JP2012032639A - Toner binder and toner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder having both excellent low-temperature fixability and hot-offset resistance (fixing temperature range), and excellent storage stability.SOLUTION: The toner binder contains: a polyester resin (A) which has a carboxylic acid component (x) and a polyol component (y) as a constitutional unit, in which (x) contains 80 mol% or more of two or more kinds of dicarboxylic acids (x1) selected from an aromatic dicarboxylic acid and an ester-forming derivative thereof in total and trivalent or higher polycarboxylic acid (x2), and (y) contains 80 mol% or more of aliphatic diol (y1) having a carbon number of 2-10, has a storage modulus [G'150] at 150°C of 20,000 dyn/cmor more, and has [G'150] and a storage modulus [G'180] at 180°C that satisfy a specific relationship; and a crystalline polyester resin (B) having a specific composition.

Description

  The present invention relates to a toner binder containing a polyester resin and a toner composition useful for dry toners used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. About.

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. Toners can be fixed even at low temperatures (low temperature fixability) and storage stability is required.
Toner compositions containing a polyester-based toner binder that are excellent in both low-temperature fixability and hot offset resistance are known (see Patent Documents 1 and 2). However, in recent years, there has been an increasing demand for storage stability and compatibility between low temperature fixability and hot offset resistance (fixing temperature range), which is still insufficient.

JP-A-12-75549 JP 2005-77930 A

  An object of the present invention is to provide a toner binder that is excellent in both low-temperature fixability and hot offset resistance (fixing temperature range) and excellent in storage stability.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention has at least a carboxylic acid component (x) and a polyol component (y) as structural units, and the carboxylic acid component (x) is at least two selected from aromatic dicarboxylic acids and ester-forming derivatives thereof. A dicarboxylic acid (x1) is contained in a total of 80 mol% or more, and further contains at least a trivalent or higher polycarboxylic acid (x2), and the polyol component (y) has 2 to 10 carbon atoms. The storage elastic modulus [G′150] at 150 ° C. containing at least 80 mol% of the group diol (y1) is 20000 dyn / cm ² or more, and the storage elasticity at [G′150] (dyn / cm ² ) and 180 ° C. rate [G'180] (dyn / cm ²⁾ is a polyester resin (a) which satisfies the following equation (1), aliphatic 9-30 carbon atoms polycarboxylic acids and their ester form A polycondensation polyester resin of a carboxylic acid component (x) and a polyol component (y) containing at least 60 mol% of at least one selected from a functional derivative, having an SP value of 9.0 to 10.5 (cal / cm ^{3) 1/2} a is a crystalline polyester resin (B) toner containing a binder; and the toner binder and a colorant, and, if necessary, a release agent, a charge control agent, and selected from fluidizing agents A toner composition containing one or more additives.
[G′150] / [G′180] ≦ 15 Formula (1)

  According to the present invention, it is possible to provide a toner binder and a toner that are excellent in both low temperature fixability and hot offset resistance (fixing temperature range) and excellent in storage stability.

The present invention is described in detail below.
The toner binder of the present invention contains a polyester resin (A) and a crystalline polyester resin (B).
The polyester resin (A) is a polyester resin having at least a carboxylic acid component (x) and a polyol component (y) as constituent units, and from the viewpoint of achieving both low temperature fixability and hot offset resistance (fixing temperature range), Contains at least 80 mol% of two or more dicarboxylic acids (x1) selected from aromatic dicarboxylic acids and ester-forming derivatives thereof, and also contains at least trivalent or higher polycarboxylic acids (x2) And a polyol component (y) containing 80 mol% or more of an aliphatic diol (y1) having 2 to 10 carbon atoms.

As two or more kinds of dicarboxylic acids (x1) selected from aromatic dicarboxylic acids and ester-forming derivatives thereof, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc. And two or more selected from these ester-forming derivatives; and the like.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc., preferably C1-C4) esters, and partial alkyl (same as above) esters. Can be mentioned. The same applies to the following ester-forming derivatives.
In the present invention, in two or more kinds of dicarboxylic acids (x1) selected from aromatic dicarboxylic acids and ester-forming derivatives thereof, aromatic dicarboxylic acids and ester-forming derivatives of the same dicarboxylic acids are one kind. Count as.
Among these (x1), from the viewpoint of achieving both low-temperature fixability and hot offset resistance, two or more selected from (1) to (3) listed below are preferable.
(1) Terephthalic acid and / or ester-forming derivatives thereof (2) Isophthalic acid and / or ester-forming derivatives thereof (3) Phthalic acid and / or ester-forming derivatives thereof Preferred combinations are (1) and (2) , And (1) and (3), and more preferably, the weight ratio of (1) and (2) is (1) / (2) = 3/7 to 7/3, The weight ratio of 3) is (1) / (3) = 3/7 to 7/3.

