JP2010276931A - Toner binder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner binder which achieves quick start of charging and charging maintainability, and does not produce odor during production while having excellent low-temperature fixability. <P>SOLUTION: The toner binder contains a polyester resin (P) having a styrenated aromatic ring, prepared by polycondensation of a carboxylic acid component (A) and an alcohol component (B). The polyester resin (P) preferably includes a styrenated aromatic ring in at least a part of terminals of the molecule. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner binder used for electrophotography, electrostatic recording, electrostatic printing and the like.

In recent years, high-speed printing of electrophotography has progressed, and a toner having low-temperature fixability has been demanded. Accordingly, the polyester toner binder constituting the toner also has a low molecular weight in order to develop a low viscosity at a low temperature.
However, when the molecular weight of the polyester toner binder is reduced, thermal movement of molecules is likely to occur and electrons are easily transferred, so that the charge rising and charge retention as a toner tend to deteriorate. In view of this, a method has been proposed in which sulfonic acid groups are introduced into the toner binder to improve the charge start-up and charge retention. (Patent Document-1)
However, when a sulfonic acid group is introduced, there is a problem such as generation of odor when the toner composition is kneaded.

JP 2008-070455 A

  An object of the present invention is to provide a toner binder that is excellent in low-temperature fixability but has excellent charge rise and charge retention and does not generate odor during production.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention provides a toner binder comprising a polyester resin (P) containing a styrenated aromatic ring formed by polycondensation of a carboxylic acid component (A) and an alcohol component (B); And a toner containing the toner binder, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.

  According to the present invention, it is possible to provide a toner binder that is excellent in low temperature fixability but excellent in charge rising and charge retention and does not generate odor during production.

The present invention is described in detail below.
The polyester resin (P) in the present invention is styrenated by polycondensation of the carboxylic acid component (A) and the alcohol component (B) from the viewpoint of achieving both low-temperature fixability, charge rise and charge retention. It is a polyester resin containing an aromatic ring.

As a method of styrenating the polyester resin (P) and adding a styrenated aromatic ring,
(1) A method of producing a polyester resin (P) by styrenating an acid component and / or an alcohol component, and (2) a polycondensation reaction between an acid component and an alcohol component, and then styrenating. Thus, there is a method for producing the polyester resin (P), but the method (1) is preferred from the viewpoint of the styrenation rate and productivity.

  The monomer for styrenization may be an acid component or an alcohol component, but an alcohol component is preferred from the viewpoint of the styrenation rate.

  The method for carrying out styrenization is not particularly limited, but Friedel-Crafts reaction is preferable. In this case, the reaction temperature is preferably 50 to 250 ° C., more preferably 70 to 200 ° C., and most preferably 90 to 180 ° C. from the viewpoint of the styrenation rate. The catalyst is preferably a Lewis acid catalyst, and the reaction time is preferably 48 hours or less from the viewpoint of productivity.

The content of the structural unit of styrene in the polyester resin (P) (hereinafter referred to as styrenation rate) is preferably 1 to 65%, more preferably 3 to 60%, from the viewpoint of the rise of charge and charge retention. Most preferably, it is 5 to 50%.
In the above and the following, “%” means “% by weight” unless otherwise specified.
The styrenization rate is the ratio of the weight of styrene used as a raw material to the total weight of the polyester resin (P), and the styrenization rate can be adjusted by the amount of styrene used in the reaction.
Further, the content of the styrene structural unit (hereinafter referred to as the styrenation rate of the toner binder) relative to the total weight of the resin constituting the toner binder (including non-styrenated resin) is the rise of charge and charge retention. In view of the above, 1 to 65% is preferable, more preferably 3 to 60%, and most preferably 5 to 50%.

  When styrenating by the method of (1) above, the styrenation target is the aromatic carboxylic acid (A1) of the carboxylic acid component (A) and / or the alcohol component (B). Of the aromatic alcohol (B1).

Among the carboxylic acid components (A), the aromatic carboxylic acid (A1) may be an aromatic dicarboxylic acid, an aromatic monocarboxylic acid, a trivalent to hexavalent or higher aromatic polycarboxylic acid.
Examples of aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), and ester-forming derivatives thereof. You may use together.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc.) esters, and partial alkyl (same as above) esters. The same applies to the following ester-forming derivatives.
Of these, phthalic acid, isophthalic acid, and terephthalic acid are preferred.

  Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, t-butylbenzoic acid, etc.), and ester-forming derivatives thereof. Also good.

Examples of the trivalent to hexavalent or higher aromatic polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and ester-forming derivatives thereof. Two or more kinds may be used in combination.
Of these, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.

Examples of the carboxylic acid component (A2) other than the aromatic carboxylic acid (A1) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipine, and sebacic acid); alicyclic dicarboxylic acids having 6 to 40 carbon atoms [ For example, dimer acid (dimerized linoleic acid)]; alkenedicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid, malein, fumar, citraconic acid, and mesaconic acid), and ester-forming derivatives thereof Is mentioned.
Among these (A2), preferred are alkane dicarboxylic acids having 4 to 20 carbon atoms; alkene dicarboxylic acids having 4 to 36 carbon atoms, and ester-forming derivatives thereof, more preferably succinic acid, adipic acid, Maleic acid, fumaric acid, and ester-forming derivatives thereof, which may be used in combination of two or more.

Among the alcohol components (B), the aromatic alcohol (B1) may be an aromatic diol, an aromatic monool, a trivalent to octavalent or higher aromatic polyol.
Examples of aromatic diols include adducts having 2 to 4 carbon atoms (hereinafter abbreviated as AO) of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) (additional moles of 2 to 30). 2 or more may be used in combination.

  Examples of the aromatic monool include AO adducts having 2 to 4 carbon atoms (phenol addition number 2 to 30) of phenols (phenol, cumylphenol, naphthanol, etc.). Good.

Examples of the aromatic polyol having 3 to 8 or more valences include AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of trisphenols (such as trisphenol PA), and novolak resins (phenol novolac and cresol). Novolak and the like: AO adduct having 2 to 4 carbon atoms having an average degree of polymerization of 3 to 60) (addition mole number of 2 to 30) and the like may be used, and two or more kinds may be used in combination.
The styrenated product of the aromatic alcohol (B1) that is an AO adduct may be obtained by a method of adding AO after styrenating an AO non-added product.

  Among the alcohol components (B2) other than the aromatic alcohol (B1), the diol includes an aliphatic diol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, neopentyl glycol, 1,7-heptanediol, and alkanediols such as dodecanediol); polyalkylene ether glycols having 4 to 36 carbon atoms (such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol); the above-mentioned fats having 2 to 36 carbon atoms Group diol carbon number 2 4 AO [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide and the like] adducts (addition mole number 2 to 30); alicyclic diol having 6 to 36 carbon atoms (1 , 4-cyclohexanedimethanol, hydrogenated bisphenol A and the like); AO adducts having 2 to 4 carbon atoms (added moles of 2 to 30) of the above alicyclic diols, and the like. Good.

  As the polyol having 3 to 8 or more valences in (B2), 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (glycerin, triethylolethane, trimethylolpropane, pentaerythritol and Sorbitol, etc.); AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of the above aliphatic polyhydric alcohols and the like, and two or more kinds may be used in combination.

From the viewpoint of charge retention, it is preferable to have a styrenated aromatic ring at the molecular terminal of the polyester resin (P). By styrenizing an aromatic monocarboxylic acid or aromatic monool and polycondensing it as a part of the raw material, a styrenated aromatic ring can be introduced at the molecular terminal of the polyester resin (P).

The aromatic carboxylic acid (A1) and aromatic alcohol (B1) to be subjected to styrenation preferably have no substituent at the meta position and / or para position from the viewpoint of the styrenation rate. Since the steric hindrance is small at the meta position and the para position, styrenization easily occurs.
From the viewpoint of the styrenation rate, it is preferable that at least a part of the alcohol component (B) is a styrenated aromatic alcohol having no substituent at the meta position and / or para position of the aromatic ring.

The polyester resin (P) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 170 to 260 ° C, particularly preferably 190 to 240 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. 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 alcohol component (B) and the carboxylic acid component (A) is preferably 2/1 to 1/2, more preferably 1.5 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. /1-1/1.3, particularly preferably 1.3 / 1-1 / 1.2.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, a catalyst described in JP-A-2006-243715. [Titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolaminate), and intramolecular polycondensates thereof], and catalysts described in JP-A No. 2007-11307 (titanium tributoxyterephthalate) , Titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), zinc acetate, and the like. Among these, a titanium-containing catalyst is preferable.

