JP5524719B2 - Toner binder and toner composition - Google Patents

Description

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

The toner binder for electrophotography, which is commonly used as an image fixing method in copying machines, printers, etc., does not fuse the toner to the heat roll even at a high fixing temperature (hot offset resistance), fixing. Toner can be fixed even at low temperatures (low temperature fixability), hard to absorb moisture under severe conditions of high temperature and high humidity, excellent charging stability, storage stability as fine particles (blocking resistance), etc. Is required.
In recent years, there is an increasing demand for color, high speed, high reliability, compactness, low cost, and energy savings in copiers and printers. In particular, in order to reduce the environmental load (energy saving), it is urgently necessary to cope with both low-temperature fixing property and blocking resistance of the toner.
It is conventionally known to use a polyester resin as a binder for the purpose of improving the low-temperature fixing performance of the toner. For the purpose of improving fixability, a method of incorporating a high acid value polyester resin has been proposed (Patent Documents 1, 2 and the like).

JP 2004-294735 A JP 2008-122931 A

However, high acid value and high hydroxyl value are expected to adversely affect the charging stability. In order to improve the low-temperature fixability, it is known that the toner binder has a low molecular weight. However, if the molecular weight is simply reduced, the glass transition point is lowered accordingly, the storage stability is deteriorated, and the There is also a problem that the hot offset property is lowered, and none satisfying the above characteristics has been obtained.
An object of the present invention is to provide a toner composition excellent in an increase in fixing temperature range accompanying an improvement in low-temperature fixability, blocking resistance, and charging stability.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, according to the present invention, in the toner binder composed of the linear polyester resin (A) and the nonlinear polyester resin (B), the peak top molecular weight of (A) is 2500 or less, the glass transition temperature [Tg] is 50 to 80 ° C., [ relationship Tg] and flow softening point [Tm] is Tm-Tg ≦ 35 (℃) , and Ri acid value of 0 to 20 (mg KOH / g) der, (a) an aromatic monocarboxylic acid ( A polyester resin obtained by polycondensation of a carboxylic acid component (x) composed of x1) and / or a polycarboxylic acid (x2) and a polyol component (y), wherein bisphenol A is contained in the polyol component (y). Bisphenol A acetylated product, bisphenol S, bisphenol S acetylated product, bisphenol S polyoxyalkylene ether (oxyal) Number 2-4) Len units, and characterized that you containing one or more (y1) of 30 mol% or more selected from the group consisting of hydrogenated bisphenol A Tonaba Lee Nda; and the toner binder, coloring And, if necessary, a toner composition containing one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.

  By using the toner binder and the toner composition of the present invention, it becomes possible to obtain a toner excellent in low-temperature fixability, and to provide a toner binder excellent in both blocking resistance and charge stability of the toner. It has become possible.

The present invention is described in detail below.
In the linear polyester resin (A) in the present invention, a carboxylic acid component (x) composed of an aromatic monocarboxylic acid (x1) and / or a polycarboxylic acid (x2) and a polyol component (y) are polycondensed. It is preferable that it is a polyester resin obtained.
Examples of the polyol component (y) include bisphenol A, acetylated product of bisphenol A, bisphenol S, acetylated product of bisphenol S, polyoxyalkylene ether of bisphenol S (2 to 4 oxyalkylene units), and hydrogenated bisphenol A. One or more types selected from the group consisting of (y1), diols other than (y1) (y2), and trivalent to octavalent or higher polyols (y3).

  Examples of the diol (y2) other than (y1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6- Hexanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol or the like); (poly) oxyalkylene of the above alicyclic diol (alkylene group having 2 to 4 carbon atoms, the same applies to the following polyoxyalkylene groups) ether [oxyalkylene unit (hereinafter AO unit) Abbreviated) Number 1-30]; and polyoxyalkylene ethers (number 2-30 of AO units) of dihydric phenol [monocyclic dihydric phenol (for example, hydroquinone) and bisphenol (bisphenol A, bisphenol F, etc.)], and the like. Two or more kinds may be used in combination.

  Of these, preferred are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 30 AO units), and combinations thereof. More preferred are polyoxyalkylene ethers of bisphenols (particularly bisphenol A) (2 and / or 3 carbon atoms of the alkylene group, 2 to 8 AO units), alkylene glycols of 2 to 12 carbon atoms (particularly ethylene glycol). , 1,2-propylene glycol), and combinations thereof (weight ratio 100: 0 to 20:80).

