JP5247173B2 - Resin for toner and toner composition - Google Patents

Description

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

In order to improve the low-temperature fixing performance of the toner, it has been proposed to use a crystalline polyester having specific heat melting characteristics (Patent Document 1, etc.).
JP 2005-77930 A

However, in the above method, it cannot be said that the blocking resistance is sufficient, and there is a demand for a resin having both a high blocking resistance and a low-temperature fixability.
An object of the present invention is to provide a toner composition excellent in low-temperature fixability and blocking resistance and a toner resin used therefor.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a toner resin containing a polyester resin (I) composed of a linear polyester (A) and a non-linear polyester (B), wherein (A) is an aliphatic polycarboxylic acid having 9 to 30 carbon atoms. A polycondensation polyester resin of a carboxylic acid component and an alcohol component containing at least 40 mol% of one or more selected from acids and ester-forming derivatives thereof, having an SP value of 9.0 to 10.5 (cal / cm ³ ) A crystalline polyester (A1) that is ^1/2 and an amorphous linear polyester (A2) other than (A1), and the content of (A1) in (A) is 5 to 95% by weight In the non-linear polyester (B), the THF-insoluble content is 1 to 36% by weight, and the peak-top molecular weight of gel permeation chromatography of the THF-soluble content is 5,000 to 20,000 A toner resin characterized by having a flow softening point of 120 to 180 ° C., an acid value of 15 to 80, and (B) satisfying the following formulas (1) and (2): And a toner composition containing a colorant and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.
Acid value / Hydroxyl value ≧ 1 Formula (1)
THF insoluble matter (% by weight) / flow softening point (° C.) ≦ 0.2 (2)

By using the toner resin of the present invention, a toner having excellent low-temperature fixability and blocking resistance can be obtained.
Further, when a crystalline polyester having a peak top molecular weight of 5,000 to 150,000 in gel permeation chromatography of THF-soluble matter is used, the low-temperature fixability and hot offset resistance when used as a toner are improved in a well-balanced manner. When a crystalline polyester having a molecular weight of less than 5000 is used, the low-temperature fixability of the toner is greatly improved.

The present invention is described in detail below.
The polyester resin (I) in the present invention is obtained, for example, by polycondensing one or more kinds of alcohol components (x) and one or more kinds of carboxylic acid components (y).
Examples of the alcohol component (x) include a diol (x1) and / or a polyol (x2) having 3 to 8 or more valences. Further, if necessary, monool (x3) of preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less may be used.
Examples of the carboxylic acid component (y) include a dicarboxylic acid (y1) and / or a polycarboxylic acid (y2) having 3 to 6 or more valences. If necessary, the monocarboxylic acid (y3) of preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less may be used.

Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. , 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol) And polytetramethylene ether glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); (poly) oxyalkylenes of the above alicyclic diols (Alkylene group having 2 to 4 carbon atoms, the same applies to the following polyoxyalkylene groups) Ether [oxyalkylene units (hereinafter abbreviated as AO units) 1 to 30]; and dihydric phenol [monocyclic dihydric phenol (for example, Hydroquinone), and polyoxyalkylene ethers of bisphenols (such as bisphenol A, bisphenol F and bisphenol S)] (number of AO units 2 to 30); and the like.
Among these (x1), 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.

Examples of the trivalent to octavalent or higher polyol (x2) include trihydric to octavalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyol 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) 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) polyoxyalkylene ether.
Among these (x2), preferred are 3 to 8 or higher aliphatic polyhydric alcohols and polyoxyalkylene ethers of novolac resins (2 to 30 AO units), and particularly preferred are novolak resins. Of polyoxyalkylene ether (number of AO units 2 to 30).

As monool (x3), C1-C30 (preferably 1-24) alkanol (methanol, ethanol, isopropanol, dodecyl alcohol, stearyl alcohol, etc.), C3-C30 (preferably 3-24) are used. Examples include alkenols (allyl alcohol, propenyl alcohol, oleyl alcohol, etc.), aromatic alcohols having 7 to 36 carbon atoms (benzyl alcohol, etc.) and the like.
Among these (x3), preferred are alkanols having 1 to 30 carbon atoms, and more preferred are dodecyl alcohol and stearyl alcohol.

Examples of the dicarboxylic acid (y1) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedioic acid, And 1,18-octadecane dicarboxylic acid); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid) Acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid); and ester-forming derivatives thereof And the like.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc.) esters, and partial alkyl (same as above) esters. The same applies to the following ester-forming derivatives.
Among these (y1), preferred are alkane dicarboxylic acids having 4 to 36 carbon atoms, alkene 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 (y2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatics having 6 to 36 carbon atoms (fatty oils). Examples thereof include polycarboxylic acids (including cyclic) (hexanetricarboxylic acid, decanetricarboxylic acid and the like), and ester-forming derivatives thereof.
Among these (y2), trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.

Among monocarboxylic acids (y3), aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids (formic acid, acetic acid, propionic acid, butane) having 1 to 30 (preferably 1 to 24) carbon atoms. Acid, isobutanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, monitoring acid, melicic acid, etc.), C3-30 (preferably 3-24) Alkene monocarboxylic acids (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.). Examples of the aromatic monocarboxylic acid in (y3) include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, phenylpropionic acid, naphthoic acid, and the like).
Among these (y3), preferred are alkane monocarboxylic acids having 1 to 30 carbon atoms, and more preferred are lauric acid, palmitic acid, stearic acid, and behenic acid.

The polyester resin (I) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be performed in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, and particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or 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.
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 (I) used for the toner resin of the present invention is composed of a linear polyester (A) and a non-linear polyester (B) from the viewpoint of achieving both low-temperature fixability and offset resistance.

