160 to 205 ° C, and more preferably 160 to 205 ° C. It is 170 to 200 ° C, particularly preferably 180 to 195 ° C.
If the kneading temperature is less than 150 ° C., the glossiness and heat-resistant storage stability may deteriorate, and if the kneading temperature exceeds 210 ° C., the hot offset resistance and image strength may deteriorate.

The urethane-modified polyester resin (D) of the present invention preferably has a urethane group and one or more functional groups selected from the group consisting of a urea group, a biuret group, and an allophanate group from the viewpoint of heat stability. .. In addition to being obtained by reaction with the molten mixture, the above four functional groups are contained in the structure in the multivalent isocyanate (C).

Among the functional groups obtained by the reaction of the present invention, the urethane group is obtained by reacting the hydroxyl group of the polyester resin (A) or the polyester resin (B) with the isocyanate group of the polyhydric isocyanate (C).

Among the functional groups obtained by the reaction of the present invention, the urea group is obtained by reacting the water contained in the polyester resin (A) or the polyester resin (B) with the isocyanate group of the polyhydric isocyanate (C).

Among the functional groups obtained by the reaction of the present invention, the biuret group is a urea group obtained by reacting the water contained in the polyester resin (A) or the polyester resin (B) with the isocyanate group of the polyhydric isocyanate (C). Is obtained by reacting with the isocyanate group of the polyhydric isocyanate (C).

Among the functional groups obtained by the reaction of the present invention, the allophanate group is a urethane bond obtained by reacting the hydroxyl group of the polyester resin (A) or the polyester resin (B) with the isocyanate group of the polyhydric isocyanate (C). It is obtained by reacting with the isocyanate group of the valent isocyanate (C).

The water content in the system is measured by a Karl Fischer trace water content measuring device (coulometric titration type automatic water content measuring device), and the measurement conditions are as follows. Specifically, first, a carrier gas (nitrogen) is flowed at 200 mL / min to anhydrous the titration cell. Then, the sample board is air-baked at 200 ° C., cooled, and 0.1 g of the sample is added to start the measurement.

Measuring device: CA-100 manufactured by Mitsubishi Chemical Corporation
Moisture vaporizer: VA-100
Anode solution: Aquamicron AX
Cathode solution: Aquamicron CXU
Carrier gas flow rate: 200 mL / min Heating temperature: 200 ° C
Sample weight: 0.1 g

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 and Oil Pink OP, etc. Alternatively, two or more types can be mixed and used. Further, if necessary, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt or nickel or a compound such as magnetite, hematite or ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder of the present invention. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

In addition to the toner binder and the colorant, the toner of the present invention contains, if necessary, one or more additives selected from a mold release agent, a charge control agent, a fluidizing agent, and the like.

The release agent preferably has a softening point [Tm] of 50 to 170 ° C. by a flow tester, and is preferably a polyolefin wax, a natural wax, an aliphatic alcohol having 30 to 50 carbon atoms, a fatty acid having 30 to 50 carbon atoms, and these. Examples include mixtures.

As the polyolefin wax, those obtained by (co) polymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof). And heat-reduced copolymers], oxides of olefin (co) copolymers with oxygen and / or ozone, maleic acid modified products of olefins (co) polymers [eg maleic anhydride and derivatives thereof (maleic anhydride, Modified products (monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meth) ) Copolymers with alkyl acrylate (1-18 carbon atoms of alkyl) and alkyl maleic anhydride (1-18 carbon atoms of alkyl)] and the like, and sazole wax and the like.

Examples of natural waxes include carnauba wax, montan wax, paraffin wax and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of fatty acids having 30 to 50 carbon atoms include triacontane carboxylic acid.

Charge control agents include niglosin dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal azo dyes, and copper phthalocyanine dyes. , Salicylate metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic ring-containing polymer and the like.

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

When a release agent is used, the release agent is preferably 0.001 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight, based on the toner weight.
When a charge control agent is used, the charge control agent is preferably 0.001 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 toner weight. Is.
When a fluidizing agent is used, the fluidizing agent is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, and particularly preferably 0.1 to 4% by weight, based on the toner weight. ..
The total amount 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 toner weight. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The toner of the present invention may be obtained by any of known methods such as a kneading and pulverizing method, an emulsion phase inversion method, and a polymerization method.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. By further classifying, the particles have a volume average particle diameter (D50) of preferably 5 to 20 μm, and then mixed with a fluidizing agent to produce the particles.
The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When toner is obtained by the emulsification phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. it can. The volume average particle size of the toner is preferably 3 to 15 μm.

