JP2009175755A - Polyester resin for toner and toner composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin for toners, which has an excellent balance between fixability at low temperatures and grindability and is excellent in glossiness after fixing. <P>SOLUTION: The polyester resin for toners is obtained by polycondensing a polyol component and a polycarboxylic acid component, wherein the polycarboxylic acid component comprises 80-100 mol% of terephthalic acid, isophthalic acid and/or 1-4C lower alkyl esters of those (a), the polyol component comprises 20-100 mol% of an aliphatic diol (80-100 mol% of which is 1,2-propylene glycol) (b), and 0.1-20 mol% of the total amount of the polyol component and the polycarboxylic acid component is a polyhydric alcohol which is trivalent or higher and/or a polycarboxylic acid which is trivalent or higher (c). The polyester resin (A3) has a softening point of 95-160°C and a glass transition temperature (Tg) of 45-75°C, and comprises a linear polyester resin (Aa) and a nonlinear polyester resin (Ab) or the nonlinear polyester resin (Ab). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

The electrostatic image developing toner used in the thermal fixing method is such that the toner does not fuse to the heat roll even at a high fixing temperature (hot offset resistance), and the toner can be fixed even at a low fixing temperature (low temperature fixing property). There is a demand for good grindability of resin during toner production. In general, low-temperature fixability and resin pulverization during toner production tend to have contradictory performance. As a toner having excellent low-temperature fixability and good resin pulverization properties during toner production, a toner comprising a toner resin containing a specific amount of a monovalent aliphatic compound having 10 to 24 carbon atoms as a monomer component is disclosed. (See Patent Document 1).
Further, as an attempt to provide a toner that satisfies the low-temperature fixability of the toner and does not cause high-temperature offset, the loss tangent tan δ in the range of the loss elastic modulus G ″ = 1 × 10 ⁴ Pa to 1 × 10 ⁶ Pa of the toner. In which a loss tangent tan δ at a loss elastic modulus G ″ = 1 × 10 ³ Pa is 0.5 or more and less than 1.0 is introduced. ing. (See Patent Document 2)
However, although the toner proposed in Patent Document 1 is excellent in low-temperature fixability, it needs to be improved in terms of both low-temperature fixability and pulverization in further higher speed and energy saving. Although the toner proposed in Patent Document 2 has good low-temperature fixability and high-temperature offset, the image quality is not satisfactory for color applications that require glossiness.

For the purpose of improving the moisture resistance and fixing performance of the polyester toner, a main chain or a side chain is obtained by cocondensing a long-chain aliphatic dicarboxylic acid or a dicarboxylic acid having a long-chain aliphatic side chain together with a trihydric or higher polyhydric alcohol. It is known to introduce a long chain aliphatic hydrocarbon unit into a polyester resin (see Patent Document 3).
However, in these polyester resins, sebacic acid or the like is used as a long-chain aliphatic dicarboxylic acid, and dodecenyl succinic acid or the like is used as a dicarboxylic acid having a long-chain aliphatic side chain. Although the carbon number of the toner is increased and the moisture resistance and fixing performance of the toner are improved, the glass transition temperature (Tg) of the polyester resin is lowered and the storage stability of the toner is inferior.

The toner for developing electrostatic images used in the thermal fixing method is such that the toner does not fuse to the heat roll even at a high fixing temperature (hot offset resistance), and the toner can be fixed even at a low fixing temperature (low temperature fixing property). It has been demanded. In order to prevent hot offset, it is effective to use wax, and in order to improve low-temperature fixability, it is effective to use a polyester resin as a binder for toner.
However, the wax and the polyester resin have poor compatibility, and the dispersed particle size of the wax in the toner becomes large. As a result, image defects associated with wax fixation and filming on the photoconductor and image defects associated with charging defects may occur. As an attempt to solve these problems, Patent Document 4 proposes to use a graft polymer having a structure in which a styrene polymer chain or a styrene (meth) acrylic polymer chain is grafted to a wax component. As a result, the particle diameter of the wax in the toner can be controlled, and a toner that has excellent hot offset resistance and does not induce filming or image defects can be provided.
However, the toner proposed in the above publication is effective from the standpoint of low-temperature fixability, although it has an effect in hot offset resistance and does not induce filming or image defects.