Furthermore, the linear polyester (A) is a polycondensation polyester resin of a carboxylic acid component and an alcohol component from the viewpoint of achieving both blocking resistance and low-temperature fixability, and has 9 to 30 carbon atoms (preferably 9 to 22 carbon atoms). 1 or more (y *) selected from aliphatic polycarboxylic acids and ester-forming derivatives thereof in the carboxylic acid component and having an SP value of 9.0 to 10.5 [(cal / cm ³ ) ^1/2 , the same shall apply hereinafter) and 5% or more of the crystalline polyester (A1). The content of (A1) in (A) is preferably 10% or more, and more preferably 20 to 95%.
In the above and the following, “%” means “% by weight” unless otherwise specified.
In the present invention, “crystalline polyester” refers to a polyester having a melting point [Tmp] of 25 ° C. or higher. Tmp is measured by the method described later.

  Furthermore, when it is desired to improve the low-temperature fixability and hot offset resistance in a well-balanced manner, as (A1), a crystalline polyester having a peak top molecular weight of gel permeation chromatography (hereinafter referred to as Mp) of 5000 to 150,000 ( A11) is preferably used. On the other hand, when it is desired to greatly improve the low-temperature fixability, it is preferable to use a crystalline polyester (A12) having an Mp of 1000 or more and less than 5000 as (A1).

The crystalline polyester (A1) contains 40 mol% or more of the alcohol component (x), one or more selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof (y *). It can be obtained by polycondensation with the carboxylic acid component (y).
Specific examples of the diol (x1) in the alcohol component (x) constituting (A1) include those described above. (X1) is preferably ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane. Diol and 1,12-dodecanediol, more preferably 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol It is.
Specific examples of the trivalent to octavalent or higher polyol (x2) include those described above. Of these (x2), glycerin and trimethylolpropane are preferred.
Specific examples of the monool (x3) include those described above. Among (x3), C1-C30 (especially 1-24) alkanol is preferable, and dodecyl alcohol and stearyl alcohol are more preferable.

Specific examples of the carboxylic acid component (y) constituting (A1) include the dicarboxylic acid (y1), the trivalent to hexavalent or higher polycarboxylic acid (y2), and the monocarboxylic acid (y3). Can be mentioned.
One or more (y *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms (preferably 9 to 22 carbon atoms) and ester-forming derivatives thereof as essential constituents in (y) Among the alkanedicarboxylic acids having 4 to 36 carbon atoms and the alicyclic dicarboxylic acids having 6 to 40 carbon atoms and ester-forming derivatives thereof having the above-mentioned (y2), Among these aliphatic (including alicyclic) polycarboxylic acids having 6 to 36 carbon atoms, those having 9 to 30 carbon atoms and ester-forming derivatives thereof are exemplified.
Of these, preferred are alkane dicarboxylic acids having 9 to 22 carbon atoms and ester-forming derivatives thereof, and more preferred are azelaic acid, zebacic acid, 1,12-dodecanedioic acid, 1,18-octadecanedicarboxylic acid, And their ester-forming derivatives, particularly preferably zebacic acid and 1,12-dodecanedioic acid.

  As (y) that constitutes (A1), in addition to (y *), trimellitic acid, pyromellitic acid, and their anhydrides in (y2), and the number of carbons in (y3) 1-30 (especially 1-24) alkane monocarboxylic acid is mentioned.

  The crystalline polyester (A1) contains at least 40 mol% of one or more (y *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof in the carboxylic acid component (y). To do. Preferably it is 50 mol% or more, More preferably, it is 60 mol% or more. When (A1) is crystalline polyester (A11), it is particularly preferably at least 70 mol%, most preferably at least 80 mol%. When the aliphatic polycarboxylic acid having 9 to 30 carbon atoms (y *) is less than 40 mol%, the rate and rate of crystallization are low, and the blocking resistance becomes insufficient.

In the present invention, in addition to (y *), in addition to (y *), a monocarboxylic acid having 1 to 30 carbon atoms (y31) in the carboxylic acid component (y) and / or the alcohol component (x) constituting the crystalline polyester (A1). ) And one or more selected from C1-C30 monools (x31) are preferable because the blocking resistance is further improved.
As C1-C30 monocarboxylic acid (y31) and C1-C30 monool (x31), it is C1-C30 among said monocarboxylic acid (y3) and said monool (x3). Things. Among these, an alkane monocarboxylic acid having 1 to 30 carbon atoms and an alkanol having 1 to 30 carbon atoms are preferable, and an alkane monocarboxylic acid having 1 to 30 carbon atoms is more preferable. In (A1), the constituent monomer of the crystalline polyester (A12) is preferably an alkane monocarboxylic acid having 10 to 30 carbon atoms and an alkanol having 10 to 30 carbon atoms, and more preferably a carbon number. 10-30 alkane monocarboxylic acids.
The polycondensation conditions of (A1) in the case of containing (y31) or (x31) as a structural unit are carried out in the same manner as in the production method of the polyester resin (I), but (y31) and / or (x31) A method of reacting (y31) and / or (x31) with the molecular terminal of the obtained polyester after preparing a crystalline polyester in advance with the carboxylic acid component (y) and the alcohol component (x) other than ()) is preferred.

  When the crystalline polyester (A11) is used as (A1), the content of the diol (x1) in the alcohol component (x) constituting (A11) is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%, most preferably 100 mol%. Further, (x1) is preferably one kind of diol.

  The content of the dicarboxylic acid (y1) in the carboxylic acid component (y) constituting (A11) is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 60 to 99 mol. %. Further, the dicarboxylic acid (y1) is preferably one kind of dicarboxylic acid.

  The ratio of (y31) and (x31) in (A11) is such that the total of (y31) and (x31) is 40 mol% or less with respect to the total number of moles of the carboxylic acid component and alcohol component constituting (A11). It is preferable that it is 1-20 mol%.