The toner of the present invention is electrically latent by being mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. Used as an image developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. Further, instead of the 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 to a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to be used as a recording material. As a method of 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. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part. Example 8 is Reference Example 1, and Example 17 is Reference Example 2.

<Manufacturing Example 1><Synthesis of polyester resin (A-1)>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer and a nitrogen introduction tube, 177 parts (8 mol%) of bisphenol A propylene oxide 2 mol addition and 301 parts (41 mol) of 3-methyl 1,5-pentanediol %), 12 parts (1 mol%) of trimethylolpropane, 508 parts (49 mol%) of terephthalic acid, and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst, and the mixture is produced at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A-1).
The peak molecular weight of the polyester resin (A-1) was 8,700, Tg was 16 ° C., acid value was 0.4, hydroxyl value was 35, number average molecular weight was 3,200, and weight average molecular weight was 9,400.

<Manufacturing Example 2><Synthesis of polyester resin (A-2)>
194 parts (9 mol%) of bisphenol A propylene oxide 2 mol addition, 298 parts (41 mol) of 3-methyl 1,5-pentanediol in a reaction vessel equipped with a condenser, a thermometer, a stirrer and a nitrogen introduction tube. %), 12 parts (1 mol%) of trimethylolpropane, 493 parts (48 mol%) of terephthalic acid, and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst, which are produced at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A-2).
The peak molecular weight of the polyester resin (A-2) was 4,300, Tg was 12 ° C., the acid value was 0.5, the hydroxyl value was 80, the number average molecular weight was 2,100, and the weight average molecular weight was 4,600.

<Manufacturing Example 3><Synthesis of polyester resin (A-3)>
171 parts (8 mol%) of bisphenol A propylene oxide 2 mol addition, 307 parts (41 mol) of 3-methyl 1,5-pentanediol in a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube. %), 11 parts (1 mol%) of trimethylolpropane, 447 parts (43 mol%) of terephthalic acid, 62 parts (7 mol%) of adipic acid, and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst. The reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A-3).
The peak molecular weight of the polyester resin (A-3) was 25,200, Tg was 15 ° C., acid value was 0.6, hydroxyl value was 10, number average molecular weight was 5,600, and weight average molecular weight was 37,300.

<Manufacturing Example 4><Synthesis of polyester resin (A-4)>
744 parts (50 mol%) of bisphenol A ethylene oxide 2 mol adduct, 163 parts (26 mol%) of adipic acid, 171 parts of terephthalic acid in a reaction vessel equipped with a cooling tube, thermometer, stirrer and nitrogen introduction tube. (24 mol%) and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and the reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A-4).
The peak molecular weight of the polyester resin (A-4) was 8,000, Tg was 40 ° C., acid value was 0.1, hydroxyl value was 15, number average molecular weight was 4,100, and weight average molecular weight was 19,500.

<Manufacturing Example 5><Synthesis of polyester resin (A-5)>
695 parts (52 mol%) of bisphenol A ethylene oxide 2 mol adduct, 275 parts (46 mol%) of adipic acid, trimellitic anhydride in a reaction vessel equipped with a condenser, a thermometer, a stirrer and a nitrogen introduction tube. 27 parts (2 mol%) and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and the reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A-4).
The peak molecular weight of the polyester resin (A-4) was 8,000, the Tg was -14 ° C, the acid value was 0.1, the hydroxyl value was 30, the number average molecular weight was 3,800, and the weight average molecular weight was 20,000. ..

<Comparative Production Example 1><Synthesis of Polyester Resin (A'-1)>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer and a nitrogen introduction tube, 195 parts (9 mol%) of bisphenol A propylene oxide 2 mol addition and 301 parts (42 mol) of 3-methyl 1,5-pentanediol %), 12 parts (2 mol%) of trimethylolpropane, 489 parts (48 mol%) of terephthalic acid, and 2 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst, and the mixture is produced at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off water. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyester resin (A'-1).
The peak molecular weight of the polyester resin (A'-1) was 4,100, Tg was 11 ° C., acid value was 0.5, hydroxyl value was 85, number average molecular weight was 2,000, and weight average molecular weight was 4,300. ..