The acid value of the polyester resin (P) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, and particularly preferably 0 to 60. When the acid value is 100 or less, the charging characteristics at the time of toner formation do not deteriorate.
The hydroxyl value of (P) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, particularly preferably 0 to 50. When the hydroxyl value is 100 or less, the hot offset resistance at the time of toner formation becomes better.

In the present invention, the acid value and hydroxyl value of the polyester resin are measured by the method defined in JIS K0070 (1992 edition).
When the sample has a solvent-insoluble component accompanying crosslinking, the sample after melt-kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

  The peak top molecular weight of the polyester resin (P) soluble in tetrahydrofuran (THF) (hereinafter referred to as Mp) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, particularly preferably 4. , 12,000 to 12,000.

In the present invention, the molecular weight [Mp and number average molecular weight (hereinafter referred to as Mn)] of the polyester resin and the alcohol component is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight is measured by dissolving a polyester resin or an alcohol component in THF and filtering out an insoluble component with a glass filter.

The glass transition temperature (Tg) of the polyester resin (P) used in the present invention is preferably from 30 to 70 ° C., more preferably from 40 to 70 ° C., particularly preferably from the viewpoint of fixability, storage stability and durability. ~ 70 ° C.
In addition, in the above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

The flow softening point [Tm] of (P) is preferably 80 to 160 ° C, more preferably 90 to 150 ° C, and particularly preferably 95 to 140 ° C. Within this range, the compatibility between hot offset resistance and low-temperature fixability is good. In the present invention, Tm is measured by the following method.
<Flow softening point [Tm]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum value of plunger descent amount This value (temperature when half of the measurement sample flows out) is taken as the flow softening point [Tm].

The polyester resin (P) used in the present invention preferably has a viscosity Eta [Tg + 40] (Pa · s) at Tg + 40 ° C. that satisfies the following formula (1) from the viewpoint of low-temperature fixability during toner formation. It is more preferable to satisfy (1 ′), and most preferable to satisfy the formula (1 ″).
Eta [Tg + 40] ≦ 7E + 5 Formula (1)
Eta [Tg + 40] ≦ 5E + 5 Formula (1 ′)
Eta [Tg + 40] ≦ 4E + 5 Formula (1 ″)
When Eta [Tg + 40] satisfies the formula (1), the viscosity in the low temperature region is small, and the low temperature fixability when used as a toner is good.
In order to adjust the viscosity Eta of (P), for example, to reduce Eta [Tg + 40], the Tm of the polyester resin (P) may be decreased, or Mp may be decreased.

In the present invention, the viscosity Eta of the polyester resin is measured using the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 8mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Temperature increase rate: 3 ° C / min

  The toner binder of the present invention may contain, in addition to the polyester resin (P), other resins usually used as a toner binder as long as the properties thereof are not impaired. Examples of the other resin include polyester resins other than (P) having a Mn of 1,000 to 1,000,000, styrene resins, resins having a structure in which a vinyl resin is grafted on a polyolefin resin, epoxy resins, and polyurethane resins. Among these, polyester resins other than (P) are preferable. Other resins may be blended with (P) or partially reacted. The content of other resins is preferably 60% or less, more preferably 50% or less.

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

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.
The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts, with respect to 100 parts of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. Above and below, parts mean parts by weight.

As the mold release agent, those having a flow softening point [Tm] of 50 to 170 ° C. are preferable, such as polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Is mentioned.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.

  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 the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine 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, and calcium carbonate powder.

  The composition ratio of the toner composition of the present invention is preferably 30 to 97%, more preferably 40 to 95%, and particularly preferably 45 to 92% of the toner binder of the present invention based on the toner weight; Preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; Of the additives, the release agent is preferably 0 to 30%, more preferably 0. 0.5 to 20%, particularly preferably 1 to 10%; charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%; fluidization The agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

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

  The toner composition of the present invention is 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.) as necessary. Used as a developer for a latent image. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a 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, a part shows a weight part.

<Production Example 1>
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of 4-α-cumylphenol and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Co., Ltd.) and stirred. Below, the inside of the system was replaced with nitrogen gas, and the temperature was raised to 150 ° C. At the same temperature, 181 parts of styrene was added dropwise over 3 hours, and further reacted at the same temperature for 5 hours. After cooling this to 30 ° C., the catalyst was filtered off to obtain 220 parts (Mn900) of 7 mol of styrene added to 1 mol of 4-α-cumylphenol. This was transferred to a pressure-resistant reaction vessel equipped with a stirrer, a nitrogen gas inlet tube and a thermometer, 0.2 parts of potassium hydroxide was added, and the mixture was heated to 120 ° C. 12 parts of PO was added thereto and reacted for 12 hours to obtain an alcohol component (B1-1) added with 2 mol of PO. It was Mn950.