When the crystalline polyester (A12) is used as (A1), (A12) is one or more selected from the alcohol component (x), an aliphatic polycarboxylic acid having 9 to 30 carbon atoms, and an ester-forming derivative thereof. An alcohol component (x) and a carboxylic acid component (y *) and at least one selected from a monocarboxylic acid having 10 to 30 carbon atoms (y311) and a monool having 10 to 30 carbon atoms (x311) Those obtained by polycondensation with y) are preferred. By containing a monocarboxylic acid (y311) having 10 to 30 carbon atoms and / or a monool (x311) having 10 to 30 carbon atoms, it has a low molecular weight but has a blocking resistance, a high crystallinity and a high crystallization speed. It is possible to achieve both.
(A12) is a monocarboxylic acid having 10 to 30 carbon atoms (y311) and / or a monool having 10 to 30 carbon atoms (x311), and is composed of 5 to 40 of all constituent monomers (total of carboxylic acid component and alcohol component). It is preferable to contain mol% (especially 10-30 mol%) from a viewpoint of crystallization speed and blocking resistance.

The equivalent ratio (OH group / COOH group) of the carboxylic acid component (y) and the alcohol component (x) constituting the crystalline polyester (A11) is preferably 0.85 to 1.18 from the viewpoint of storage stability, More preferably, it is 0.90 to 1.16, and particularly preferably 0.93 to 1.14.
The equivalent ratio (OH group / COOH group) of the carboxylic acid component (y) and the alcohol component (x) constituting the crystalline polyester (A12) is preferably 1.40 to 2.00 from the viewpoint of molecular weight. More preferably, it is 1.45 to 1.95, and particularly preferably 1.50 to 1.90.

The acid value of the crystalline polyester (A1) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, and particularly preferably 0 to 60. When the acid value is 100 or less, the charging characteristics at the time of toner formation do not deteriorate.
The hydroxyl value of (A1) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, particularly preferably 0 to 50. When the hydroxyl value is 100 or less, the hot offset resistance at the time of toner formation becomes better.

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

The SP value (solubility parameter) of the crystalline polyester (A1) 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 nonlinear polyester (B) 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 number average molecular weight (hereinafter referred to as Mn) of the tetrahydrofuran (THF) soluble part of the crystalline polyester (A11) is preferably 2,000 to 15,000, more preferably 3,000 to 10,000, particularly preferably. 4,000 to 9,000.
On the other hand, the Mn of the crystalline polyester (A12) is preferably 500 to 5000, more preferably 1000 to 4500, and particularly preferably 1000 to 4000.
Mp of the THF soluble part of (A11) is usually 5000 to 150,000, preferably 8000 to 100,000, more preferably 10,000 to 90,000.
On the other hand, Mp of (A12) is usually 1000 or more and less than 5000, preferably 1200 to 4900, more preferably 1500 to 4500, and particularly preferably 2000 to 4400.

In the present invention, the molecular weight [Mp, Mn, and weight average molecular weight (Mw)] 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% THF (tetrahydrofuran) 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 melting point [Tmp] of the crystalline polyester (A1) 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. . 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, and the temperature corresponding to the maximum peak of the endothermic heat generation is defined as the melting point [Tmp].

The flow softening point [Tm] of (A1) is preferably 50 to 150 ° C, more preferably 60 to 130 ° C, particularly preferably 65 to 110 ° C. Within this range, the low-temperature fixability and blocking resistance are further improved. In the present invention, Tm is measured by the following method.
<Flow softening point [Tm]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount The value (temperature when half of the measurement sample flows out) is taken as the flow softening point [Tm].

The crystalline polyester (A1) has a ratio {[Tm] / [Tmp]} of “flow softening point [Tm]” and “melting point [Tmp]” from the viewpoint of crystallization speed at the time of toner formation and blocking resistance. , Preferably 0.8 to 1.8.
When (A1) is (A11), {[Tm] / [Tmp]} is more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.4. When (A1) is (A12), {[Tm] / [Tmp]} is preferably 0.8 to 1.4.

The number average molecular weight (Mn), peak top molecular weight (Mp), melting point [Tmp], flow softening point [Tm], and ratio {[Tm] / [Tmp]} of the crystalline polyester (A1) are within the above ranges. Includes one or more selected from the equivalent ratio (OH group / COOH group) of the alcohol component (x) to the carboxylic acid component (y), a polycarboxylic acid having 9 to 22 carbon atoms, and an ester-forming derivative thereof (y *) 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 increases, Tm and Tmp both increase, and when away from 1, Mn decreases and both Tm and Tmp decrease. Further, when the number of carbon atoms in (y *) increases, both Tm and Tmp decrease, but Tmp decreases more greatly. Therefore, {[Tm] / [Tmp]} can be controlled by adjusting the carbon number and equivalent ratio (OH group / COOH group) of the carboxylic acid of (y *).

In the linear polyester (A), if necessary, an amorphous linear polyester (A2) other than the crystalline polyester (A1) may be contained.
The linear polyester (A2) can be obtained, for example, by polycondensation of the diol (x1) and the dicarboxylic acid (y1), and the molecular terminal is further converted to (y1) or (y2) of the carboxylic acid component (y). ) May be modified with an anhydride or the like. In these, what modified | denatured the molecular terminal with the anhydride of (y1) or (y2) is preferable. The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 3/1 to 1/3, more preferably 2.5 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. /1-1/2.5, particularly preferably 2 / 1-1 / 2.

  The acid value of the linear polyester (A2) is preferably 5 to 100, more preferably 10 to 80, and particularly preferably 15 to 60. When the acid value is 5 or more, the low-temperature fixability at the time of toner formation is good, and when it is 100 or less, the charging characteristics at the time of toner formation do not deteriorate.

  The hydroxyl value of (A2) is preferably 10 to 125, more preferably 20 to 100. When the hydroxyl value is 10 or more, the compatibility with the non-linear polyester (B) is good, and the glossiness (gloss) after fixing at the time of toner formation is good. Further, when the hydroxyl value is 125 or less, the hot offset resistance at the time of toner formation becomes better.