<Manufacturing Example 6><Synthesis of polyester resin (B-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 654 parts (46 mol%) of bisphenol A propylene oxide 2 mol adduct, 67 parts (14 mol%) of benzoic acid, and titanium diisopropoxy as a condensation catalyst. One part of bistriethanolaminate was added, and the mixture was reacted at 200 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Next, 244 parts (36 mol%) of terephthalic acid and 1 part of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and then the reaction was carried out under a reduced pressure of 5 to 20 mmHg for 4 hours while gradually raising the temperature to 230 ° C. It was. Next, the mixture was cooled to 180 ° C., 32 parts (4 mol%) of trimellitic anhydride was added, and the reaction was carried out under normal pressure sealing for 2 hours, then reacted at 220 ° C. and normal pressure, and taken out when the hydroxyl value became less than 1. , Polyester resin (B-1) was obtained.
The obtained polyester resin (B-1) had a hydroxyl value of 0.1, an acid value of 16, Tg of 56 ° C., a number average molecular weight of 2,500, and a weight average molecular weight of 7,100.

<Manufacturing Example 7><Synthesis of polyester resin (B-2)>
634 parts (46 mol%) of bisphenol A propylene oxide 2 mol adduct, 95 parts (14 mol%) of pt-butylbenzoic acid, condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube. As a whole, 1 part of titanium diisopropoxybistriethanol aminated was added, and the mixture was reacted at 200 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Next, 238 parts (36 mol%) of terephthalic acid and 1 part of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and then the reaction was carried out under a reduced pressure of 5 to 20 mmHg for 4 hours while gradually raising the temperature to 230 ° C. It was. Next, the mixture was cooled to 180 ° C., 30 parts (4 mol%) of trimellitic anhydride was added, and the reaction was carried out under normal pressure sealing for 2 hours, then reacted at 220 ° C. and normal pressure, and taken out when the hydroxyl value became less than 1. , Polyester resin (B-2) was obtained.
The obtained polyester resin (B-2) had a hydroxyl value of 0.1, an acid value of 16, Tg of 63 ° C., a number average molecular weight of 2,300, and a weight average molecular weight of 7,000.

<Manufacturing Example 8><Synthesis of polyester resin (B-3)>
689 parts (49 mol%) of bisphenol A propylene oxide 2 mol adduct, 85 parts (11 mol%) of pt-butylbenzoic acid, condensation catalyst in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. As a whole, 1 part of titanium diisopropoxybistriethanol aminated was added, and the mixture was reacted at 200 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Next, 257 parts (36 mol%) of terephthalic acid and 1 part of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and then the reaction was carried out under a reduced pressure of 5 to 20 mmHg for 4 hours while gradually raising the temperature to 230 ° C. It was. Next, the mixture was cooled to 180 ° C., 33 parts (4 mol%) of trimellitic anhydride was added, and the reaction was carried out under normal pressure sealing for 2 hours, then reacted at 220 ° C. and normal pressure, and taken out when the hydroxyl value became less than 1. , Polyester resin (B-3) was obtained.
The obtained polyester resin (B-3) had a hydroxyl value of 5, an acid value of 16, Tg of 60 ° C., a number average molecular weight of 2,100, and a weight average molecular weight of 6,200.

<Comparative Manufacturing Example 2><Synthesis of Polyester Resin (B'-1)>
649 parts (48 mol%) of bisphenol A propylene oxide 2 mol adduct, 58 parts (8 mol%) of benzoic acid, and titanium diisopropoxy as a condensation catalyst in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. One part of bistriethanolaminate was added, and the mixture was reacted at 200 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Next, 275 parts (42 mol%) of terephthalic acid and 1 part of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and then the reaction was carried out under a reduced pressure of 5 to 20 mmHg for 4 hours while gradually raising the temperature to 230 ° C. It was. Next, the mixture was cooled to 180 ° C., 16 parts (2 mol%) of trimellitic anhydride was added, and the mixture was reacted under normal pressure for 2 hours, then reacted at 220 ° C. and normal pressure to be taken out to obtain a polyester resin (B'-1). It was.
The obtained polyester resin (B'-1) had a hydroxyl value of 10, an acid value of 17, Tg of 63 ° C., a number average molecular weight of 2,400, and a weight average molecular weight of 6,800.
The polyester resin (B'-1) is a polyester resin that satisfies the conditions of the polyester resin (A).