<Production Example 2>
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of bisphenol A and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Industry Co., Ltd.). The gas was replaced with gas, and the temperature was raised to 150 ° C. At the same temperature, 168 parts of styrene was added dropwise over 3 hours, and further reacted at the same temperature for 5 hours. After cooling this to 30 ° C., the catalyst was filtered off to obtain 220 parts of 7 mol of styrene added to bisphenol A (Mn960). This was transferred to a pressure-resistant reaction vessel equipped with a stirrer, a nitrogen gas inlet tube and a thermometer, 0.2 parts of potassium hydroxide was added, and the mixture was heated to 120 ° C. 23 parts of PO was added thereto and reacted for 12 hours to obtain an alcohol component (B1-2) added with 2 mol of PO. Mn was 1060.

<Production Example 3>
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of phenol and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Industry Co., Ltd.), and the system was filled with nitrogen under stirring. The gas was replaced with gas, and the temperature was raised to 150 ° C. At the same temperature, 284 parts of styrene was added dropwise over 3 hours, and further reacted at the same temperature for 5 hours. After cooling this to 30 ° C., the catalyst was filtered off to obtain 330 parts (Mn620) having 5 moles of styrene added to phenol. This was transferred to a pressure-resistant reaction vessel equipped with a stirrer, a nitrogen gas inlet tube and a thermometer, 0.2 parts of potassium hydroxide was added, and the mixture was heated to 120 ° C. 27 parts of PO was added thereto and reacted for 12 hours to obtain an alcohol component (B1-3) added with 1 mol of PO. It was Mn670.

<Production Example 4>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 41 parts (0.13 mole) of bisphenol A / EO 2 mole adduct, 457 parts (1.14 mole) of bisphenol A / PO3 mole adduct, phenol 9 parts (0.01 mol) of PO6 mol adduct of novolak (average functional group number 5.6), 166 parts (1.0 mol) of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were added at 230 ° C. with nitrogen. The reaction was carried out for 5 hours while distilling off the water produced under an air stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (PR-1).
The acid value of the polyester resin (PR-1) was 1.8, the hydroxyl value was 46, Mp was 5,500, the softening point was 98 ° C, and the glass transition point was 60 ° C.

<Production Example 5>
622 parts of polyester resin (PR-1), 41 parts (0.21 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase in the system with nitrogen, the reaction was carried out at 180 ° C. for 2 hours under sealed at atmospheric pressure, then reacted at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point became 135 ° C., the belt cooler And was pulverized into particles. This is designated as polyester resin (PR-2).
The acid value of the polyester resin (PR-2) was 20, the hydroxyl value was 10, Mp was 11000, the softening point was 135 ° C., the glass transition point was 61 ° C., and the THF insoluble content was 6%.

<Production Example 6>
1960 parts (1.8 mol) of (B1-2), 166 parts (1.0 mol) of terephthalic acid, and tetrabutoxy titanate as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 3 parts were added and reacted at 230 ° C. for 5 hours while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (P-1).
The acid value of the polyester resin (P-1) was 1.8, the hydroxyl value was 45, Mp was 5600, the softening point was 97 ° C., the glass transition point was 60 ° C., and the styrenization rate was 63%.

<Production Example 7>
622 parts of polyester resin (P-1), 41 parts (0.21 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase in the system with nitrogen and reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, the reaction was carried out at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point reached 130 ° C. And was pulverized into particles. This is designated as polyester resin (P-2).
The polyester resin (P-2) had an acid value of 20, a hydroxyl value of 10, Mp of 10,000, a softening point of 130 ° C., a glass transition point of 60 ° C., a THF insoluble content of 6%, and a styrenation rate of 61%. .

<Production Example 8>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 435 parts (1.25 mol) of bisphenol A · PO2 mol adduct, 128 parts (0.18 mol) of (B1-3), terephthalic acid 166 parts (1.0 mol) and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 230 ° C. for 5 hours while distilling off the water generated under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (P-3).
The acid value of the polyester resin (P-3) was 1.5, the hydroxyl value was 31, Mp was 5700, the softening point was 100 ° C., the glass transition point was 62 ° C., and the styrenization rate was 14%.