The glass transition temperature [Tg] of (A2) is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 70 ° C. When Tg is 75 ° C. or lower, the low-temperature fixability at the time of toner formation is improved. Further, when Tg is 45 ° C. or higher, the blocking resistance at the time of toner formation is good.
In this invention, glass transition temperature [Tg] is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20 and SSC / 580.

The Mn of the linear polyester (A2) is preferably 1000 to 10000, more preferably 1500 to 9000. When Mn is 1000 or more, the resin strength necessary for fixing is expressed, and when it is 10,000 or less, the low-temperature fixability at the time of toner formation is good.
Further, the Mp of (A2) is preferably 2000 to 12000, more preferably 3000 to 10000, from the viewpoint of the balance of resin strength, low-temperature fixability, and resin grindability.

The THF insoluble content in the linear polyester (A2) is preferably 5% or less from the viewpoint of low-temperature fixability at the time of toner formation. More preferably, it is 4% or less, and particularly preferably 3% or less.
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.

The nonlinear polyester (B) used in the present invention comprises a polyol (x2) having 3 to 8 or more valences and / or a polycarboxylic acid (y2) having 3 to 6 or more valences, an alcohol component (x) and A polycondensate obtained by reacting at least a part of the carboxylic acid component (y) is preferred.
(B) is more preferably a resin obtained by further reacting a polyester resin (a) which is a polycondensation reaction product of (x) and (y) with one or more carboxylic acids (b). .

  In the polyester resin (a), the reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 1.4 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. It is 1.01 / 1, more preferably 1.35 / 1 to 1.1 / 1, and particularly preferably 1.35 / 1 to 1.2 / 1. In addition, the said reaction ratio is a ratio which excluded the part, when there exists a component removed out of a system during reaction.

The polyester resin (a) preferably has an acid value of 6 or less and a hydroxyl value of 10 to 70. The acid value is preferably 5 or less, more preferably 4 or less, and the hydroxyl value is preferably 15 to 65, more preferably 20 to 60. When the acid value is 6 or less or the hydroxyl value is 70 or less, the polycondensation of the polyester resin (a) is sufficient, the low molecular weight component is small, and the storage stability is good. When the hydroxyl value is greater than 10, the reaction efficiency with the carboxylic acid (b) is good.
In order to set the acid value and the hydroxyl value of (a) within these ranges, it is effective to adjust the reaction ratio between the alcohol component (x) and the carboxylic acid component (y).

  As for the molecular weight of (a), it is preferable that Mp is 2000-10000, and it is further more preferable that Mp is 3000-8000.

  When the nonlinear polyester (B) is obtained by the reaction of (a) and (b), the polyester resin (a) and the carboxylic acid (b) are derived from the equivalent of the hydroxyl group derived from (a) from OHa and (b). When the equivalent of the carboxyl group to be converted is COOHb, one obtained by reacting at an equivalent ratio of OHa / COOHb = 0.1 to 1.0 is preferable. OHa / COOHb is more preferably 0.2 to 0.9, and particularly preferably 0.3 to 0.8. When OHa / COOHb is 0.1 or more, the molecular weight becomes sufficiently large, and the hot offset resistance at the time of toner formation is improved. When it is 1.0 or less, the fluidity of the resin becomes good, and the low-temperature fixability and glossiness at the time of toner formation are improved.

As the carboxylic acid (b), any of a monocarboxylic acid and a polycarboxylic acid can be used, and specific examples thereof include the dicarboxylic acid (y1), the tri- or hexavalent or higher polycarboxylic acid (y2). And the same monocarboxylic acid (y3).
The ratio of monocarboxylic acid to polycarboxylic acid (2 to 6 or more) is derived from the carboxyl group derived from monocarboxylic acid and polycarboxylic acid when the equivalent of all carboxyl groups of carboxylic acid used in the reaction is 100 (0-50) / (50-100) is preferable, and (0-20) / (80-100) is more preferable. When the ratio of the carboxyl derived from the monocarboxylic acid is 50 or less, the crosslinking is not insufficient and the strength of the resin is sufficiently obtained. Moreover, it is easy to adjust the acid value of the reaction product within a predetermined range.

  (B) is preferably an aromatic polycarboxylic acid having a valence of 2 or more in (y), and an aromatic polycarboxylic acid having 9 to 20 carbon atoms in the carboxylic acid (y2) having a valence of 3 to 6 or more. Carboxylic acid is more preferable, and trimellitic acid and trimellitic anhydride are particularly preferable.

  The content of the aromatic polycarboxylic acid having 9 to 20 carbon atoms of 3 to 6 or more in the carboxylic acid component constituting the nonlinear polyester (B) is preferably 30 mol% or less, more preferably 1 to 20 mol%. When it is 30 mol% or less, the fluidity of the resin is good, and the low-temperature fixability at the time of toner formation is improved.

The acid value of (B) is preferably 15 to 80, more preferably 18 to 60. The hydroxyl value is preferably 40 or less, and more preferably 25 or less.
When the acid value is 15 or more, the fixing strength at the time of toner formation is sufficient. Further, when the hydroxyl value is 40 or less or the acid value is 80 or less, it is hardly affected by environmental conditions and the stability is good.
In the present invention, the acid value and hydroxyl value of (B) preferably satisfy the relationship of the following formula (1), and more preferably satisfy the relationship of the formula (1 ′).
Acid value / Hydroxyl value ≧ 1 Formula (1)
Acid value / Hydroxyl value ≧ 1.1 Formula (1 ′)
When (acid value / hydroxyl value) is 1 or more, the glossiness at the time of toner formation and the glossiness in the fixing temperature range are good. In addition, in order to manufacture polyester resin (I) which satisfy | fills Formula (1), it can achieve by adjusting the reaction ratio of polyester resin (a) and carboxylic acid (b).