<Example 1><Manufacturing of toner binder (TB-1)>
As shown in Table 3, 10 parts of polyester resin (A-1), 90 parts of polyester resin (B-1), and at the same time, isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals). 3 parts are supplied to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that the weight ratio is (A-1) / (B-1) / (C-1) = 10/90/3. Then, the reaction was carried out at a reaction temperature of 190 ° C. and a residence time of 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-1) containing a urethane-modified polyester resin (D-1).

<Example 2><Manufacturing of toner binder (TB-2)>
10 parts of polyester resin (A-2), 90 parts of polyester resin (B-1), and 7 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) by weight (A-2) ) / (B-1) / (C-1) = 10/90/7 and supplied to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) and reacted at a reaction temperature of 190 ° C. and a residence time of 14 minutes. Was done.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-2) containing a urethane-modified polyester resin (D-2).

<Example 3><Manufacturing of toner binder (TB-3)>
10 parts of polyester resin (A-3) and 90 parts of polyester resin (B-1) and 2 parts of biuret-type trivalent isocyanate duranate 24A-100 (C-2) (manufactured by Asahi Kasei Chemicals) by weight ratio ( Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that A-3) / (B-1) / (C-2) = 10/90/2, and the reaction temperature is 190 ° C., residence time 14 The reaction was carried out in minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-3) containing a urethane-modified polyester resin (D-3).

<Example 4><Manufacturing of toner binder (TB-4)>
10 parts of polyester resin (A-4) and 90 parts of polyester resin (B-1) and 3 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals) by weight ratio Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that (A-4) / (B-1) / (C-1) = 10/90/3, and the reaction temperature stays at 190 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-4) containing a urethane-modified polyester resin (D-4).

<Example 5><Manufacturing of toner binder (TB-5)>
10 parts of polyester resin (A-5) and 90 parts of polyester resin (B-1) and 3 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals) by weight ratio Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that (A-5) / (B-1) / (C-1) = 15/85/5, and the reaction temperature stays at 190 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-5) containing a urethane-modified polyester resin (D-5).

<Example 6><Manufacturing of toner binder (TB-6)>
10 parts of polyester resin (A-1), 90 parts of polyester resin (B-2), and 3 parts of polyvalent isocyanate duranate TPA-100 (C-1) at the same time, by weight ratio (A-1) / (B) It was supplied to a twin-screw kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that -2) / (C-1) = 10/90/3, and the reaction was carried out at a reaction temperature of 190 ° C. and a residence time of 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-4) containing a urethane-modified polyester resin (D-4).

<Example 7><Manufacturing of toner binder (TB-7)>
10 parts of polyester resin (A-1) and 90 parts of polyester resin (B-3) and 3 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals) by weight ratio Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that (A-1) / (B-3) / (C-1) = 10/90/3, and the reaction temperature stays at 190 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-7) containing a urethane-modified polyester resin (D-7).

<Example 8><Manufacturing of toner binder (TB-8)>
At the same time as 30 parts of polyester resin (A-1) and 70 parts of polyester resin (B-1), 11 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals) by weight ratio. Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that (A-1) / (B-1) / (C-1) = 30/70/11, and the reaction temperature stays at 155 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-8) containing a urethane-modified polyester resin (D-8).

<Example 9><Manufacturing of toner binder (TB-9)>
5 parts of polyester resin (A-1) and 95 parts of polyester resin (B-1) and 2 parts of isocyanurate-type trivalent isocyanate duranate TPA-100 (C-1) (manufactured by Asahi Kasei Chemicals) by weight ratio Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that (A-1) / (B-1) / (C-1) = 5/95/2, and the reaction temperature stays at 205 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB-9) containing a urethane-modified polyester resin (D-9).

<Comparative Example 1><Manufacturing of Toner Binder (TB'-1)>
As shown in Table 3, 10 parts of the polyester resin (A-1), 90 parts of the polyester resin (B-1), and 3 parts of the polyhydric isocyanate duranate TPA-100 (C-1) were added in a weight ratio (A). -1) / (B-1) / (C-1) = 10/90/3 and supplied to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) at a reaction temperature of 160 ° C. and a residence time of 14 The reaction was carried out in minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB'-1) containing a urethane-modified polyester resin (D'-1).

<Comparative Example 2><Manufacturing of Toner Binder (TB'-2)>
As shown in Table 3, 10 parts of the polyester resin (A-1), 90 parts of the polyester resin (B-1), and 3 parts of the polyhydric isocyanate duranate TPA-100 (C-1) were added in a weight ratio (A). -1) / (B-1) / (C-1) = 10/90/3, supplied to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) at a reaction temperature of 240 ° C. and a residence time of 14 The reaction was carried out in minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB'-2) containing a urethane-modified polyester resin (D'-2).