<Production Example 9>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 290 parts (0.31 mol) of (B1-1), 2100 parts (1.99 mol) of A1-2, 166 parts of terephthalic acid ( 1.0 mol), and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 230 ° C. for 5 hours while distilling off the water generated in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (P-4).
The acid value of the polyester resin (P-4) was 1.7, the hydroxyl value was 30, Mp was 5800, the softening point was 102 ° C., the glass transition point was 63 ° C., and the styrenization rate was 65%.

<Production Example 10>
622 parts of polyester resin (P-4), 41 parts (0.21 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase in the system with nitrogen and reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, the reaction was carried out at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point reached 140 ° C. And was pulverized into particles. This is designated as polyester resin (P-5).
Polyester resin (P-5) had an acid value of 21, a hydroxyl value of 1, Mp of 11000, a softening point of 140 ° C., a glass transition point of 65 ° C., a THF insoluble content of 8%, and a styrenization rate of 65%. .

<Examples 1 to 5>, <Comparative Examples 1 and 2>
The polyester resin (PR-1), (PR-2) and (P-1) to (P-5) were used as toner binders according to the blending ratios in Table 1, and toners were formed by the following method. (Carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation], carnauba wax, charge control agent T-77 [Hodogaya Chemical Co., Ltd.])
First, premixing was performed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], and then kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) in a sample mill, and the toner compositions (T-1) to (T-5) of the present invention and comparison were made. Toner compositions (RT-1) and (RT-2) were obtained. No odor was generated in any case during the preparation of the toner composition.
Table 2 shows the evaluation results evaluated by the following evaluation methods and the value of the styrenization rate of the toner binder.

[Evaluation methods]
[1] Minimum fixing temperature (MFT)
An unfixed image developed using a commercial copying machine (AR5030; manufactured by Sharp) was evaluated using a fixing machine of a commercial copying machine (AR5030; manufactured by Sharp). The case where the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more was judged as good fixing.
A: Good fixing at a fixing roll temperature of 140 ° C.
○: Fixing is good at a fixing roll temperature of 150 ° C.
X: No fixing at a fixing roll temperature of 150 ° C.
[2] Rise of charging Under an environment of a temperature of 20 ° C. and a humidity of 50%, 100 parts of a ferrite carrier (F-150; manufactured by Powdertech) and 5 parts of a toner composition are charged into a stainless steel pot and placed on a ball mill stand. Rotational mixing was performed at 300 rpm. The developer was stopped after 15 seconds, 30 seconds and 60 seconds from the start of rotation, and the charge amount of the obtained developer was measured with a blow-off device.
A: Charge amount becomes maximum within 15 seconds.
○: The charge amount becomes maximum between 15 and 30 seconds.
X: Charge amount becomes maximum in 30 seconds or more. Alternatively, the charge amount continues to increase until 60 seconds.
[3] Charge retention In an environment of a temperature of 20 ° C. and a humidity of 50%, 100 parts of a ferrite carrier (F-150; manufactured by Powdertech Co., Ltd.) and 5 parts of a toner composition are charged into a stainless steel pot and placed on a ball mill stand. Rotational mixing was performed at 300 rpm. The developer was stopped after 60 seconds and 600 seconds from the start of rotation, and the charge amount of the obtained developer was measured with a blow-off device, and the rate of change was evaluated.
A: 20% or less.
○: 30% or less.
X: 30% or more.

  The toner binder and toner of the present invention are useful as an electrostatic charge image developing toner having excellent low-temperature fixability and chargeability.

Claims (6)

  A toner binder comprising a polyester resin (P) containing a styrenated aromatic ring formed by polycondensation of a carboxylic acid component (A) and an alcohol component (B). The toner binder according to claim 1, wherein the polyester resin (P) has a styrenated aromatic ring at least at a part of the molecular terminals.   The toner binder according to claim 1 or 2, wherein at least a part of the alcohol component (B) is a styrenated aromatic alcohol having no substituent at the meta position and / or para position of the aromatic ring.   The toner binder according to any one of claims 1 to 3, wherein the content of the structural unit of styrene in the polyester resin (P) is 1 to 65% by weight.   The polyester resin (P) is obtained by polycondensation of a carboxylic acid component (A) and an alcohol component (B) in the presence of a titanium-containing catalyst (t). Toner binder.   A toner comprising the toner binder according to claim 1, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.