JP 2003-337443 A JP 2003-280241 A JP-A-62-78568 JP 2001-134209 A

One of the objects of the present invention is to obtain toner resin particles having excellent low-temperature fixability and good resin pulverization properties during toner production.
Another object of the present invention is to obtain resin particles for toner that are further excellent in gloss.
A further object of the present invention is to obtain toner resin particles having good moisture resistance and fixing performance when used as a toner, and good toner storage stability.
It is a further object of the present invention to obtain a resin composition for toner that is excellent in hot offset resistance, does not induce image defects, and obtains a toner excellent in low-temperature fixability.
A further object of the present invention is to obtain a non-magnetic one-component toner having excellent low-temperature fixability, good resin pulverization properties during toner production, and excellent glossiness and transparency as a color toner.

The inventor has intensively studied to solve these problems, and has reached the present invention.
That is, the present invention is the following four inventions ([3] to [6]). ([1] and [2] are reference inventions.)
[1] In a polyester resin for toner obtained by polycondensation of a polyol component and a polycarboxylic acid component, the molar average cohesive energy of the polyol component is 7.0 × 10 ^{4 to} 1.4 × 10 ⁵ J, and 150 ° C. A polyester resin for toner, comprising 20 to 100% by weight of one or more polyester resins (A1) having a storage elastic modulus of 2.5 × 10 ³ Pa to 5 × 10 ⁶ Pa.
[2] One type of polyester resin for toner obtained by polycondensation of a polyol component and a polycarboxylic acid component, having a softening point of 120 ° C. to 180 ° C. and a loss tangent at 130 ° C. to 200 ° C. of 0.9 or more. A polyester resin for toner, comprising 20 to 100% by weight of the above polyester resin (A2).
[3] In a polyester resin for toner obtained by polycondensation of a polyol component and a polycarboxylic acid component, the polycarboxylic acid component is 80 to 100 mol% of terephthalic acid, isophthalic acid, and / or their lower alkyl (alkyl). Carbon number of group: 1 to 4) Consists of ester (a), polyol component is 20 to 100 mol% aliphatic diol (80 to 100 mol% of the aliphatic diol is 1,2-propylene glycol) (B), 0.1 to 20 mol% of the total of the polyol component and the polycarboxylic acid component is a trihydric or higher polyhydric alcohol and / or a trivalent or higher polycarboxylic acid (c), and a softening point Is 95 to 160 ° C., glass transition temperature (Tg) is 45 to 75 ° C., linear polyester resin (Aa) and nonlinear polyester resin (Ab) Or a polyester resin for toner (A3), which comprises a non-linear polyester resin (Ab).
[4] A toner comprising the toner resin (B) comprising the polyester resin for toner of [3] and a modified product (w1) in which at least a part of the wax (w) is modified with a vinyl monomer (m). Polyester resin composition.
[5] The polyester resin for toner of the above [3] and a colorant, or one or more selected from the polyester resin for toner, a colorant, a release agent, a charge control agent, and a fluidizing agent. A toner composition comprising an additive.
[6] In the non-magnetic one-component toner used in the image forming method for developing the latent image by supplying the toner to the latent image carrier, the toner is the polyester resin (A3) for toner of the above [3], and coloring. When the glass transition temperature (Tg) of (A3) is a variable on the x-axis and the softening point (sp) is plotted on the xy coordinates as a variable on the y-axis, it is expressed by the following formulas (1) to (4). A non-magnetic one-component toner having physical properties within a range surrounded by a straight line and containing one or more fine particle additives on the surface of the toner particles.
Formula (1) sp = 4Tg-110
Formula (2) sp = 4Tg-170
Formula (3) sp = 90
Formula (4) sp = 130

By using the polyester resin for toner and the toner composition of the first, second, or fifth invention, a toner having excellent low-temperature fixability can be obtained. Further, since the resin is excellent in pulverizability at the time of toner production, the toner can be produced economically during industrial production. Further, since a high temperature offset does not occur in a temperature range of 130 ° C. to 200 ° C., the smoothness of the toner surface after fixing is maintained, and a glossy image can be provided.
The polyester resin of the third invention is excellent in blocking resistance, melt fluidity, low-temperature fixability and charging characteristics even under high humidity. Moreover, even when a tin compound is not used as a catalyst, it has good resin performance.
By using the resin composition for toner according to the fourth aspect of the present invention, a toner having excellent hot offset resistance, inducing image defects and excellent in low-temperature fixability can be obtained.
By using the toner of the sixth aspect of the invention, excellent low-temperature fixability can be obtained, and glossiness and transparency as a color toner in high image quality can be exhibited. In addition, since the toner is excellent in pulverization at the time of toner production, the toner can be produced economically during industrial production.