<Comparative Example 3><Manufacturing of Toner Binder (TB'-3)>
As shown in Table 3, 10 parts of the polyester resin (A-1), 90 parts of the polyester resin (B'-1), and 3 parts of the polyhydric isocyanate duranate TPA-100 (C-1) were added in a weight ratio ( Supply to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) so that A-1) / (B'-1) / (C-1) = 10/90/3 and stay at a reaction temperature of 190 ° C. The reaction was carried out in 14 minutes.
The obtained kneaded reaction product was cooled to obtain a toner binder (TB'-3) containing a urethane-modified polyester resin (D'-3).

<Example 10><Preparation of toner (T-1)>
For 85 parts of toner binder (TB-1) containing urethane-modified polyester resin (D-1), 6 parts of carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation], 4 parts of carnauba wax, charge control agent T -77 [Hodogaya Chemical Co., Ltd.] 4 parts were added to make toner by the following method. First, it was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Machinery Co., Ltd.] and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Industries, Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industries, Ltd.], and the volume average particle size is increased. Toner particles having a D50 of 8 μm were obtained.
Then, 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) was mixed with 100 parts of the toner particles by a sample mill to obtain the toner (T-1) of the present invention.

<Examples 11 to 18><Preparation of toners (T-2) to (T-9)>
The composition of the raw materials was carried out except that the toner binders (TB-2) to (TB-9) containing urethane-modified polyester resins (D-2) to (D-9) were changed as shown in Table 4. Toners were produced in the same manner as in Example 10 to obtain toners (T-2) to (T-9). Next, evaluation was carried out in the same manner as in Example 10, and the results are shown in Table 4.

<Comparative Examples 4 to 6><Preparation of Toner (T'-1) to (T'-3)>
As for the composition of the raw materials, the toner binders (TB'-1) to (TB'-3) containing the urethane-modified polyester resins (D'-1) to (D'-3) are changed as shown in Table 4. Toners were produced in the same manner as in Example 10 except for the above, and toners (T'-1) to (T'-3) for comparison were obtained. Next, evaluation was carried out in the same manner as in Example 10, and the results are shown in Table 4.

[Evaluation methods]
The following are the measurement methods and evaluation methods for low-temperature fixability, glossiness, hot offset resistance, fluidity, heat storage stability, charge stability, crushability, image strength, bending resistance, and document offset test of the obtained toner. Will be described including the judgment criteria.

<Low temperature fixability>
The toner is evenly placed on the paper surface so as to be 0.85 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed is used. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
The temperature at which cold offset occurs (MFT) (° C.) when this paper is passed through a pressure roller under the conditions of fixing speed (heating roller peripheral speed) 213 mm / sec and fixing pressure (pressurized roller pressure) 10 kg / cm ^2. It was measured.
The lower the temperature at which the cold offset is generated, the better the low temperature fixability.

<Glossy>
Fixation evaluation is performed in the same manner as low temperature fixability. A white cardboard was laid under the image, and the glossiness (%) of the printed image was measured at an incident angle of 60 degrees using a glossiness meter (“IG-330” manufactured by HORIBA, Ltd.). The higher the glossiness, the better the glossiness.

<Hot offset resistance (hot offset generation temperature)>
Fixation was evaluated in the same manner as low-temperature fixability, and the presence or absence of hot offset in the fixed image was visually evaluated. The temperature at which the hot offset occurred after passing through the pressure roller was defined as the hot offset resistance (° C.).

<Liquidity>
The bulk density (g / 100 ml) of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity was judged according to the following criteria.

[Criteria]
⊚: 33 or more ○: 28 or more and less than 33 Δ: 25 or more and less than 28 ×: less than 25

<Heat-resistant storage>
The toner was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria.

[Criteria]
⊚: No blocking has occurred.
◯: Slight blocking has occurred.
Δ: Blocking has occurred in a part.
X: Blocking has occurred throughout.

<Charging stability>
(1) 0.5 g of toner and 20 g of a ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) are placed in a 50 ml glass bottle, and the humidity is adjusted at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stir welding was performed at 50 rpm for 20 minutes and 60 minutes with a tubler shaker mixer, and the amount of charge at each time was measured.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
"Charge amount of friction time 60 minutes / charge amount of friction time 10 minutes" was calculated and used as an index of charge stability.