  Examples of the trivalent to octavalent or higher polyol (y3) include trihydric to octavalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylenes of the above aliphatic polyhydric alcohols Ether (number of AO units 1-30); polyoxyalkylene ether of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); novolak resin (phenol novolak, cresol novolac, etc.) average degree of polymerization 3 60) Etc. (the number 2 to 30 of AO units) oxyalkylene ether and the like, may be used in combination of two or more thereof.

  Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and polyoxyalkylene ethers of novolac resins (number of AO units 2 to 30), and more preferred are polyoxyalkylenes of novolac resins. Ether (number of AO units 2 to 30).

  Bisphenol A in the polyol component (y), acetylated product of bisphenol A, bisphenol S, acetylated product of bisphenol S, polyoxyalkylene ether of bisphenol S (number of oxyalkylene units 2 to 4), and hydrogenated bisphenol A The content of one or more diols (y1) selected from the group is preferably at least 30 mol%, more preferably at least 45 mol%, particularly preferably at least 55 mol%, from the viewpoint of storage stability.

  Among the carboxylic acid component (x) that is a constituent unit of the linear polyester resin (A), as the aromatic monocarboxylic acid (x1), benzoic acid having 7 to 14 carbon atoms and derivatives thereof (derivatives are those of benzoic acid. Meaning one having one or more hydrogens in the aromatic ring substituted with a hydrocarbon group or acyl group having 1 to 7 carbon atoms, for example, benzoic acid, 4-phenylbenzoic acid, para-tert-butyl Benzoic acid, toluic acid, ortho-benzoylbenzoic acid, and naphthoic acid.), And derivatives of acetic acid having an aromatic substituent having 8 to 14 carbon atoms (the derivative is one other than those contained in the carboxyl group of acetic acid) This means that the above hydrogen has a structure substituted with an aromatic group having 6 to 12 carbon atoms, such as diphenylacetic acid, phenoxyacetic acid, and α-phenoxypropio. Acid.), And the like, may be used in combination of two or more thereof. Of these, benzoic acid having 7 to 14 carbon atoms and derivatives thereof are preferable, and benzoic acid is more preferable.

Examples of the polycarboxylic acid (x2) include dicarboxylic acid (x21) and tri- or hexavalent or higher polycarboxylic acid (x22).
Examples of the dicarboxylic acid (x21) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic, adipine, and sebacic acid) and alkenyl succinic acids (for example, dodecenyl succinic acid); alicyclic dicarboxylic acids having 6 to 40 carbon atoms [for example, Dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acids having 4 to 36 carbon atoms (eg malee, fumarate, citracone, and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthal, isophthal, terephthal, and Naphthalenedicarboxylic acid, etc.); and ester-forming derivatives thereof [for example, anhydrides, lower alkyl (C1-4) esters (methyl esters, ethyl esters, isopropyl esters, etc.), etc.]; You may use the above together. Of these, preferred are alkane dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof.

Examples of the tricarboxylic acid having a valence of 3 to 6 or more (x22) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic polycarboxylic acids having 6 to 36 carbon atoms. (Hexane tricarboxylic acid, etc.) and ester-forming derivatives thereof may be mentioned, and two or more of them may be used in combination.
Among these, trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof are preferable.

  The carboxylic acid component (x) of the linear polyester resin (A) preferably contains an aromatic monocarboxylic acid (x1) from the viewpoint of storage stability. The content of (x1) in (x) is preferably 60 mol% or less, more preferably 1 to 55 mol%, and particularly preferably 20 to 50 mol%.

The linear polyester resin (A) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction temperature of the polyol component (y) and the carboxylic acid component (x) is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably in an inert gas (nitrogen gas or the like) atmosphere. It can carry out by making it react at 170-235 degreeC. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.
The reaction ratio between the polyol component (y) and the carboxylic acid component (x) 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. As an example of the esterification catalyst, it is preferable to use an esterification catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel, and aluminum from the viewpoint of reactivity and environmental protection. More preferably, it is used.
Examples of the titanium-containing catalyst include titanium alkoxide, potassium oxalate titanate, titanium terephthalate, and catalysts described in JP-A-2006-243715 [titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolaminate). And their intramolecular polycondensates], and catalysts described in JP-A 2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) and the like. .
Antimony trioxide etc. are mentioned as an antimony containing catalyst.
Zirconyl acetate etc. are mentioned as a zirconium containing catalyst.
Nickel acetylacetonate etc. are mentioned as a nickel containing catalyst.
Examples of the aluminum-containing catalyst include aluminum hydroxide and aluminum triisopropoxide.