Examples of the carboxylic acid component (x) other than the dicarboxylic acid (x1) include dicarboxylic acids other than (x1), trivalent or higher polycarboxylic acids (x2), and monocarboxylic acids (x3).
Among the carboxylic acid components (x), dicarboxylic acids other than (x1) 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. [E.g., dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acids having 4 to 36 carbon atoms (e.g., alkenyl succinic acid such as dodecenyl succinic acid, malee, fumar, citraconic, and mesaconic acid) and ester-forming derivatives thereof; Etc.
Of these, preferred are alkenedicarboxylic acids having 4 to 20 carbon atoms; alkenedicarboxylic acids having 4 to 36 carbon atoms and ester-forming derivatives thereof, and more preferred are succinic acid, adipic acid, maleic acid, Fumaric acid and / or ester-forming derivatives thereof.

Examples of the tricarboxylic or higher (preferably 3 to 6) polycarboxylic acid (x2) include aromatic carboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and fatty acids having 6 to 36 carbon atoms. Group (including alicyclic) carboxylic acids (hexanetricarboxylic acid, decanetricarboxylic acid and the like), and ester-forming derivatives thereof.
Of these, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.

Examples of the monocarboxylic acid (x3) include aliphatic (including alicyclic) monocarboxylic acid (x31) and aromatic monocarboxylic acid (x32).
As aliphatic (including alicyclic) monocarboxylic acid (x31), C1-C30 (preferably 1-24) alkane monocarboxylic acid (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, capryl) Acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, monitoring acid, melicic acid, etc.), alkene monocarboxylic acid having 3 to 30 (preferably 3 to 24) carbon atoms ( Acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.).

  As aromatic monocarboxylic acid (x32), benzoic acid having 7 to 14 carbon atoms and derivatives thereof (derivative means that one or more hydrogens in the aromatic ring of benzoic acid are substituted with organic groups having 1 to 7 carbon atoms. For example, benzoic acid, 4-phenylbenzoic acid, para-tert-butylbenzoic acid, toluic acid, ortho-benzoylbenzoic acid, and naphthoic acid.), And C8-14 A derivative of acetic acid having an aromatic substituent of (the derivative has a structure in which one or more hydrogen other than hydrogen contained in the carboxyl group of acetic acid is substituted with an aromatic group having 6 to 12 carbon atoms. For example, diphenylacetic acid, phenoxyacetic acid, and α-phenoxypropionic acid.) And the like may be used in combination. Of these, benzoic acid having 7 to 14 carbon atoms and derivatives thereof are preferable, and benzoic acid is more preferable. When (x32) is used, the blocking resistance when used for toner becomes better.

The amount of the dicarboxylic acid (x1) in the carboxylic acid component (x) is 80 mol% or more, preferably 83 to 98 mol%, more preferably 85 to 95 mol%.
Further, the amount of the polycarboxylic acid (x2) in (x) is preferably 20 mol% or less, more preferably 1 to 15 mol%, and particularly preferably 2 to 12 mol%.
The amount of the aromatic monocarboxylic acid (x32) in (x) is preferably 10 mol% or less, more preferably 0.1 to 9.5 mol%, particularly preferably 0.5 to 9 mol%. is there.

Examples of the aliphatic diol (y1) having 2 to 10 carbon atoms used for the polyol component (y) include alkylene glycols having 2 to 10 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol); alkylene ether glycols having 4 to 10 carbon atoms (diethylene glycol, triethylene glycol, Dipropylene glycol, etc.);
Among these (y1), from the viewpoint of achieving both low-temperature fixability and hot offset resistance, an unbranched aliphatic diol (ethylene glycol, 1,3-propylene glycol, 1,4) having a primary hydroxyl group at the molecular end. -Butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol).
From the viewpoint of storage stability, ethylene glycol, 1,3-propylene glycol, and 1,4-butanediol are more preferable, and ethylene glycol is particularly preferable.

Examples of the polyol component (y) other than the aliphatic diol (y1) include diols other than (y1) and trivalent or higher polyols.
Among the polyol component (y), diols other than (y1) include alkylene glycols having 11 to 36 carbon atoms (1,12-dodecanediol, etc.); alkylene ether glycols having 11 to 36 carbon atoms (polyethylene glycol, polypropylene glycol) And polytetramethylene ether glycol, etc.); C6-C36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); (poly) oxyalkylenes (alkylenes) of the above alicyclic diols Group having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) and the following polyoxyalkylene groups) ether [number 1 to 30 oxyalkylene units (hereinafter abbreviated as AO units)]; Cyclic dihydric phenols (eg hydroquinone), Fine bisphenols (number of AO units 2-30) polyoxyalkylene ether (bisphenol A, bisphenol F and bisphenol S, etc.)]; and the like.
Of these, preferred are polyoxyalkylene ethers of bisphenols (number of AO units: 2 to 30).

Trivalent or higher (preferably 3 to 8) polyols include 3 to 8 or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin). , Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols (Number of AO units 1 to 30); polyoxyalkylene ether of trisphenols (trisphenol PA and the like) (number of AO units 2 to 30); novolak resin (phenol novolak and cresol novolak and the like, average polymerization degree 3 to 60 ) Poly Carboxymethyl and the like (the number 2 to 30 of AO units) alkylene ether.
Of these, preferred are aliphatic polyhydric alcohols having 3 to 8 valences or higher, and polyoxyalkylene ethers of novolac resins (number of AO units: 2 to 30), and particularly preferred are polyoxyalkylenes of novolac resins. An alkylene ether (number of AO units 2 to 30).