It is a graph showing the relationship between the glass transition temperature (Tg) and the softening point (Sp) of the polyester resin concerning this invention.

The present invention is described in detail below.
The molar average cohesive energy of the polyol which is a constituent component of the polyester resin (A1) of the first invention is usually 7.0 × 10 ^{4 to} 1.4 × 10 ⁵ J. The lower limit is preferably 7.05 × 10 ⁴ J, more preferably 7.1 × 10 ⁴ J. The upper limit is preferably 1.25 × 10 ⁵ J, more preferably 1 × 10 ⁵ J. When the molar average cohesive energy is 7.0 × 10 ⁴ J or more, the heat resistant storage stability is good, and when it is 1.4 × 10 ⁵ J or less, the grindability is good.
The storage elastic modulus at 150 ° C. of the resin (A1) composed of the polyol having the molar average cohesive energy is usually 2.5 × 10 ³ Pa to 5 × 10 ⁶ Pa. The lower limit is preferably 3.0 × 10 ³ Pa, more preferably 3.2 × 10 ³ Pa, and the upper limit is preferably 4.5 × 10 ⁶ Pa, more preferably 4.3 × 10 ⁶ Pa. is there.
Hot offset is good at 2.5 × 10 ³ Pa or more, and low-temperature fixability is good at 5 × 10 ⁶ Pa or less.
The constituent molar ratio of each polyol when two or more polyols are present is determined by calculation from the amount of polyol used and the amount of polyol recovered during the reaction.
Regarding the molar average cohesive energy, see, for example, Fedors et al., Polymer Engineering and Science, February, 1974, Vol. 14, no. 2, pages 147-154.
In order to adjust the value of the molar average cohesive energy, since the cohesive energy is a value inherent to each polyol, the molar ratio of the polyol may be adjusted. In order to adjust the storage elastic modulus of the resin, for example, the molecular weight of the resin or the number of crosslinking points may be increased or decreased.
The polyester resin (A1) of the first invention is preferably also a polyester resin (A2) of the second invention described later and / or a polyester resin (A3) of the third invention described later.

The softening point of the polyester resin (A2) of the second invention is usually 120 ° C to 180 ° C. The lower limit is preferably 125 ° C, more preferably 130 ° C, and the upper limit is preferably 175 ° C. When the softening point is 120 ° C. or higher, hot offset resistance is improved, and when it is 180 ° C. or lower, low-temperature fixability is improved.
Unless otherwise specified, the softening point in the present invention is heated at a constant speed under the following conditions using a flow tester CFT-500 manufactured by Shimadzu Corp. Let it be a point.
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

The loss tangent of (A2) at 130 ° C. to 200 ° C. is usually 0.9 or more, preferably 1.0 or more, more preferably 1.02 or more, particularly preferably 1.05 to 30, and most preferably 1.1. ~ 20. When the loss tangent is 0.9 or more, the glossiness is improved.
In order to adjust the softening point and loss tangent of the resin, for example, the molecular weight of the resin and the number of crosslinking points may be increased or decreased.

In the present invention, the storage elastic modulus and loss tangent of the polyester resin are 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
From the value obtained by the measurement, the temperature-loss tangent relationship is plotted, and the loss tangent at 130 ° C. to 200 ° C. is read.
The polyester resin (A2) of the second invention is preferably also the polyester resin (A1) of the first invention and / or the polyester resin (A3) of the third invention described later.

The polyester resin (A1) or (A2) used in the first and second inventions is usually obtained by polycondensation of one or more polyol components and one or more polycarboxylic acid components.
The polyol component used for the resin (A1) or (A2) is preferably composed of 30 to 100 mol% of an aliphatic diol having 2 to 6 carbon atoms. Further, the diol preferably contains 1,2-propylene glycol as at least a part. The content of the aliphatic diol having 2 to 6 carbon atoms in the polyol component is more preferably 70 to 100 mol%, more preferably 85 to 100 mol%, particularly preferably 90 to 100 mol%, most preferably 100 mol. %. When the content is 30 mol% or more, the resin strength is increased and the low-temperature fixability is improved.