The amount of the catalyst added is desirably determined as appropriate so as to maximize the reaction rate. The addition amount is preferably 10 ppm to 1.9%, more preferably 100 ppm to 1.7%, based on the total raw materials. The amount added is preferably 10 ppm or more, so that the reaction rate is increased.
In the above and the following, “%” means “% by weight” unless otherwise specified.

  The acid value (mgKOH / g, the same applies hereinafter) of the linear polyester resin (A) used in the present invention is 0 to 20, preferably 0 to 18, and more preferably 0 to 15. If the acid value exceeds 20, the charging characteristics deteriorate.

The hydroxyl value of (A) (mgKOH / g, hereinafter the same) is preferably 0 to 50, more preferably 0 to 40, and particularly preferably 0 to 30. When the hydroxyl value is 50 or less, the hot offset resistance becomes better.
The acid value and hydroxyl value in the present invention are measured by the method defined in JIS K0070.

The glass transition temperature [Tg] of the linear polyester resin (A) is 45 ° C to 80 ° C, preferably 50 ° C to 70 ° C. When Tg exceeds 80 ° C., the low-temperature fixability deteriorates. Moreover, blocking resistance will worsen that Tg is less than 45 degreeC.
In the above and the following, the glass transition temperature [Tg] is measured by a method (DSC method) defined in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.

  The flow softening point [Tm] of (A) is not particularly limited, but is preferably 60 ° C to 110 ° C, and more preferably 70 ° C to 100 ° C. When Tm is 60 ° C. or higher, the hot offset resistance is good, and when Tm is 110 ° C. or lower, the fixability is good.

In the above and the following, the flow softening point [Tm] is a temperature at which the flow rate is raised at a constant speed under the following conditions using a flow tester, and the outflow amount becomes 1/2.
Apparatus: Flow tester CFT-500D manufactured by Shimadzu Corporation
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

In (A), the difference (Tm−Tg) between the flow softening point [Tm] (° C.) and the glass transition temperature [Tg] (° C.) is 35 ° C. or less. (Tm−Tg) is preferably 34 ° C. or lower, more preferably 33 ° C. or lower. When (Tm−Tg) exceeds 35 ° C., the low-temperature fixability deteriorates.
(Tm-Tg) can be reduced to 35 ° C. or lower by reducing the molecular weight to lower [Tm] and increasing the acid value, etc., by bonds other than covalent bonds (hydrogen bonds, intermolecular forces, etc.) [ Examples thereof include a method of increasing [Tg] without increasing [Tm] and a method of decreasing [Tm] without decreasing [Tg] by adding a crystalline plasticizer (stearic acid, magnesium stearate, etc.).

  The peak top molecular weight (hereinafter referred to as Mp) of the linear polyester resin (A) soluble in tetrahydrofuran (THF) is 2500 or less, preferably 1000 to 2400. When Mp exceeds 2500, the low-temperature fixability deteriorates.

In the above and below, the number-average molecular weight (hereinafter referred to as Mn) and Mp of the THF-soluble matter of the polyester resin and Mp are 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 solution Injection volume: 100 μl
Detection apparatus: 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 toner binder used in the present invention contains the non-linear polyester resin (B) together with the linear polyester resin (A) from the viewpoint of achieving both low-temperature fixability and offset resistance.

In the nonlinear polyester resin (B) used in the present invention, a carboxylic acid component (x) composed of an aromatic monocarboxylic acid (x1) and / or a polycarboxylic acid (x2) and a polyol component (y) are polycondensed. To be obtained.
(B) is usually the above-mentioned aromatic monocarboxylic acid (x1) and / or dicarboxylic acid (x21) and the diol (y2) together with the above-mentioned tri- or hexavalent polycarboxylic acid (x22). ) And / or trivalent to octavalent or higher polyol (y3).

Polyol component (y) [In this section, it means a polyol component which is a constituent unit of the non-linear polyester resin (B) excluding those removed outside the system during the polycondensation reaction. The proportion of the alkylene glycol having 2 to 12 carbon atoms is preferably 85 to 100 mol%, more preferably 90 to 100 mol%, from the viewpoint of mechanical strength.
In particular, the content of ethylene glycol in (y) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol% from the viewpoint of mechanical strength.