  The amount of the aliphatic diol (y1) having 2 to 10 carbon atoms in the polyol component (y) [excluding those distilled out of the system during the polycondensation reaction, and so on. ] Is 80 mol% or more, preferably 83 mol% or more, more preferably 85 mol% or more.

The 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 carboxylic acid component (x) and the polyol component (y) is preferably 150 to 280 ° C., more preferably 170 to 260 ° C., particularly preferably in an inert gas (nitrogen gas or the like) atmosphere. It can carry out by making it react at 190-240 degreeC. 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 polyol component (y) and the polycarboxylic acid component (x) is preferably 2/1 to 1/2, more preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 5/1 to 1 / 1.3, particularly preferably 1.3 / 1 to 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 2006-243715 A [Titanium dihydroxybis (triethanolaminate), 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 catalysts (for example, zirconyl acetate), zinc acetate, and the like. Among these, a titanium-containing catalyst is preferable.

The polyester resin (A) used in the present invention has, in addition to the carboxylic acid component (x) and the polyol component (y), a polyisocyanate (i) and a polyamine (j) and / or water as a structural unit. Further, it may be a modified polyester resin (A1) containing a urethane group and a urea group.
The modified polyester resin (A1) is preferable from the viewpoint of securing the fixing temperature range of the toner.

  As said polyisocyanate (i), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 fat (except the carbon in a NCO group). Cyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups) And oxazolidone group-containing modified products) and mixtures of two or more thereof.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcapro. And bis (2-isocyanatoethyl) fumarate.

  Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

As an example of polyamine (j), as aliphatic diamines (C2 to C18),
[1] Aliphatic diamine {C2-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine [diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]};
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substitutes [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5-hexamethylenediamine, methyliminobispropylamine, etc.];
[3] Alicyclic or heterocyclic-containing aliphatic diamine {alicyclic diamine (C4 to C15) [1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene Dianiline), etc.], heterocyclic diamines (C4-C15) [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane etc.];
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.);

As aromatic diamines (C6-C20),
[1] Unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine) , Diaminodiphenylsulfone, benzidine, thiodianiline, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine and the like;
[2] Aromatic diamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], such as 2,4- and 2,6-tolylenediamine, crude tri Rangeamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2, 4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 4,4′-diamino-3,3′-dimethyldiphenylmethane, etc.), and mixtures of these isomers in various proportions;
[3] Aromatic diamine [methylene bis-o-chloroaniline, 4-chloro-o] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) -Phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5- Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline, etc.];
[4] Aromatic diamine having a secondary amino group [partial or partial -NH ₂ of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl Etc.] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].

  As polyamine (j), in addition to these, by polycondensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (alkylenediamine, polyalkylenepolyamine etc.) Low molecular weight polyamide polyamine obtained, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol etc.), etc.] and the like.

  As the concentration of the urethane group / urea group contained in the modified polyester resin (A1), (A1) with respect to the total weight of (A1), from the viewpoint that both G′180 and Eta [Tg + 40] described later are within a preferable range. The total amount of water that reacts with polyisocyanate (i), polyamine (j), and (i) used as a raw material of [i.e., (i), (j), and ( The total content of water reacting with i): calculated value] is preferably 55% by weight or less, more preferably 0.1 to 50% by weight, and particularly preferably 0.3 to 35% by weight.

From the viewpoint of G′180, the molar ratio of the urethane group / urea group to be introduced is preferably urethane group / urea group = 50/50 to 95/5, and more preferably 55/45 to 90/10.
The said molar ratio is contained in (A1) from the weight of the water which reacts with polyisocyanate (i) used when manufacturing modified polyester resin (A1), and polyamine (j) and (i). The ratio between the number of moles of urethane groups (—NHCOO—) and the number of moles of urea groups (—NHCONH—) is obtained by calculation.

Although it does not specifically limit as a method to manufacture a modified polyester resin (A1), The method containing either of the following three types of manufacturing methods is preferable.
Production method [1]: An organic solvent (S) solution of a polyester resin (a) having a hydroxyl group, obtained by polycondensation of a carboxylic acid component (x) and a polyol component (y), is added to a polyisocyanate (i). And then reacting the reaction product having unreacted isocyanate groups with polyamine (j) to produce a modified polyester resin (A1).
Production method [2]: Polyester resin (a) having a hydroxyl group obtained by polycondensation of carboxylic acid component (x) and polyol component (y) is reacted with polyisocyanate (i) in a liquid state, Next, a method for producing a modified polyester resin (A1) by reacting a reaction product having an unreacted isocyanate group with a polyamine (j).
Production method [3]: Polyisocyanate (i) and polyamine (j) are converted into an equivalent ratio of [isocyanate group in (i)] / [amino group in (j)] = 1.5 / 1 to 3/1. And then reacting the reaction product having an unreacted isocyanate group with the polyol component (y), the polyol component (y) containing the modified polyol (y1), and the carboxylic acid component (x). A method of producing a modified polyester resin (A1) by polycondensation.