  The THF-insoluble content of the non-linear polyester (B) is preferably 1 to 36%, more preferably 2 to 33%. When the THF insoluble content is 1% or more, the hot offset resistance at the time of toner formation is good, and when it is 36% or less, the low-temperature fixability at the time of toner formation is good.

  The glass transition temperature [Tg] of (B) is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 70 ° C. When Tg is 75 ° C. or lower, the low-temperature fixability at the time of toner formation is improved. Further, when Tg is 45 ° C. or higher, the blocking resistance at the time of toner formation is good.

  The flow softening point [Tm] of (B) is preferably 120 to 180 ° C, more preferably 122 to 170 ° C. Within this range, the blocking resistance is further improved.

In the present invention, the THF-insoluble matter and the flow softening point of (B) preferably satisfy the relationship of the following formula (2), and more preferably satisfy the relationship of the formula (2 ′).
THF insoluble matter (%) / flow softening point (° C.) ≦ 0.2 Formula (2)
0.01 ≦ THF insoluble matter (%) / flow softening point (° C.) ≦ 0.19 Formula (2 ′)
When (THF insoluble matter / flow softening point) is 0.2 or less, (A) and (B) are easily mixed uniformly, so that the low-temperature fixability and hot offset resistance at the time of toner formation are good. In addition, the glossiness at the glossiness expression temperature and the fixing temperature range is good.
In order to produce the non-linear polyester (B) satisfying the formula (2), for example, after producing the polyester resin (a), (B) is reacted by reacting (a) with the carboxylic acid (b). This can be achieved by adjusting the hydroxyl value of (a) to 10 to 70 mg KOH / g and adjusting the reaction ratio of (a) and (b).

As for the molecular weight of nonlinear polyester (B), it is preferable that Mp is 5000-20000, and it is further more preferable that it is 5500-15000. The weight average molecular weight (hereinafter referred to as Mw) is preferably 30000-300000, more preferably 40000-250,000. Further, the ratio of Mw and Mn (hereinafter referred to as Mw / Mn) showing the molecular weight distribution is preferably 15 to 100, and more preferably 20 to 90.
When Mp, Mw, and Mw / Mn are within the above ranges, the balance between hot offset resistance and low-temperature fixability at the time of toner formation is good.

In the present invention, the non-linear polyester (B) preferably has a difference in flow softening point [Tm] before and after being melted by heating at 200 ° C., preferably 10 ° C. or less, and more preferably 5 ° C. or less.
The difference in Tm before and after being melted by heating at 200 ° C. is measured, for example, as follows.
A test tube containing 3 g of (B) is placed in a block bath adjusted to 200 ° C., heated and dissolved for about 10 minutes, and then dissolved (B) is put into ice water together with the test tube and cooled. The flow softening point [Tm] is measured for (I) that has been heat-melted and (B) before heat-melting, and the difference is determined.

In the present invention, the nonlinear polyester (B) preferably has a Mp change rate of a component soluble in THF before and after being melted by heating at 200 ° C. of 10% or less, and more preferably 9% or less.
Note that the method of heat-melting treatment at 200 ° C. is the same as the method described in the previous section.
As a method for reducing the difference in Tm before and after melting at 200 ° C. and the difference in Mp of components soluble in THF before and after heating and melting at 200 ° C., for example, after completion of the reaction of (a) and (b) The nonlinear polyester (B) can be cooled in a shorter time using a belt cooler, drum cooler or the like.

  In the polyester resin (I), the weight ratio [(A) / (B)] of the linear polyester (A) and the non-linear polyester (B) is determined from the viewpoint of the balance between hot offset resistance and low-temperature fixability at the time of toner formation. The ratio is preferably 10/90 to 80/20, more preferably 15/85 to 75/25, and particularly preferably 25/75 to 70/30.

The polyester resin (I) containing the crystalline polyester (A11) contained in the resin for toner of the present invention has a loss elastic modulus (G ″) of 30000 dyne / cm ² from the viewpoint of low-temperature fixability at the time of toner formation. The temperature [T3000] is preferably 130 ° C. or lower, more preferably 125 ° C. or lower.
Further, from the viewpoint of achieving both low-temperature fixability and hot offset resistance at the time of toner production, the loss elastic modulus at 100 ° C. [G ″ 100] (dyn / cm ² ) and the loss elastic modulus at 150 ° C. [G ″ 150] (Dyn / cm ² ) preferably satisfies the following formula (3), and more preferably satisfies the formula (3 ′).
[G "100] / [G" 150] ≦ 50 Formula (3)
[G "100] / [G" 150] ≤45 (3 ')
When [G "100] and [G" 150] satisfy the formula (3), it is considered that the viscosity in the low temperature region is small and the viscosity does not become too low in the high temperature region. Is wide.
In order to adjust the loss elastic modulus (G ″) of (I), for example, the amount of crystalline polyester (A11), the molecular weight of the resin in (A), and the number of crosslinking points may be increased or decreased.

In the present invention, the loss elastic modulus (G ″) of the polyester resin is measured using the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 25mm parallel plate Frequency: 20Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

The polyester resin (I) containing the crystalline polyester (A12) contained in the resin for toner of the present invention has a crystallinity at the first temperature increase when DSC measurement is performed from the viewpoint of blocking resistance at the time of toner formation. It is preferable that the melting heat quantity Q1 of the melting peak derived from the polyester (A12) and the melting heat quantity Q2 of the melting peak derived from the crystalline polyester (A12) in the second temperature increase satisfy the following formula (4). It is further preferable to satisfy ').
0.6 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4)
0.7 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4 ′)
When [Q2] / [Q1] satisfies the formula (4), the crystallization speed and the degree of crystallization are high, and the blocking resistance when used as a toner is good.
In order to adjust [Q2] / [Q1] of (I), the SP value of the crystalline polyester (A12) may be increased or decreased. For example, to increase [Q2] / [Q1] (closer to 1), the SP value may be decreased. Conversely, to decrease [Q2] / [Q1], the SP value may be increased. . Moreover, as means for reducing the SP value, the amount of the monocarboxylic acid having 10 to 30 carbon atoms (y311) and the monool having 10 to 30 carbon atoms (x311) in (A12) is increased, or in (A12) Of the aliphatic polycarboxylic acids (y *) having 9 to 30 carbon atoms, those having a large carbon number may be used. Conversely, in order to increase the SP value, the amount of the monocarboxylic acid having 10 to 30 carbon atoms (y311) and the monool having 10 to 30 carbon atoms (x311) in (A12) is reduced, or in (A12) What is necessary is just to use what has a small carbon number in C9-C30 aliphatic polycarboxylic acid (y *).