  The aromatic monocarboxylic acid (x1) is preferably 30 mol% or less, more preferably 1 to 25 mol%, particularly preferably 2 with respect to the total carboxylic acid component (x) from the viewpoint of storage stability. ~ 20 mol%.

  Moreover, the sum total of 3-8 valence or more polyol (y3) and 3-6 valence or more polycarboxylic acid (x22) in the sum total of a carboxylic acid component (x) and a polyol component (y). Is preferably 0.1 to 15 mol%, more preferably 0.2 to 12 mol%. When the amount is 0.1 mol% or more, the storage stability of the toner is good, and when the amount is 15 mol% or less, the charging characteristics of the toner are good.

  Method for producing a nonlinear polyester resin (B) by polycondensation of a carboxylic acid component (x) composed of an aromatic monocarboxylic acid (x1) and a polycarboxylic acid (x2) and a polyol component (y) Is not particularly limited, and the mixture of (x1) and (x2) and (y) can be polycondensed together, but at least a part of (x2) and (y) After polycondensation at an equivalent ratio such that the hydroxyl group of (y) becomes excessive, it is preferable to react the hydroxyl group of the obtained polycondensate (B0) with the carboxyl group of (x1) to further polycondense. . If necessary, after the polycondensation of (B0) and (x1), a polycarboxylic acid having 3 to 6 or more valences (x22) may be added and further polycondensed.

The polycondensation of the carboxylic acid component (x) and the polyol component (y) when producing the nonlinear polyester resin (B) can be performed using a known esterification reaction. As a general method, for example, in the presence of a polymerization catalyst in an inert gas (nitrogen gas or the like) atmosphere, the reaction temperature is preferably 150 to 280 ° C, more preferably 180 to 270 ° C, and particularly preferably 200 to 260. It can carry out by making it react at ° 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 in the reaction of the polyol component (y) and at least a part of the polycarboxylic acid (x2) in the first stage is preferably 2 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. The ratio is 1-1 / 1, more preferably 1.5 / 1 to 1.01 / 1, and particularly preferably 1.3 / 1 to 1.02 / 1.
The ratio of all polyol components (y) and all carboxylic acid components (x) used in the production of (B) is preferably 2/1 as an equivalent ratio [OH] / [COOH] of hydroxyl groups to carboxyl groups. ½, more preferably 1.5 / 1 to 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

  The glass transition temperature [Tg] of the non-linear polyester resin (B) is preferably 45 ° C to 80 ° C, and more preferably 50 ° C to 70 ° C. When Tg is 80 ° C. or lower, the low-temperature fixability is improved. Moreover, blocking resistance is favorable in Tg being 45 degreeC or more.

  The flow softening point [Tm] of (B) is not particularly limited, but is preferably 90 ° C to 170 ° C, and more preferably 120 ° C to 160 ° C. When Tm is 90 ° C. or higher, the hot offset resistance is good, and when Tm is 170 ° C. or lower, the fixability is good.

  The Mp of the tetrahydrofuran (THF) soluble part of the nonlinear polyester resin (B) is preferably 2000 to 12000, and more preferably 3000 to 10,000.

The THF insoluble content in the nonlinear polyester resin (B) is preferably 3 to 50% from the viewpoint of low temperature fixability. More preferably, it is 5 to 40%, and particularly preferably 10 to 35%. When the THF-insoluble content is 50% or less, the glossiness (gloss) of the image is good.
The THF-insoluble matter in the present invention is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling, the insoluble content is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample. In addition, this filtrate is used for GPC measurement as a THF soluble part.

The sum of the acid value and the hydroxyl value of the nonlinear polyester resin (B) is preferably 3 to 40, more preferably 10 to 40, and particularly preferably 18 to 39. When the sum of the acid value and the hydroxyl value is 3 or more, the storage stability is good, and when it is 40 or less, the charging stability is improved.
The acid value of the non-linear polyester resin (B) is preferably 3 to 40, more preferably 10 to 38, and the hydroxyl value is preferably 0 to 30, more preferably 0 to 10.

  The weight ratio [(A) / (B)] of the linear polyester resin (A) and the non-linear polyester resin (B) is preferably 90/10 in terms of both low-temperature fixability, hot offset resistance and grindability. -20/80, more preferably 80 / 20-30 / 70.