The acid value of the polyester resin (A) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter). When the acid value is 100 or less, the charging characteristics at the time of toner formation do not deteriorate.
In the case of the modified polyester resin (A1), the acid value is more preferably 0 to 80, and particularly preferably 0 to 60. In the case of the polyester resin (A) other than (A1), from the viewpoint of charge amount, it is more preferably 4 to 80, particularly preferably 10 to 60.
The hydroxyl value of (A) 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 version).
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 (A) soluble in tetrahydrofuran (THF) (hereinafter referred to as Mp) is preferably 2000 to 20000, more preferably 3000 from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner. -10500, particularly preferably 4000-9000.

In the present invention, the molecular weight [Mp and number average molecular weight (hereinafter referred to as Mn)] of the polyester resin is measured using gel permeation chromatography (GPC) under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 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 molecular weight is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The glass transition temperature (Tg) of the polyester resin (A) used in the present invention is preferably from 30 to 75 ° C., more preferably from 40 to 72 ° 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 softening point [Tm] measured by the flow tester (A) when (A) is other than the modified polyester resin (A1) is preferably 120 to 170 ° C, more preferably 125 to 160 ° C, and particularly preferably 130. ~ 150 ° C. Moreover, Tm of (A1) becomes like this. Preferably it is 120-230 degreeC, More preferably, it is 123-225 degreeC, Most preferably, it is 125-220 degreeC.
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.
<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 plunger descent amount This value (temperature when half of the measurement sample flows out) is taken as the softening point [Tm].

The polyester resin (A) used in the present invention has a storage elastic modulus at 150 ° C. [also referred to as G′150 in the present specification] from the viewpoint of resistance to hot offset during toner formation. ] (Dyn / cm ²⁾ is at 20000dyn / cm ² or more, and G'150, and in storage modulus at 180 ° C. [herein, referred to G'180 both. (Dyn / cm ² ) needs to satisfy the following formula (1), preferably satisfies the formula (1 ′), and more preferably satisfies the formula (1 ″).
[G′150] / [G′180] ≦ 15 Formula (1)
[G′150] / [G′180] ≦ 14 Formula (1 ′)
[G′150] / [G′180] ≦ 13 (1)

When G′150 and G′180 satisfy the formula (1), it is considered that the viscosity is not too low in a practical range even in a high temperature range, and the hot offset resistance when used as a toner becomes good.
In order to adjust the storage elastic modulus (G ′) of the polyester resin (A), for example, when G′150 / G′180 is decreased, the Tm of the polyester resin (A) is increased. This can be achieved by increasing the ratio, increasing the number of crosslinking points, increasing the molecular weight, or increasing the Tg.

In the present invention, the storage elastic modulus (G ′) of the polyester resin is measured using the following viscoelasticity measuring device.
Apparatus: ARES-24A (Rheometric)
Jig: 25 mm parallel plate Frequency: 1 Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

The polyester resin (A) has a viscosity at Tg + 40 ° C. (also expressed as Eta [Tg + 40] in the present specification) (Pa · s) (Pa · s) in the following formula (2) from the viewpoint of low-temperature fixability at the time of toner formation. It is preferable to satisfy the formula, more preferably to satisfy the formula (2 ′), and most preferably to satisfy the formula (2 ″).
Eta [Tg + 40] ≦ 7 × 10 ⁵ Formula (2)
Eta [Tg + 40] ≦ 6 × 10 ⁵ Formula (2 ′)
Eta [Tg + 40] ≦ 5 × 10 ⁵ Formula (2 ″)

When Eta [Tg + 40] satisfies the formula (2), 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 the polyester resin (A), for example, when Eta [Tg + 40] is decreased, the Tm of the polyester resin (A) is decreased or Mp is 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 contains a crystalline polyester resin (B) together with the polyester resin (A).
The crystalline polyester resin (B) is a polycondensation polyester resin of the carboxylic acid component (x) and the polyol component (y), and an aliphatic polycarboxylic acid having 9 to 30 carbon atoms (preferably 9 to 22 carbon atoms). One or more kinds (x *) selected from acids and ester-forming derivatives thereof are contained in the carboxylic acid component in an amount of 60 mol% or more, and the SP value is 9.0 to 10.5 [(cal / cm ³ ) ^{1 / 2} , the same shall apply hereinafter).
In the present invention, the “crystalline polyester resin” refers to a polyester having a melting point [Tmp] of 25 ° C. or higher. Tmp is measured by the method described later.
Specific examples of the diol in the polyol component (y) constituting the crystalline polyester resin (B) are the same as the aliphatic diols having 2 to 10 carbon atoms (y1) and diols other than (y1). Is mentioned. The diol is preferably ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, And 1,12-dodecanediol, more preferably ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.
Specific examples of the trivalent or higher polyol in (y) include those described above. Of these, glycerin and trimethylolpropane are preferred.

  The content (mol%) of the diol in the polyol component (y) constituting (B) is preferably 60 to 100, more preferably 80 to 100, particularly preferably 90 to 100, and most preferably 100. . The diol is preferably one kind of diol.