  The toner resin of the present invention may contain, in addition to the polyester resin (I), other resins usually used as a toner resin as long as the properties thereof are not impaired. Examples of other resins include polyester resins other than (A) and (B) whose Mn is 1,000 to 1,000,000, styrene resins, resins having a structure in which a vinyl resin is grafted on a polyolefin resin, epoxy resins, and polyurethane resins. 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.

In the present invention, the mixing method of (A) and (B) or the mixing method when mixing of (A1) and (A2) is required is not particularly limited, and may be a known method that is usually performed. Any of melt mixing may be used. 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 resin of the present invention as a binder resin, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, a fluidizing agent, and the like. To do.

  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.

As the mold release agent, those having a flow softening point [Tm] of 50 to 170 ° C. are preferable, such as polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Is mentioned.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (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 from 30 to 97%, more preferably from 40 to 95%, particularly preferably from 45 to 92%, based on the toner weight, the toner resin of the present invention; , Preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; among additives, a release agent is preferably 0 to 30%, more preferably 0.5-20%, particularly preferably 1-10%; charge control agent is preferably 0-20%, more preferably 0.1-10%, particularly preferably 0.5-7.5%; flow The agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

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

  The toner composition of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary. Used as a developer for a latent image. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to 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 titanium-containing catalyst>
Place 1000 parts of ethyl acetate and 800 parts of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube capable of bubbling in liquid, and gradually raise the temperature to 60 ° C. while bubbling in liquid with nitrogen. While adding 600 parts of titanium tetraisopropoxide dropwise, the mixture was reacted at 60 ° C. for 4 hours to obtain a slurry-like reaction mixture. The reaction mixture was filtered off with a filter paper and dried at 40 ° C./20 kPa · s, so that a titanium-containing catalyst (t1) composed of a mixture of titanium triisopropoxyterephthalate and unreacted terephthalic acid (titanium triisopropoxyterephthalate concentration 65% )

Production Example 2 <Synthesis of Crystalline Polyester (A11) (1)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out 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 taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-1).
Crystalline polyester (A11-1) had Tmp of 66 ° C., Tm of 73 ° C. (Tm / Tmp = 1.1), Mp of 13,500, acid value of 1, and SP value of 9.6.
The number of moles in parentheses means a relative molar ratio (the same applies hereinafter).

Production Example 3 <Synthesis of Crystalline Polyester (A11) (2)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 121 parts (1.03 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out 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 taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-2).
Crystalline polyester (A11-2) 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 4 <Synthesis of Crystalline Polyester (A11) (3)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 343 parts (1.0 mol) of 1,18-octadecanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out 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 taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-3).
Crystalline polyester (A11-3) 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 5 <Synthesis of Crystalline Polyester (A11) (4)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 69 parts (1.12 mol) of ethylene glycol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and tetrabutoxy as a condensation catalyst. 3 parts of titanate was added and reacted at 200 ° C. for 5 hours while distilling off the water generated under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-4).
Crystalline polyester (A11-4) had Tmp of 108 ° C., Tm of 110 ° C. (Tm / Tmp = 1.0), Mp of 10,500, acid value of 2, and SP value of 10.0.

Production Example 6 <Synthesis of Crystalline Polyester (A11) (5)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. 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 acid value was adjusted to 2 or less. Next, 355 parts (0.16 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-5).
Crystalline polyester (A11-5) had Tmp of 70 ° C., Tm of 75 ° C. (Tm / Tmp = 1.1), Mp of 11000, acid value of 2, and SP value of 9.6.

Production Example 7 <Synthesis of Crystalline Polyester (A12) (1)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 477 parts (4.04 moles) of 1,6-hexanediol, 620 parts of 1,12-dodecanedioic acid (2.7 moles), and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. 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 acid value was adjusted to 2 or less. Next, 497 parts (1.74 mol) of stearic acid was added, and the reaction was allowed to proceed for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-1).
Crystalline polyester (A12-1) had Tmp of 66 ° C., Tm of 65 ° C. (Tm / Tmp = 1.0), Mp of 4400, acid value of 2, hydroxyl value of 1, and SP value of 9.5. It was.

Production Example 8 <Synthesis of Crystalline Polyester (A12) (2)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 547 parts (4.63 moles) of 1,6-hexanediol, 551 parts (2.73 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. 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 acid value was adjusted to 2 or less. Next, 488 parts (1.71 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-2).
Crystalline polyester (A12-2) had Tmp of 57 ° C., Tm of 52 ° C. (Tm / Tmp = 0.9), Mp of 2700, acid value of 1, hydroxyl value of 38, and SP value of 9.5. It was.

Production Example 9 <Synthesis of Crystalline Polyester (A12) (3)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 547 parts (4.63 moles) of 1,6-hexanediol, 551 parts (2.73 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. 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 acid value was adjusted to 2 or less. Next, 733 parts (2.57 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-3).
The crystalline polyester (A12-3) had a Tmp of 60 ° C., a Tm of 58 ° C. (Tm / Tmp = 1.0), an Mp of 2700, an acid value of 1, a hydroxyl value of 6, and an SP value of 9.4. It was.