  The toner binder of the present invention may contain other resins usually used as a toner binder as long as the properties are not impaired. Examples of other resins include polyester resins other than (A) and (B) with 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 urethane resins. Can be mentioned. Other resins may be blended with (A) and (B) or may be partially reacted. The content of other resins is preferably 10% or less, more preferably 5% 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 for toner 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 release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof.
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 (C1-C1 of alkyl 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%; among toner additives, a release agent is preferably 0 to 30%, and more preferably 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%; The fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of the toner 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 electrically mixed with carrier particles such as ferrite coated on the surface with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as necessary. Used as a latent image developer. The weight ratio of toner to carrier particles is preferably 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner 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 the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

Production Example 1 [Synthesis of Linear Polyester Resin (A1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 110 parts (51.7 mol%) of phthalic anhydride, 400 parts (100.0 mol%) of bisphenol S / ethylene oxide 2 mol adduct, benzoic acid 85 parts (48.3 mol%) of acid and 2.5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst were added and reacted at 210 ° C. for 3 hours while distilling off the water produced in a nitrogen stream. The reaction was carried out under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1).
Tg of (A1) was 58 ° C., Tm was 91 ° C. (Tm-Tg: 33 ° C.), Mp was 2,400, acid value was 1, and hydroxyl value was 30.
In addition, mol% in () means mol% in the carboxylic acid component or polyol component (the same applies hereinafter).

Production Example 2 [Synthesis of Linear Polyester Resin (A2)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 110 parts (56.1 mol%) of succinic acid, 430 parts (100.0 mol%) of hydrogenated bisphenol A, 100 parts of benzoic acid (39.3 mol). Mol%) 2.5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added and reacted at 210 ° C. for 3 hours while distilling off the water generated under a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg. The reaction was continued until the acid value was 2 or less. Furthermore, 15 parts (4.6 mol%) of trimellitic anhydride was added and reacted under normal pressure for 1 hour. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A2).
Tg of (A2) was 58 ° C, Tm was 90 ° C (Tm-Tg: 32 ° C), Mp was 1,800, acid value was 14, and hydroxyl value was 18.

Production Example 3 [Synthesis of Linear Polyester Resin (A3)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 110 parts (52.4 mol%) of succinic acid, bisphenol A / acetylated compound (bisphenol A and acetic anhydride at a molar ratio of 1: 3 at 80 ° C., 430 parts (100.0 mol%) was added and reacted at 140 ° C. for 2 hours. Next, 180 parts (47.6 mol%) of tert-butylbenzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A3).
Tg of (A3) was 45 ° C., Tm was 78 ° C. (Tm−Tg: 33 ° C.), Mp was 1900, acid value was 1, and hydroxyl value was 0.

Production Example 4 [Synthesis of Linear Polyester Resin (A4)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 110 parts (52.2 mol%) of succinic acid, bisphenol S / acetylated product (bisphenol S and acetic anhydride at a molar ratio of 1: 3 at 80 ° C., 430 parts (100.0 mol%) was added and reacted at 140 ° C. for 2 hours. Next, 180 parts (47.8 mol%) of tert-butylbenzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A4).
Tg of (A4) was 50 ° C., Tm was 84 ° C. (Tm-Tg: 34 ° C.), Mp was 2000, acid value was 0, and hydroxyl value was 0.

Production Example 5 [Synthesis of linear polyester resin (A5)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 110 parts (58.0 mol%) of phthalic anhydride, 415 parts (100.0 mol%) of bisphenol S / ethylene oxide 2 mol adduct, tert -81 parts (35.7 mol%) of butylbenzoic acid and 2.5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst were reacted for 3 hours while distilling off the water produced at 210 ° C under a nitrogen stream. Then, the reaction was carried out under a reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Furthermore, 15 parts (6.3 mol%) of trimellitic anhydride was added and reacted under normal pressure for 1 hour. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A5).
Tg of (A5) was 62 ° C., Tm was 96 ° C. (Tm-Tg: 34 ° C.), Mp was 2400, acid value was 15, and hydroxyl value was 40.