Examples of the aliphatic diol having 2 to 6 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, Examples include alkanediols such as 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, and neopentyl glycol, and two or more of them may be used in combination. Among these, ethylene glycol, 1,2-propylene glycol and neopentyl glycol are preferable, ethylene glycol and 1,2-propylene glycol are more preferable, and 1,2-propylene glycol is particularly preferable. is there.
30 to 100 mol% in the polyol component is 1,2-propylene glycol, and 0 to 30 mol% is composed of another polyol containing an aliphatic diol having 2 to 6 carbon atoms other than 1,2-propylene glycol. A polyol component is also preferred. In this case, the content of 1,2-propylene glycol in the polyol component is more preferably 70 to 100 mol%, more preferably 85 to 100 mol%, particularly preferably 90 to 100 mol%, and most preferably 100 mol. %. When the content is 30 mol% or more, the resin strength is increased and the low-temperature fixability is improved.

The polyol component may contain a polyhydric alcohol other than the aliphatic diol having 2 to 6 carbon atoms.
Among the polyhydric alcohols, dihydric alcohols (diols) include aliphatic diols having 7 to 36 carbon atoms (1,7-heptanediol, dodecanediol, etc.); polyalkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, etc.); C2-C4 alkylene oxide (hereinafter abbreviated as AO) of the aliphatic diol having 2 to 6 and 7 to 36 carbon atoms [ethylene oxide (hereinafter abbreviated as EO) ), Propylene oxide (hereinafter abbreviated as PO) and butylene oxide, etc.] adducts (addition mole number 2-30); alicyclic diols having 6-36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A) Etc.); C 2-4 of the alicyclic diol AO adducts (added mole number 2 to 30); bisphenols (bisphenol A, bisphenol F and bisphenol S, etc.) Number 2-4 AO adducts of carbon atoms in the (number of moles added: 2 to 30), and the like.

Among the polyhydric alcohols, alcohols having 3 to 8 or more valences include 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (glycerin, triethylolethane, trimethylolpropane, pentaerythritol, Sorbitol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, 1,2,5-pentanetriol, and 1,3 , 5-trihydroxymethylbenzene, etc.); AO adduct having 2 to 4 carbon atoms of the above aliphatic polyhydric alcohol (addition mole number of 2 to 30); C2-4 of trisphenols (trisphenol PA, etc.); AO adduct (addition mole number 2-30); novolak resin (phenol novolak, cresol novolak, etc .: average degree of polymerization 3 60) Number 2-4 AO adducts of carbon atoms in the (number of moles added: 2 to 30), and the like.
Among these polyhydric alcohols, preferably, a polyalkylene ether glycol having 4 to 36 carbon atoms, an alicyclic diol, an AO adduct having 2 to 4 carbon atoms of an alicyclic diol having 6 to 36 carbon atoms, and bisphenol. C2-4 AO adducts and novolak resin C2-4 AO adducts, more preferably bisphenol C2-3 AO (EO and PO) adducts, and novolacs It is an AO (EO and PO) adduct having 2 to 3 carbon atoms of the resin.

Among the polycarboxylic acid components, aliphatic (including alicyclic) dicarboxylic acids include alkane dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, and sebacic acid). And alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid).
Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid).

Among the polycarboxylic acid components, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids include aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid) and unsaturated carboxylic acids. Examples include acid vinyl polymers [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer and the like).
Among the polycarboxylic acid components, trivalent to hexavalent or higher aromatic polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and unsaturated carboxylic acids. Vinyl polymers [Mn: 450 to 10000] (such as styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumaric acid copolymer).
As the polycarboxylic acid component, anhydrides and lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these polycarboxylic acids may be used.