[Criteria]
⊚: 0.8 or more ○: 0.7 or more and less than 0.8 Δ: 0.6 or more and less than 0.7 ×: less than 0.6

<Crushability>
A coarse crushed product (8.6 mesh pass to 30 mesh-on) kneaded and cooled by a twin-screw kneader is finely crushed by a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Industries, Ltd.] under the following conditions. Crushed.
Crushing pressure: 0.5 MPa
Crushing time: 10 minutes Adjuster ring: 15 mm
Louver size: Medium Without classifying this, the volume average particle size (μm) was measured with a Coulter counter-TAII (manufactured by Coulter Electronics, USA), and the pulverizability was evaluated according to the following criteria.
Since the toner (T'-5) of Comparative Example 10 was not subjected to the pulverization step, the evaluation of pulverization property was omitted.

[Criteria]
⊚: less than 8 μm ○: 8 μm or more and less than 10 μm Δ: 10 μm or more and less than 12 μm ×: 12 μm or more

<Image strength>
The image fixed by the evaluation of low temperature fixability was subjected to a scratch test by applying a load of 10 g from directly above the pencil fixed at an angle of 45 degrees according to JIS K5600, and the image strength was evaluated from the hardness of the pencil without scratches. .. The higher the pencil hardness, the better the image strength.

[Criteria]
⊚: H or more ○: HB to F
Δ: B to HB
×: 2B or less

<Bending resistance>
The image fixed by the evaluation of low temperature fixability is folded on paper so that the image surface is on the inside, and rubbed twice with a load of 30 g. The paper was unfolded and the presence or absence of white streaks on the image after bending was visually determined.
[Criteria]
◎: No white streaks ○: Slightly white spots △: Slightly white streaks ×: White streaks

<Document offset property>
Two sheets of A4 paper on which the image obtained by the evaluation of low temperature fixability is fixed are overlapped with each other on the fixed surfaces, a weight of 420 g (0.68 g / cm ² ) is applied, and the paper is allowed to stand at 60 ° C. for 60 minutes. ..
The document offset property was evaluated based on the following criteria for the state when the overlapped papers were pulled apart.

[Criteria]
◎: No resistance ○: There is some resistance when pulling apart △: There is a crisp sound, but the image does not peel off from the paper surface ×: The image peels off from the paper surface

As is clear from the evaluation results in Table 4, the toners of the examples of the present invention obtained results equal to or better than those of the conventional ones in all the evaluation items.
On the other hand, what is the toner (T'-1) of the comparative example having a low reaction temperature of 160 ° C., the toner (T'-2) of the comparative example having a high reaction temperature of 240 ° C., and the toner (T'-3) of the comparative example? At least one performance item was defective.

The toner binder and toner of the present invention are excellent in low temperature fixability, glossiness and hot offset resistance, and are suitable for toner fluidity, heat storage resistance, charge stability, crushability, image strength, bending resistance and document offset resistance. It is excellent and 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.
Further, it is suitable for applications such as paint additives, adhesive additives, and electronic paper particles.

Claims (6)

A method for producing a toner binder containing a urethane-modified polyester resin (D) in which a polyester resin (A), a polyester resin (B), and a polyvalent isocyanate (C) are kneaded and reacted at 190 to 210 ° C. hydroxyl value OHV _a of resin (a) is a 10~80KOHmg / g, Ri hydroxyl value OHV _B is 10 KOH mg / g less der of the polyester resin (B),
A method for producing a toner binder in which the polyisocyanate (C) is a 3- to 8-valent polyisocyanate (C1) . The method for producing a toner binder according to claim 1 , wherein the glass transition temperature Tg _A of the polyester resin (A) is 35 to 65 ° C. The method for producing a toner binder according to claim 1 or 2, wherein the glass transition temperature Tg _B of the polyester resin (B) is 45 to 80 ° C. The method for producing a toner binder according to any one of claims 1 to 3, wherein the weight ratio (A) / (B) of the polyester resin (A) to the polyester resin (B) is 2/98 to 50/50. The method for producing a toner binder according to any one of claims 1 to 4, wherein the urethane-modified polyester resin (D) has one or more functional groups selected from the group consisting of a urea group, a biuret group and an allophanate group. A method for producing a toner containing a toner binder and a colorant obtained by the method for producing a toner binder according to any one of claims 1 to 5 .