Production Example 6 [Synthesis of Linear Polyester Resin (A6)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 120 parts (66.3 mol%) of succinic acid, 420 parts (100.0 mol%) of hydrogenated bisphenol A, 89 parts of tert-butylbenzoic acid ( 27.2 mol%), 2.5 parts of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added and reacted at 210 ° C. for 3 hours while distilling off the water generated under a nitrogen stream, and then 5 to 20 mmHg. The reaction was continued until the acid value was 2 or less. Further, 23 parts (6.4 mol%) of trimellitic anhydride was added and reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A6).
Tg of (A6) was 58 ° C., Tm was 89 ° C. (Tm-Tg: 31 ° C.), Mp was 1900, acid value was 17, and hydroxyl value was 37.

Production Example 7 [Synthesis of Linear Polyester Resin (A7)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 82 parts (68.1 mol%) of succinic acid, bisphenol A / acetylated compound (bisphenol A and acetic anhydride at a molar ratio of 1: 3 at 80 ° C., 385 parts (100.0 mol%) were added and reacted at 140 ° C. for 2 hours. Next, 60 parts (28.2 mol%) of tert-butylbenzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Furthermore, 9 parts (3.7 mol%) of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A7).
Tg of (A7) was 50 ° C., Tm was 84 ° C. (Tm−Tg: 34 ° C.), Mp was 2100, the acid value was 8, and the hydroxyl value was 45.

Production Example 8 [Synthesis of linear polyester resin (A8)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 78 parts (68.0 mol%) of succinic acid, bisphenol S / acetylated compound (bisphenol S and acetic anhydride at a molar ratio of 1: 3 at 80 ° C., 390 parts (100.0 mol%) was added and reacted at 140 ° C. for 2 hours. Next, 57 parts (28.1 mol%) of tert-butylbenzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Furthermore, 9 parts (3.9 mol%) of trimellitic anhydride was added and reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A8).
Tg of (A8) was 55 ° C., Tm was 89 ° C. (Tm-Tg: 34 ° C.), Mp was 2200, the acid value was 6, and the hydroxyl value was 40.

Production Example 9 [Synthesis of Linear Polyester Resin (A9)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 140 parts (67.1 mol%) of maleic anhydride and 470 parts (100.0 mol%) of bisphenol A were allowed to react at 140 ° C. for 2 hours. It was. Next, 72 parts (27.3 mol%) of benzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Furthermore, 23 parts (5.5 mol%) of trimellitic anhydride was added and reacted under normal pressure for 1 hour. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A9).
Tg of (A9) was 58 ° C., Tm was 93 ° C. (Tm-Tg: 35 ° C.), Mp was 2,300, acid value was 18, and hydroxyl value was 40.

Production Example 10 [Synthesis of Linear Polyester Resin (A10)]
115 parts (66.7 mol%) of maleic anhydride and 435 parts (100.0 mol%) of bisphenol S were placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, and reacted at 140 ° C for 2 hours. It was. Next, 62.0 parts (28.5 mol%) of benzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Further, 16 parts (4.8 mol%) of trimellitic anhydride was added and reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A10).
Tg of (A10) was 57 ° C., Tm was 91 ° C. (Tm-Tg: 34 ° C.), Mp was 2,400, acid value was 14, and hydroxyl value was 45.

Production Example 11 [Synthesis of Linear Polyester Resin (A11)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 220 parts (64.4 mol%) of phthalic anhydride, 180 parts (55.0 mol%) of hydrogenated bisphenol A, and propylene oxide adduct of bisphenol A : New Pole BP-2P (manufactured by Sanyo Chemical Industries: 2 mol adduct of propylene oxide) was added and reacted at 140 ° C. for 2 hours. Next, 68 parts (28.0 mol%) of benzoic acid was added and reacted at 140 ° C. for 2 hours, followed by reaction under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. Further, 20 parts of trimellitic anhydride (7.6 mol%) was added and reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A11).
Tg of (A11) was 56 ° C., Tm was 91 ° C. (Tm-Tg: 35 ° C.), Mp was 2,400, the acid value was 18, and the hydroxyl value was 38.

Production Example 12 [Synthesis of Nonlinear Polyester Resin (B1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 388 parts (44.5 mol%) terephthalic acid, 388 parts (44.5 mol%) isophthalic acid, 21 parts adipic acid (2.8 mol) %), Ethylene glycol 600 parts (100.0 mol%), titanium diisopropoxy bistriethanolamate 0.5 part as a polymerization catalyst, and distilled for 5 hours at 210 ° C. while distilling off the water generated in a nitrogen stream After making it react, it was made to react under reduced pressure of 5-20 mmHg for 1 hour. Subsequently, 17 parts (2.6 mol%) of benzoic acid was added and reacted under normal pressure for 3 hours. Furthermore, 57 parts (5.7 mol%) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 20 to 40 mmHg and taken out at a predetermined softening point. The recovered ethylene glycol was 280 parts. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B1).
Mp of (B1) was 8000, Tg was 60 ° C., Tm was 145 ° C., the acid value was 26, and the hydroxyl value was 1.