Specific examples of the carboxylic acid component (x) constituting the crystalline polyester resin (B) include the dicarboxylic acid (x1), a dicarboxylic acid other than (x1), the trivalent or higher polycarboxylic acid (x2), And the monocarboxylic acid (x3).
One or more (x *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof, which are essential constituents in (x), are dicarboxylic acids other than the above (x1). Among alkane dicarboxylic acids having 4 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 40 carbon atoms, those having 9 to 30 carbon atoms and their ester-forming derivatives, carbon number in the above (x2) Among the 6-36 aliphatic (including alicyclic) polycarboxylic acids, those having 9-30 carbon atoms and ester-forming derivatives thereof can be mentioned.
Of these, preferably an alkanedicarboxylic acid having 9 to 22 carbon atoms and an ester-forming derivative thereof, more preferably azelaic acid, zebacic acid, 1,10-decanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, And their ester-forming derivatives, particularly preferably 1,10-decanedicarboxylic acid.

  As (x) that constitutes (B), in addition to (x *), preferred are trimellitic acid, pyromellitic acid, and their anhydrides in (x2), and the number of carbons in (x3) 1-30 (especially 1-24) alkane monocarboxylic acid is mentioned.

The crystalline polyester resin (B) contains 60 mol% or more of one or more (x *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof in the carboxylic acid component (x). contains. Preferably it is 70 mol% or more, More preferably, it is 90 mol% or more. When the aliphatic polycarboxylic acid having 9 to 30 carbon atoms is less than 60 mol%, the rate and rate of crystallization are low, and the blocking resistance becomes insufficient.
Moreover, 60-100 are preferable, as for content (mol%) of dicarboxylic acid in the carboxylic acid component (x) which comprises (B), More preferably, it is 80-100, Especially preferably, it is 90-100. Further, the dicarboxylic acid is preferably one kind of dicarboxylic acid.

  The equivalent ratio (OH group / COOH group) of the carboxylic acid component (x) and the polyol component (y) constituting the crystalline polyester resin (B) is preferably 0.95 to 1.18 from the viewpoint of storage stability. More preferably, it is 1.0 to 1.16, and particularly preferably 1.01 to 1.14.

The acid value of (B) is preferably 0 to 100, more preferably 0 to 80, 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.
Further, the hydroxyl value of (B) is preferably 0 to 50, more preferably 0 to 40. When the hydroxyl value is 50 or less, the hot offset resistance at the time of toner formation becomes better.

The SP value (solubility parameter) of the crystalline polyester resin (B) is usually 9.0 to 10.5, preferably 9.1 to 10.2, more preferably 9.2 to 10.1, particularly preferably. 9.3 to 10.0.
When the SP value is less than 9.0, the compatibility with the polyester resin (A) is insufficient and the durability is insufficient, and when it exceeds 10.5, the Tg is lowered and the blocking resistance is deteriorated.
The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"

  The Mp of the tetrahydrofuran (THF) soluble part of the crystalline polyester resin (B) is preferably 5000 to 150,000, more preferably 8000 to 100,000, particularly preferably 10,000 to 90,000 from the viewpoints of storage stability and low-temperature fixability. is there.

The melting point [Tmp] of the crystalline polyester resin (B) is preferably from 50 to 120 ° C., more preferably from 55 to 110 ° C., particularly preferably from 60 to 90 ° C. from the viewpoints of fixability, storage stability and durability. is there. In the present invention, Tmp is measured by the following method.
<Melting point [Tmp]>
Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated to 10 ° C. The temperature is increased at a time per minute and the change in endothermic heat is measured. A graph of “endothermic heat generation” and “temperature” is drawn.

  The softening point [Tm] by the flow tester (B) is preferably 50 to 150 ° C, more preferably 60 to 130 ° C, and particularly preferably 65 to 110 ° C. Within this range, the low-temperature fixability and blocking resistance are further improved.

  (B) is preferably a ratio {[Tm] / [Tmp]} of “softening point [Tm]” and “melting point [Tmp]” from the viewpoint of crystallization speed and blocking resistance at the time of toner formation. It is 0.0-1.8, More preferably, it is 1.0-1.4.

The number average molecular weight (Mn), peak top molecular weight (Mp), melting point [Tmp], softening point [Tm], and ratio {[Tm] / [Tmp]} of the crystalline polyester resin (B) are within the above ranges. Includes one or more selected from the equivalent ratio (OH group / COOH group) of the polyol component (y) and the carboxylic acid component (x), a polycarboxylic acid having 9 to 30 carbon atoms, and an ester-forming derivative thereof (x *) Can be easily performed by adjusting the content, type, etc. or selecting reaction conditions.
That is, when the equivalent ratio (OH group / COOH group) approaches 1, Mn and Mp increase, and both Tm and Tmp increase, and when away from 1, Mn and Mp decrease and both Tm and Tmp increase. Lower. Further, when the number of carbon atoms in (x *) increases, both Tm and Tmp decrease, but Tmp decreases more greatly. Therefore, {[Tm] / [Tmp]} can be controlled by adjusting the carbon number of the carboxylic acid (x *) and the equivalent ratio (OH group / COOH group).