Production Example 10 <Synthesis of Crystalline Polyester (A12) (4)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 516 parts (4.37 moles) of 1,6-hexanediol, 589 parts (2.92 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. 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 acid value was adjusted to 2 or less. Next, 878 parts (2.57 mol) of behenic acid was added, and the reaction was allowed to proceed for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-4).
Crystalline polyester (A12-4) had Tmp of 66 ° C., Tm of 67 ° C. (Tm / Tmp = 1.0), Mp of 2800, acid value of 1, hydroxyl value of 7, and SP value of 9.4. It was.

Production Example 11 <Synthesis of Crystalline Polyester (A12) (5)>
238 parts (2.02 mol) 1,6-hexanediol, 903 parts (3.93 mol) 1,12-dodecanedioic acid, and condensation in a reactor equipped with a condenser, stirrer and nitrogen inlet 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the hydroxyl value was adjusted to 2 or less. Next, 516 parts (1.91 mol) of stearyl alcohol was added and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the hydroxyl value became 2 or less. This is designated as crystalline polyester (A12-5).
The crystalline polyester (A12-5) had a Tmp of 59 ° C., a Tm of 62 ° C. (Tm / Tmp = 1.1), an Mp of 2500, an acid value of 42, a hydroxyl value of 1, and an SP value of 9.4. It was.

Production Example 12 <Synthesis of linear polyester (A2) other than (A1) (1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 592 parts (3 mol) of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 194 parts (1 mol) of dimethyl terephthalate, and 3 parts of tetrabutoxy titanate was added as a condensation catalyst, and the reaction was allowed to proceed for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while the temperature was gradually raised to 230 ° C., the reaction was carried out while distilling off propylene glycol produced under a nitrogen stream, and when Tm reached 78 ° C., the reaction was cooled to 180 ° C. and 68 parts of trimellitic anhydride (0. 36 mol) was added, and the mixture was taken out after reaction for 1 hour under normal pressure. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (A2-1).
The linear polyester (A12-1) had a Tg of 58 ° C., a Tm of 96 ° C., an Mp of 4000, an acid value of 40, a hydroxyl value of 55, and a THF-insoluble content of 0%.

Production Example 13 <Synthesis of Linear Polyester (A) (1)>
Put 400 parts of (A2-1) and 600 parts of (A11-1) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-1).

Production Example 14 <Synthesis of Linear Polyester (A) (2)>
Put 400 parts of (A2-1) and 600 parts of (A11-2) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-2).

Production Example 15 <Synthesis of Linear Polyester (A) (3)>
Put 400 parts of (A2-1) and 600 parts of (A11-3) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-3).

Production Example 16 <Synthesis of Linear Polyester (A) (4)>
Put 400 parts of (A2-1) and 600 parts of (A11-4) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-4).

Production Example 17 <Synthesis of Linear Polyester (A) (5)>
500 parts of (A2-1) and 500 parts of (A11-5) are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, heated to 180 ° C. and melt blended for 1 hour, then taken out. It was. This is designated as linear polyester (A-5).

Production Example 18 <Synthesis of Linear Polyester (A) (6)>
Place 800 parts of (A2-1) and 200 parts of (A12-1) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-6).

Production Example 19 <Synthesis of Linear Polyester (A) (7)>
Put 400 parts of (A2-1) and 600 parts of (A12-2) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-7).

Production Example 20 <Synthesis of Linear Polyester (A) (8)>
Place 900 parts of (A2-1) and 100 parts of (A12-3) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-8).

Production Example 21 <Synthesis of Linear Polyester (A) (9)>
Place 900 parts of (A2-1) and 100 parts of (A12-4) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-9).

Production Example 22 <Synthesis of Linear Polyester (A) (10)>
Place 900 parts of (A2-1) and 100 parts of (A12-5) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-10).

Production Example 23 <Synthesis of Nonlinear Polyester (B) (1)>
Propylene oxide of 41 parts (0.13 mole) of bisphenol A / ethylene oxide 2 mole adduct, 457 parts (1.14 mole) of bisphenol A / propylene oxide 3 mole adduct, phenol novolak (average functional group number: 5.6) 9 parts (0.01 mole) of 6 mole adduct, 166 parts (1.0 mole) of terephthalic acid, 93 parts (0.8 mole) of fumaric acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst The reaction was carried out for 5 hours while distilling off the water produced under a nitrogen stream. 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 mixture 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 nonlinear polyester (B-1).
Nonlinear polyester (B-1) has a Tg of 58 ° C., Tm of 135 ° C., Mp of 11,300, an acid value of 20, a hydroxyl value of 5 (acid value / hydroxyl value = 4), and a THF insoluble content of 6% (THF Insoluble matter / flow softening point = 0.04).

Production Example 24 <Synthesis of Nonlinear Polyester (B) (2)>
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 of terephthalic acid ( 1.0 mol), and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 230 ° C. in a nitrogen stream for 5 hours while distilling off the generated water. 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. , 230 ° C., 5 to 20 mmHg under reduced pressure, and 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 nonlinear polyester (B-2).
The nonlinear polyester (B-2) has a Tg of 57 ° C., Tm of 145 ° C., Mp of 8300, an acid value of 20, a hydroxyl value of 18 (acid value / hydroxyl value = 1.1), and a THF-insoluble content of 28%. (THF insoluble matter / flow softening point = 0.19).

Comparative Production Example 1 <Synthesis of Comparative Crystalline Polyester (1)>
1,4-butanediol 117 parts (1.3 mol), fumaric acid 116 parts (1.0 mol), and tetrabutoxy titanate as a condensation catalyst in a reactor equipped with a condenser, stirrer and nitrogen inlet tube 3 parts were added and reacted at 200 ° C. for 5 hours while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and after 5 hours, the water was removed when it was no longer distilled off. This is designated as crystalline polyester (A11′-6).
Crystalline polyester (A11′-6) had Tmp of 123 ° C., Tm of 82 ° C. (Tm / Tmp = 0.7), and SP value of 10.7. Mp and acid value could not be measured because they were insoluble in the measurement solvent.