  Among these polycarboxylic acid components, preferred are alkane dicarboxylic acids having 2 to 50 carbon atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and 9 to 20 carbon atoms. An aromatic polycarboxylic acid, more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and combinations thereof Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

  Moreover, as a polycarboxylic acid component, what consists of aromatic polycarboxylic acid and aliphatic polycarboxylic acid, and contains 60 mol% or more of aromatic polycarboxylic acids is preferable. The lower limit of the content of the aromatic polycarboxylic acid is more preferably 70 mol%, particularly preferably 80 mol%, and the upper limit is more preferably 99 mol%, particularly preferably 98 mol%. By containing 60 mol% or more of aromatic polycarboxylic acid, the resin strength increases and the low-temperature fixability is further improved.

The polyester resin for toner (A3) of the third invention is obtained by polycondensation of one or more polyol components and one or more polycarboxylic acid components, and the polycarboxylic acid component is 80-100 mol%. , Terephthalic acid, isophthalic acid, and / or their lower alkyl ester (a) having 1 to 4 carbon atoms, and the polyol component is 20 to 100 mol% of an aliphatic diol (80 to 100 mol of the aliphatic diol). % Is 1,2-propylene glycol), and 0.1 to 20 mol% of the total of the polyol component and the polycarboxylic acid component is a trihydric or higher polyhydric alcohol and / or a trihydric or higher poly Carboxylic acid (c).
The toner polyester resin (A3) of the third invention is preferably also the polyester resin (A1) of the first invention and / or the polyester resin (A2) of the second invention.

(A) is at least one selected from terephthalic acid, isophthalic acid, and lower alkyl esters having 1 to 4 carbon atoms of the alkyl group, and the lower alkyl ester having 1 to 4 carbon atoms is hydroxyalkyl Used to include esters.
Specific examples of the lower alkyl ester include dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, propylene glycol diester terephthalate, propylene glycol diester isophthalate, and the like. Among these (a), terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, propylene glycol diester terephthalate, and propylene glycol diester isophthalate are preferable in terms of reaction rate and cost.
(A) has the effect of increasing the glass transition temperature (hereinafter referred to as Tg) of the resulting polyester resin and improving the blocking resistance of the toner, and is usually 80 to 100 moles relative to the total polycarboxylic acid component. %, Preferably 85 to 100 mol%, more preferably 90 to 100 mol%.

  As dicarboxylic acid other than (a) in the polycarboxylic acid component constituting the polyester resin, the alkane dicarboxylic acid having 2 to 50 carbon atoms, the alkene dicarboxylic acid having 4 to 50 carbon atoms, and the carbon number other than (a). Examples include 8-36 aromatic dicarboxylic acids (such as naphthalenedicarboxylic acid); their anhydrides or lower alkyl (carbon number 1 to 4) esters [(anhydrous) phthalic acid]. These can be used alone or in combination of two or more.

In the third invention, as the aliphatic diol (b), the aliphatic diol having 2 to 6 carbon atoms, the aliphatic diol having 7 to 36 carbon atoms, the polyalkylene ether glycol having 4 to 36 carbon atoms, C2-C4 AO adduct of C2-C6 and C7-C36 aliphatic diol, C6-C36 alicyclic diol, C2-C4 AO addition of alicyclic diol These can be used alone or in combination of two or more.
Among these, from the viewpoint of the balance between the toner fixing performance and the environment dependency, 80 mol% or more of the aliphatic diol used is preferably 1,2-propylene glycol. Other aliphatic diols used in addition to 1,2-propylene glycol are preferably ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. Since these (b) have the effect of lowering the melt viscosity of the polyester resin, the toner fixing performance is improved. The content thereof is preferably in the range of 20 to 100 mol%, more preferably 45 to 100 mol%, particularly preferably 60 to 100 mol%, most preferably 70 to 100 mol%, based on the total polyol component. By setting the content of (b) to 20 mol% or more, it is possible to improve the toner fixing performance and to suppress a decrease in moisture resistance.
Examples of the diol other than (b) in the polyol component constituting the polyester resin include AO adducts having 2 to 4 carbon atoms of the bisphenols.