  The weight ratio (A / B) of the polyester resin (A) and the crystalline polyester resin (B) in the toner binder of the present invention is preferably from 5/95 to the viewpoint of both low-temperature fixability and hot offset resistance. 80/20, more preferably 10/90 to 70/30, particularly preferably 20/80 to 50/50.

In the present invention, the mixing method of the polyester resin (A) and the crystalline polyester resin (B) is not particularly limited, and may be a known method that is usually performed, and may be either powder mixing or melt mixing. Further, it may be mixed at the time of toner formation.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll.
Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferable.

  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 softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and these A mixture etc. are 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 (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 based on the toner weight (% in this item is% by weight), and the toner binder of the present invention is preferably 30 to 97%, more preferably 40 to 95%, Particularly preferably 45 to 92%; Colorant, preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; , Preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; the 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%, and 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, “%” represents “% by weight”.

Production Example 1
[Synthesis of Polyester Resin (A-1)]
In the reaction vessel, 440 parts (2.7 moles) of terephthalic acid, 235 parts (1.4 moles) of isophthalic acid, 7 parts (0.05 moles) of adipic acid, 554 parts (8.9 moles) of ethylene glycol, polymerization After adding 0.5 parts of tetrabutoxytitanate as a catalyst and reacting at 210 ° C. for 5 hours while distilling off water and ethylene glycol generated under a nitrogen stream, the reaction was carried out for 1 hour under reduced pressure of 5 to 20 mmHg. Subsequently, 103 parts (0.54 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then reacted under reduced pressure of 20 to 40 mmHg and taken out at a predetermined softening point. The recovered ethylene glycol was 219 parts (3.5 mol). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-1).
Polyester resin (A-1) had a Tg of 56 ° C., a Tm of 135 ° C., an Mp of 4800, an acid value of 37, a hydroxyl value of 50, and a THF insoluble content of 5%.

Production Example 2
[Synthesis of polyester resin (A-2)]
In a reaction vessel, 310 parts (1.9 moles) of terephthalic acid, 465 parts (2.8 moles) of isophthalic acid, 36 parts (0.25 moles) of adipic acid, 610 parts (9.8 moles) of ethylene glycol, polymerization After adding 0.5 parts of tetrabutoxytitanate as a catalyst and reacting at 210 ° C. for 5 hours while distilling off water and ethylene glycol generated under a nitrogen stream, the reaction was carried out for 1 hour under reduced pressure of 5 to 20 mmHg. Subsequently, 52 parts (0.27 mol) of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure, and then reacted under reduced pressure of 20 to 40 mmHg, and taken out at a predetermined softening point. The recovered ethylene glycol was 262 parts (4.2 mol). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-2).
Polyester resin (A-2) had a Tg of 60 ° C., a Tm of 150 ° C., an Mp of 10,500, an acid value of 10, a hydroxyl value of 0, and a THF insoluble content of 1%.

Production Example 3
[Synthesis of polyester resin (A-3)]
In a reaction vessel, 460 parts (2.8 moles) of terephthalic acid, 307 parts (1.8 moles) of isophthalic acid, 573 parts (9.2 moles) of ethylene glycol, and 3 parts of tetrabutoxy titanate as a polymerization catalyst were added. The reaction was carried out for 5 hours while distilling off the water and ethylene glycol produced at 210 ° C. under a nitrogen stream, and then for 1 hour under reduced pressure of 5 to 20 mmHg. Next, 52 parts (0.27 mol) of trimellitic anhydride was added, and the mixture was kept at 180 ° C. for 1 hour and then taken out. The recovered ethylene glycol was 200 parts (3.2 mol). The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-3-1). Tg of (A-3-1) was 59 ° C., Tm was 97 ° C., Mp was 7000, acid value was 49, hydroxyl value was 77, and THF-insoluble matter was 0%.
Next, 200 parts (0.07 mol) of (A-3-1) and 800 parts of tetrahydrofuran were placed in a reaction vessel and heated to 80 ° C. to dissolve. Under a nitrogen stream, 60 parts (0.27 mol) of isophorone diisocyanate (IPDI) was added and reacted for 24 hours. Further, 23 parts (0.13 mol) of isophoronediamine (IPDA) was added and stirred for 3 hours. Then, while heating to 200 ° C., tetrahydrofuran was distilled off under reduced pressure of 5 to 20 mmHg over 10 hours and taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-3).
Polyester resin (A-3) had a Tg of 59 ° C., a Tm of 140 ° C., an Mp of 7,300, an acid value of 45, a hydroxyl value of 1, and a THF insoluble content of 4%. The equivalent ratio [OH] / [NCO] between the hydroxyl group of (A-3-1) and the isocyanate group of IPDI is 1 / 1.89, and the unreacted isocyanate group and IPDA of the reaction product of (A-3-1) and IPDI. The equivalent ratio of amino groups of [NCO] / [NH ₂ ] is 0.95 / 1, the total content of structural units of polyisocyanate and polyamine in the polyester resin (A-3) is 29.3%, urethane group The molar ratio of / urea group was 1/1.