Production Example 13
[Synthesis of Nonlinear Polyester Resin (B2)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 298.9 parts (58.5 mol%) terephthalic acid, 128 parts (25.1 mol%) isophthalic acid, 4 parts adipic acid (0. 8 mol%), 320 parts of ethylene glycol (100.0 mol%), 0.5 part of titanium diisopropoxybistriethanolamate as a polymerization catalyst, and while distilling off the water produced at 210 ° C. under a nitrogen stream After reacting for 5 hours, it was reacted for 1 hour under a reduced pressure of 5 to 20 mmHg. Subsequently, 31 parts (8.3 mol%) of benzoic acid was added, and the mixture was reacted for 3 hours under normal pressure. Furthermore, 43 parts (7.3 mol%) of trimellitic anhydride was added and reacted at normal pressure for 1 hour, and then reacted at a reduced pressure of 20 to 40 mmHg and taken out at a predetermined softening point. The recovered ethylene glycol was 225 parts. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B2).
Mp of (B2) was 5000, Tg was 65 ° C., Tm was 155 ° C., the acid value was 18, and the hydroxyl value was 1.

Comparative Production Example 1 [Synthesis of Comparative Linear Polyester Resin (RA1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 125 parts (100.0 mol%) of phthalic anhydride, 390 parts (100.0 mol%) of hydrogenated bisphenol A, titanium diisopropoxy as a polymerization catalyst Add 3.5 parts of bistriethanolaminate, react for 3 hours while distilling off the water generated at 210 ° C. under a nitrogen stream, and then react under reduced pressure of 5-20 mmHg, resulting in an acid value of 2 or less. Reacted until. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA1).
(RA1) had a Tg of 65 ° C., a Tm of 110 ° C. (Tm-Tg: 45 ° C.), an Mp of 2800, an acid value of 1, and a hydroxyl value of 110.

Comparative Production Example 2 [Synthesis of Comparative Linear Polyester Resin (RA2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 155 parts (88.4 mol%) of succinic acid, 600 parts (100.0 mol%) of hydrogenated bisphenol A, titanium diisopropoxybistris as a polymerization catalyst Put 3.5 parts of ethanolaminate, react for 3 hours while distilling off the water generated at 210 ° C under a nitrogen stream, and then react under reduced pressure of 5 to 20 mmHg until the acid value becomes 2 or less. Reacted. Furthermore, 40 parts (11.6 mol%) of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA2).
(RA2) had a Tg of 62 ° C., a Tm of 100 ° C. (Tm-Tg: 38 ° C.), an Mp of 2000, an acid value of 30, and a hydroxyl value of 90.

Comparative Production Example 3 [Synthesis of Comparative Linear Polyester Resin (RA3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 115 parts (100.0 mol%) of phthalic anhydride, 115 parts (30.9 mol%) of hydrogenated bisphenol A, and propylene oxide adduct of bisphenol A : New Paul BP-2P (manufactured by Sanyo Chemical Industries: Propylene oxide 2 mol adduct) 380 parts (69.1 mol%), Titanium diisopropoxybistriethanolaminate 3.0 parts as a polymerization catalyst, at 210 ° C. The reaction was carried out for 3 hours while distilling off the water produced under a nitrogen stream, and then the reaction was carried out under reduced pressure of 5 to 20 mmHg until the acid value was 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA3).
(RA3) had a Tg of 36 ° C., a Tm of 74 ° C. (Tm-Tg: 38 ° C.), an Mp of 1400, an acid value of 1, and a hydroxyl value of 150.