As the trihydric or higher (3 to 8 or higher) polyhydric alcohol and / or trivalent or higher (3 to 8 or higher) polycarboxylic acid (c) used in the third invention, the carbon An aliphatic polyhydric alcohol having 3 to 36 or more valences of 3 to 36; an AO adduct having 2 to 4 carbon atoms of the aliphatic polyhydric alcohol, and an AO adduct having 2 to 4 carbon atoms of the trisphenol. , An AO adduct having 2 to 4 carbon atoms of the novolak resin, an aliphatic tricarboxylic acid having 6 to 36 carbon atoms, a vinyl polymer of the unsaturated carboxylic acid, 3 to 6 valences having 9 to 20 carbon atoms, or Examples thereof include the above aromatic polycarboxylic acids and vinyl polymers of the unsaturated carboxylic acids.
Among these, preferably, an AO adduct of 2 to 4 carbon atoms (average addition mole number of 2 to 30) of a novolak resin and an aromatic polycarboxylic acid having 3 to 6 or more valences of 9 to 20 carbon atoms ( Trimellitic acid, pyromellitic acid, and the like), and more preferably an AO (particularly EO and / or PO) adduct (average number of added moles of 2 to 30) of a novolak resin. These can be used alone or in combination of two or more. These (c) have the effect of increasing the non-offset property of the toner by crosslinking or branching the polyester resin.
The content of (c) is preferably 0.1 to 20 mol%, more preferably 0.5 to 18 mol%, based on the total of the polyol component and the polycarboxylic acid component. By setting the content to 0.1 mol% or more, a polyester resin having an appropriate viscosity and Tg can be obtained, and both non-offset property and storage stability of the toner can be achieved. By setting it as 20 mol% or less, it is possible to prevent the polyester resin from being crosslinked at an appropriate viscosity range or less, and to widen the non-offset region.

  In the third aspect of the present invention, other monomers other than the above, for example, benzoic acid, in the range of 10 mol% or less with respect to the total of the polyol component and the polycarboxylic acid component, unless the characteristics of the polyester resin are impaired. Monocarboxylic acids such as p-substituted benzoic acid, o-substituted benzoic acid, acetic acid, propionic acid, butyric acid and the like, and methyl, ethyl ester and the acid anhydride thereof; benzyl alcohol, p-substituted benzyl alcohol, o -Monools such as substituted benzyl alcohol, lauryl alcohol, mistyl alcohol and stearyl alcohol, ε-caprolactone, methylvalerolactone and the like, and hydroxycarboxylic acid derivatives such as ring-opening polymers thereof can also be used.

  The polyester resin of the third invention formed by polycondensation of the above components has a softening point of usually 95 to 160 ° C., preferably the lower limit is 100 ° C., the upper limit is 150 ° C., and more preferably the upper limit is less than 120 ° C. Yes, Tg is usually 45 to 75 ° C, preferably the lower limit is 50 ° C and the upper limit is 70 ° C.

By setting the softening point to 95 ° C. or higher, the toughness of the polyester resin is improved. On the other hand, by setting the softening point to 160 ° C. or lower, the melt fluidity and low-temperature fixability of the toner can be improved.
When the Tg is 45 ° C. or higher, the toner has good blocking resistance, and when it is 75 ° C. or lower, the toner fixing performance can be improved.
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.

  In the present invention, the polyester resins (A1) to (A3) can be produced in the same manner as in a normal polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 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.

At this time, an esterification catalyst may be used as necessary. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide, dioctyltin oxide, dioctyltin dilaurate), antimony-containing catalysts (eg, antimony trioxide), titanium-containing catalysts (eg, titanium alkoxide, potassium oxalate titanate, and Titanium terephthalate), zirconium containing catalysts (eg zirconyl acetate), nickel containing catalysts (eg nickel acetylacetonate), aluminum containing catalysts (eg aluminum hydroxide, aluminum triisopropoxide), zinc acetate, manganese acetate, etc. It is done. In these, the catalyst containing 1 or more types of metals chosen from titanium, antimony, a zirconium, nickel, and aluminum from the point of reactivity and environmental hygiene is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The amount of the catalyst added is desirably determined as appropriate so as to maximize the reaction rate. The addition amount is preferably 10 ppm to 1.9%, more preferably 100 ppm to 1.7%, based on the total raw materials. The amount added is preferably 10 ppm or more, so that the reaction rate is increased. In the above and below, “%” means “% by weight” unless otherwise specified.

  Polyester resins (A1) to (A3) of the first to third inventions (hereinafter referred to as (A) as a general term for (A1) to (A3)). The reaction ratio between the polyol component and the polycarboxylic acid component in the production of [1] 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.