Production Example 4
[Synthesis of Crystalline Polyester Resin (B-1)]
In a reaction vessel, 132 parts (1.12 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and 3 parts of tetrabutoxy titanate as a polymerization catalyst were placed at 210 ° C. For 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the product was taken out when the acid value became 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as crystalline polyester resin (B-1).
Crystalline polyester resin (B-1) had Tmp of 66 ° C., Tm of 73 ° C. (Tm / Tmp = 1.1), Mp of 13500, acid value of 1, and SP value of 9.6.

Production Example 5
[Synthesis of Crystalline Polyester Resin (B-2)]
In a reaction vessel, 121 parts (1.03 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and 3 parts of tetrabutoxy titanate as a polymerization catalyst were put at 210 ° C. For 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the product was taken out when the acid value became 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as crystalline polyester resin (B-2).
Crystalline polyester resin (B-2) had Tmp of 73 ° C., Tm of 93 ° C. (Tm / Tmp = 1.3), Mp of 90000, acid value of 1, and SP value of 9.6.

Production Example 6
[Synthesis of Crystalline Polyester Resin (B-3)]
In a reaction tank, 132 parts (1.12 mol) of 1,6-hexanediol, 343 parts (1.0 mol) of 1,18-octadecanedicarboxylic acid, and 3 parts of tetrabutoxy titanate as a polymerization catalyst were added at 210 ° C. For 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the product was taken out when the acid value became 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as crystalline polyester resin (B-3).
Crystalline polyester resin (B-3) had Tmp of 68 ° C., Tm of 95 ° C. (Tm / Tmp = 1.4), Mp of 20000, acid value of 1, and SP value of 9.3.

Production Example 7
[Synthesis of Crystalline Polyester Resin (B-4)]
In a reaction vessel, 69 parts (1.12 mol) of ethylene glycol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid and 3 parts of tetrabutoxy titanate as a polymerization catalyst were placed at 200 ° C. under normal pressure. The reaction is carried out for 5 hours while distilling off the water produced. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the product was taken out when the acid value became 2 or less. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as crystalline polyester resin (B-4).
The crystalline polyester resin (B-4) had a Tmp of 108 ° C., a Tm of 110 ° C. (Tm / Tmp = 1.0), an Mp of 10,500, an acid value of 2, and an SP value of 10.0.

Comparative production example 1
[Synthesis of polyester resin (RA-1)]
In the reaction vessel, 41 parts (0.13 mol) of bisphenol A · ethylene oxide 2 mol adduct, 457 parts (1.14 mol) of bisphenol A · propylene oxide 3 mol adduct, phenol novolac (average number of functional groups: 5. 6) 9 parts (0.01 mol) of propylene oxide 6 mol adduct, 166 parts (1.0 mol) of terephthalic acid, 93 parts (0.8 mol) of fumaric acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst. The mixture was allowed to react for 5 hours while distilling off the water produced under a nitrogen stream at 230 ° C. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., and 41 parts (0.21 mol) of trimellitic anhydride was added. The reaction was further carried out at 230 ° C. under a reduced pressure of 5 to 20 mmHg, and the product was taken out when Tm reached 132 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-1).
Polyester resin (RA-1) had a Tg of 58 ° C., a Tm of 135 ° C., an Mp of 11,300, an acid value of 20, a hydroxyl value of 5, and a THF insoluble content of 6%.

Comparative production example 2
[Synthesis of polyester resin (RA-2)]
In the reaction vessel, 486 parts (1.21 mol) of bisphenol A / propylene oxide 3 mol adduct, 23 parts (0.29 mol) of propylene oxide 6 mol adduct of phenol 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 and reacted for 5 hours while distilling off generated water under a nitrogen stream at 230 ° C. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., added with 40 parts (0.21 mol) of trimellitic anhydride, and reacted for 2 hours under sealed at atmospheric pressure. The reaction was further carried out at 230 ° C. under a reduced pressure of 5 to 20 mmHg, and it was taken out when Tm reached 140 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-2).
Polyester resin (RA-2) had a Tg of 57 ° C., a Tm of 145 ° C., an Mp of 8,300, an acid value of 20, a hydroxyl value of 18, and a THF insoluble content of 28%.

Comparative production example 3
[Synthesis of polyester resin (RA-3)]
In a reaction vessel, 470 parts (2.8 moles) of terephthalic acid, 311 parts (2.1 moles) of phthalic acid, 599 parts (9.66 moles) of ethylene glycol and 0.5 part of tetrabutoxy titanate as a condensation catalyst are placed. The reaction was carried out for 5 hours while distilling off the generated water under a nitrogen stream at 210 ° C., and then for 1 hour under reduced pressure of 5 to 20 mmHg. Next, when the acid value became 2 or less, it was cooled to 180 ° C., 83 parts (0.43 mol) of trimellitic anhydride was added, and after reaction for 1 hour under atmospheric pressure sealing, further 230 ° C., 5-20 mmHg. The reaction was carried out under reduced pressure, and the product was taken out when a predetermined softening point was reached. The recovered ethylene glycol was 235 parts. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-3).
Polyester resin (RA-3) had a Tg of 59 ° C., a Tm of 142 ° C., an Mp of 8400, an acid value of 1, a hydroxyl value of 19, and a THF insoluble content of 2%.