Comparative Production Example 2 <Synthesis of Comparative Linear Polyester (1)>
The linear polyester (A2-1) obtained in Production Example 12 is used as a comparative linear polyester (A′-11) as it is.

Comparative Production Example 3 <Synthesis of Comparative Linear Polyester (2)>
After placing 400 parts of (A2-1) and 600 parts of (A11′-6) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the temperature was raised to 180 ° C. and melt blending was conducted for 1 hour. I took it out. This is designated as comparative linear polyester (A′-12).

Comparative Production Example 4 <Synthesis of Comparative Linear Polyester (3)>
970 parts of (A2-1) and 30 parts of (A11-1) are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, heated to 180 ° C. and melt blended for 1 hour, then taken out. It was. This is designated as comparative linear polyester (A′-13).

Examples 1 to 14 <Toner Resin>
In the blending ratio shown in Table 1, linear polyesters (A-1) to (A-10) and nonlinear polyesters (B-1) and (B-2) were jacketed at 130 ° C. and residence time with a continuous kneader. Melt mixed in 3 minutes. The molten resin was cooled to room temperature, pulverized by a pulverizer, and pulverized to obtain toner resins (I-1) to (I-14) for the present invention.
Table 1 shows the measurement results of [T30000], [G "100] / [G" 150] and [Q2] / [Q1] of the toner resin.

Comparative Examples 1 to 3 <Comparative Toner Resin>
With the blending ratio shown in Table 1, (A′-11) to (A′-13) and (B-2) were melt-mixed with a continuous kneader at a jacket temperature of 130 ° C. and a residence time of 3 minutes. After the molten resin was cooled to room temperature, it was pulverized by a pulverizer and formed into particles to obtain comparative toner resins (I′-15) to (I′-17).
Table 1 shows the measurement results of [T30000] and [G "100] / [G" 150] and [Q2] / [Q1] for the comparative resin for toner.

Examples 15-28 and Comparative Examples 4-6
For each 100 parts of the toner resins (I-1) to (I-14) and comparative toner resins (I′-15) to (I′-17) of the present invention, cyanine blue KRO (Sanyo) 8 parts of pigment) and 5 parts of carnauba wax were added to form a toner by the following method.
First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher lab 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 the particle size D50 is 8 μm toner particles were obtained. Then, 100 parts of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) in a sample mill, and the toner compositions (T-1) to (T-14) of the present invention and comparison were made. Toner compositions (T′-15) to (T′-17) were obtained.
Table 2 shows the evaluation results evaluated by the following evaluation methods.

[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 placed in a 200 ml polycup and left standing 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.

  As described above, the toner compositions (Examples 15 to 28) of the present invention using the toner resin of the present invention are all significantly better than the toner compositions of the comparative examples (Comparative Examples 4 to 6). Results were obtained.

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

Claims (9)

In a toner resin containing a polyester resin (I) composed of a linear polyester (A) and a non-linear polyester (B), (A) is an aliphatic polycarboxylic acid having 9 to 30 carbon atoms and its ester formability. A polycondensation polyester resin of a carboxylic acid component and an alcohol component containing at least 40 mol% of one or more selected from derivatives, and having an SP value of 9.0 to 10.5 (cal / cm ³ ) ^1/2 A crystalline polyester (A1) and an amorphous linear polyester (A2) other than (A1) are contained, and the content of (A1) in (A) is 5 to 95% by weight. B) has a THF insoluble content of 1 to 36% by weight, a THF soluble content of gel permeation chromatography having a peak top molecular weight of 5,000 to 20,000, and a flow softening point of 12. A toner resin having a temperature of 0 to 180 ° C., an acid value of 15 to 80, and (B) satisfying the following formulas (1) and (2):
Acid value / Hydroxyl value ≧ 1 Formula (1)
THF insoluble matter (% by weight) / flow softening point (° C.) ≦ 0.2 (2)   The carboxylic acid component and / or the alcohol component constituting the crystalline polyester (A1) further contains one or more selected from monocarboxylic acids having 1 to 30 carbon atoms and monools having 1 to 30 carbon atoms. Item 1. The toner resin according to Item 1.   The crystalline polyester (A1) has a melting point [Tmp] of 50 to 120 ° C., a flow softening point [Tm] of 50 to 150 ° C., and [Tm] / [Tmp] of 0.8 to 1.8. The resin for toner according to claim 1 or 2.   The resin for toner according to claim 1, wherein the crystalline polyester (A1) is a crystalline polyester (A11) having a peak top molecular weight of 5,000 to 150,000 in gel permeation chromatography of a THF-soluble component. The temperature [T30000] at which the loss elastic modulus (G ″) of the polyester resin (I) reaches 30000 (dyn / cm ² ) is 130 ° C. or less, and the loss elastic modulus [G ″ 100] (dyn / cm ² ) at 100 ° C. And a loss elastic modulus [G "150] (dyn / cm < ² >) at 150 [deg.] C. satisfying the following formula (3).
[G "100] / [G" 150] ≦ 50 (3)   The resin for toner according to any one of claims 1 to 3, wherein the crystalline polyester (A1) is a crystalline polyester (A12) having a peak top molecular weight of not less than 1000 and less than 5000 in gel permeation chromatography of a THF-soluble component. .   The resin for toner according to claim 6, wherein 5 to 40 mol% of all the constituent monomers of the crystalline polyester (A12) is a monocarboxylic acid having 10 to 30 carbon atoms and / or a monool having 10 to 30 carbon atoms. The amount of heat of fusion Q1 of the melting peak derived from the crystalline polyester (A12) at the first temperature increase and the melting peak derived from the crystalline polyester (A12) at the second temperature increase when the linear polyester (A) was subjected to DSC measurement. The toner resin according to claim 6 or 7, wherein the heat of fusion Q2 of the above satisfies the following formula (4).
0.6 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4)   A toner composition comprising the toner resin 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.