Obtained in Production Examples 12 and 13, linear polyester resins (A1) to (A11) and Comparative Linear Polyester Resins (RA1) to (RA3) obtained in Production Examples 1 to 11 and Comparative Production Examples 1 to 3. The non-linear polyester resins (B1) and (B2) thus obtained are put into a plastmill at the ratio shown in Table 1, and are stirred and melt-mixed at 140 ° C. for 5 minutes, and the toner binders (TB1) to (TB14) of the present invention are compared. Toner binders (RTB1) to (RTB3) were obtained. To 100 parts of each toner binder of these resins, 8 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 5 parts of carnauba wax were added to form a toner by the following method.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.] and then classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.] Toner particles having (D50) of 8 μm were obtained. Next, 100 parts of the toner particles are mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toner compositions (T1) to (T14) of the present invention and a comparative toner composition are mixed. (RT1) to (RT3) were obtained.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

[Evaluation method]
[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 fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was set as the minimum fixing temperature.
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
[3] Blocking resistance 10.0 g of the sample was put in a 200 ml polycup and allowed to stand in a circulating dryer at 40 ° C. After 5 days, the sample was taken out from the dryer, and the fluidity of the sample was confirmed.
(Judgment)
A: Flows when the cup is tilted.
○: It flows when the cup is tilted and patted with a spatula.
Δ: Flows when the cup is tilted and pucked strongly with a spatula.
X: The cup does not flow even when tilted and spatula strongly.
A judgment of ◯ or more is judged to have good blocking resistance.
[4] Charging stability 0.5 g of the toner composition and 20 g of ferrite carrier (Powder Tech Co., Ltd., F-150) were placed in a 50 ml glass bottle, which was placed at 23 ° C., 50% R.D. H. After adjusting the humidity for 8 hours or more, the mixture was frictionally stirred at 50 rpm × 10 for 60 minutes with a tumbler shaker mixer, and the charge amount was measured at each time. For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used. The charge amount was calculated by calculating the charge amount of 60 minutes of friction time / charge amount of 10 minutes of friction time.
Evaluation criteria for charging stability ◎: 0.8 or more ○: 0.7 or more, less than 0.8 △: 0.6 or more, less than 0.7 ×: less than 0.6

  As described above, the toner compositions of the present invention using the toner binder of the present invention (Examples 1 to 14) all showed significantly better results than the comparative toner compositions using the comparative toner binder. Obtained.

  The toner composition of the present invention is useful as a toner for developing an electrostatic image, particularly a color toner, which is excellent in low-temperature fixability, blocking resistance and charge stability.

Claims (6)

In a toner binder composed of a linear polyester resin (A) and a non-linear polyester resin (B), the peak top molecular weight of (A) is 2500 or less, the glass transition temperature [Tg] is 45 to 80 ° C., and the flow softening is [Tg]. a relationship Tm-Tg ≦ 35 between the point [Tm] (° C.), and an acid value 0 to 20 (mg KOH / g) der Ri, (a) an aromatic monocarboxylic acid (x1) and / or A polyester resin obtained by polycondensation of a carboxylic acid component (x) composed of a polycarboxylic acid (x2) and a polyol component (y), wherein bisphenol A and acetyl of bisphenol A are contained in the polyol component (y). , Bisphenol S, acetylated bisphenol S, polyoxyalkylene ether of bisphenol S (number 2 of oxyalkylene units) ), And Tonaba Lee Nda, wherein one or more that you containing more than 30 mol% of (y1) is selected from the group consisting of hydrogenated bisphenol A. The carboxylic acid component (x) contains an aromatic monocarboxylic acid (x1), and the aromatic monocarboxylic acid (x1) contains at least one of benzoic acid having 7 to 14 carbon atoms and derivatives thereof. The toner binder according to 1 . Polyester in which the non-linear polyester resin (B) is a polycondensation of a carboxylic acid component (x) composed of an aromatic monocarboxylic acid (x1) and / or a polycarboxylic acid (x2) and a polyol component (y). a resin, 85 to 100 mol% of the polyol component (y) is an alkylene glycol having 2 to 12 carbon atoms, Tonaba Lee Nda according to claim 1 or 2, wherein. Nonlinear Polyester flow softening point of the resin (B) [Tm] is 90 to 170 ° C., a peak top molecular weight is 2,000 to 12,000, Tonaba Lee Nda according to any one of claims 1-3. The weight ratio of the linear polyester resin (A) and non-linear polyester resin (B) [(A) / (B)] is 90 / 10-20 / 80, according to any one of claims 1-4 Tonaba Lee Nda . Toner binder according to any one of claims 1 to 5, a coloring agent, and a release agent if necessary, a charge control agent, and toner compositions containing one or more additives selected from the fluidizing agent.