<Examples 1-6>, <Comparative Examples 1-4>
Polyester resins (A-1) to (A-3) obtained in the above production examples, crystalline polyester resins (B-1) to (B-4), and polyester resins (RA-) obtained in comparative production examples. 1) to (RA-3) were blended according to the blending ratio (parts) shown in Table 1 to obtain the toner binder of the present invention and the comparative toner binder, which were converted into toners by the following method.
First, 8 parts of carbon black MA-100 [Mitsubishi Chemical Co., Ltd.], 5 parts of carnauba wax, 1 part of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] are added, and a Henschel mixer [Mitsui Miike Chemical Industries ( FM10B] was premixed and then kneaded with a twin-screw kneader [Ikegai PCM-30]. 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.) using a sample mill, and the toner compositions (T-1) to (T-6) of the present invention and a comparison were made. Toner compositions (RT-1) to (RT-4) were obtained.
Table 2 shows the evaluation results evaluated by the following evaluation methods.

[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 lower limit temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was defined 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 upper limit temperature at which hot offset does not occur after passing through the fixing roll was defined as hot offset generation temperature.
[3] Toner blocking resistance test The toner composition was tested at 50 ° C. and 85% R.V. H. Was conditioned for 48 hours in a high temperature and high humidity environment. Under the same environment, the blocking state of the developer was visually determined, and the image quality when copying with a commercially available copying machine (AR5030: manufactured by Sharp) was observed.
Criteria A: There is no toner blocking, and the image quality after copying 3000 sheets is good.
○: There is no toner blocking, but a slight disturbance is observed in the image quality after copying 3000 sheets.
X: Toner blocking is visible, and no image is produced by 3000 sheets.

  The toner composition and toner binder of the present invention are excellent in low-temperature fixability, hot offset resistance, and blocking resistance, and useful as an electrostatic image developing toner and toner binder for use in electrophotography, electrostatic recording, electrostatic printing, etc. It is.

Claims (8)

Two or more dicarboxylic acids (x1) having at least a carboxylic acid component (x) and a polyol component (y) as structural units, wherein the carboxylic acid component (x) is selected from aromatic dicarboxylic acids and ester-forming derivatives thereof. In total, and also contains at least a trivalent or higher polycarboxylic acid (x2), and the polyol component (y) is an aliphatic diol (y1) having 2 to 10 carbon atoms. The storage elastic modulus [G′150] at 150 ° C. is 20,000 dyn / cm ² or more, and the storage elastic modulus [G′180] at 180 ° C. and [G′150] (dyn / cm ² ). ] (dyn / cm ²⁾ is a polyester resin (a) which satisfies the following equation (1), selected from aliphatic polycarboxylic acids and their ester-forming derivatives of 9 to 30 carbon atoms That one or more of a polycondensation polyester resin of the carboxylic acid component (x) and the polyol component (y) containing more than 60 mol%, SP value of 9.0~10.5 (cal / cm ^{3) 1} A toner binder containing a crystalline polyester resin (B) which is / ² .
[G′150] / [G′180] ≦ 15 Formula (1) The toner binder according to claim 1, wherein the polyester resin (A) has a glass transition point (Tg) of 30 to 70 ° C., and a viscosity Eta [Tg + 40] (Pa · s) at Tg + 40 ° C. satisfies the following formula (2): .
Eta [Tg + 40] ≦ 7 × 10 ⁵ Formula (2) The toner binder according to claim 1 or 2, wherein the dicarboxylic acid (x1) constituting the polyester resin (A) is at least two selected from the following (1) to (3).
(1) Terephthalic acid and / or its ester-forming derivative (2) Isophthalic acid and / or its ester-forming derivative (3) Phthalic acid and / or its ester-forming derivative   The polyester resin (A) is a modified polyester resin (A1) containing a urethane group and a urea group, further having polyisocyanate (i) and polyamine (j) and / or water as constituent units. The toner binder according to any one of the above.   The polyester resin (A) has a molecular weight of 2000 to 20000 as a peak top in gel permeation chromatography of a tetrahydrofuran-soluble component, and a softening point [Tm] by a flow tester of 120 to 170 ° C. A toner binder according to any one of the above.   The crystalline polyester resin (B) has a peak-top molecular weight of 5,000 to 150,000 in gel permeation chromatography of tetrahydrofuran-soluble content, a melting point [Tmp] of 50 to 120 ° C., and a softening point [Tm] of 50 to 150 by a flow tester. The toner binder according to claim 1, wherein the toner binder has a temperature of [Tm] / [Tmp] of 1.0 to 1.8.   The toner binder according to claim 1, wherein the weight ratio (A / B) of the polyester resin (A) and the crystalline polyester resin (B) is 5/95 to 80/20. A toner composition 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.