As for Mn of the tetrahydrofuran (THF) soluble part of resin (A), 1000-9500 are preferable. More preferably, it is 1200-9300, Most preferably, it is 1400-9100. When the Mn is 1000 or more, the resin strength is improved, and when it is 9500 or less, the low-temperature fixability and the resin grindability are improved.
In addition, the peak top molecular weight (hereinafter referred to as Mp) of the THF-soluble component of (A) is preferably 1200 to 50000, more preferably from the viewpoint of the balance of resin strength, low-temperature fixability, and resin grindability. Is 1500-40000.

  The amount of the component having a molecular weight of 500 or less in the gel permeation chromatography of the soluble matter of THF in (A) is preferably 3% or less, more preferably 2.5% or less. When the amount of the component having a molecular weight of 500 or less is 3% or less, when used as a toner, the fluidity is further improved, and the image stability during continuous printing is improved. When two or more kinds of resins are used as (A), it is preferable that (A) as a whole is within the above range even if a resin having a large amount of components having a molecular weight of 500 or less is contained.

In the above and below, the amount of Mn, Mp, and a component having a molecular weight of 500 or less is measured under the following conditions using GPC.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μL
Detector: Refractive index detector Reference substance: Standard polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The amount of the component having a molecular weight of 500 or less is obtained from the integral values from 0 to 500 in the molecular weight distribution list. In measurement, an arbitrary particle in the resin particles is taken out and dissolved in THF as a sample solution. This sample solution is measured for 10 particles.

  The Tg of the polyester resins (A1) and (A2) of the first and second inventions is preferably 40 to 90 ° C., more preferably 45 to 85 ° C., particularly preferably from the viewpoint of heat resistant storage stability and low temperature fixability. 50-80 ° C.

The THF-insoluble content in the resin (A) is preferably 70% or less from the viewpoint of low-temperature fixability. The lower limit is more preferably 1%, particularly preferably 2%, most preferably 3%, and the upper limit is more preferably 40%, particularly preferably 30%.
Above and below, the THF-insoluble matter 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 hydroxyl value (mgKOH / g) of (A) is preferably 70 or less, more preferably 5 to 40, and particularly preferably 10 to 30. When the hydroxyl value is 70 or less, environmental stability and charge amount are improved. The acid value (mgKOH / g) of (A) is preferably 40 or less, more preferably 1 to 30, particularly preferably 2 to 25, and most preferably 5 to 20. Environmental stability improves that an acid value is 40 or less. In addition, it is preferable to have an appropriate acid value from the viewpoint of improving the rising of charging.

Two or more kinds of the polyester resin (A) of the present invention may be used in combination. From the viewpoint of compatibility between low-temperature fixability, hot offset resistance and pulverization, a linear polyester resin (Aa) and a non-linear polyester resin (Ab) May be used in combination of one or more.
The linear polyester resin (Aa) is usually obtained by polycondensation of the diol and dicarboxylic acid. Moreover, what modified | denatured the molecular terminal with the anhydride of the said polycarboxylic acid (a trivalent or more thing is included) may be used.
The nonlinear polyester resin (Ab) is usually obtained by reacting the above tricarboxylic acid and / or trihydric polyhydric alcohol together with the dicarboxylic acid and diol.
Examples of the trivalent or higher polycarboxylic acid and / or the trivalent or higher polyhydric alcohol include novolak resin having 2 to 4 carbon atoms of AO (average added mole number of 2 to 30), and 3 of 9 to 20 carbon atoms. A hexavalent or higher valent aromatic polycarboxylic acid (trimellitic acid, pyromellitic acid, etc.) is preferred, and a trivalent to hexavalent or higher valent aromatic polycarboxylic acid is more preferred.
In the case of obtaining (Ab), the ratio of the polycarboxylic acid having a valence of 3 or more and the polyhydric alcohol having a valence of 3 or more is such that the sum of these moles is the sum of the moles of all polyol components and polycarboxylic acid components. The amount is preferably 0.1 to 40 mol%, more preferably 1 to 25 mol%, and particularly preferably 3 to 20 mol%.

The THF-insoluble content of (Aa) is preferably 3% or less, more preferably 1% or less, and particularly preferably 0%. A smaller amount of (Aa) insoluble in THF is preferred from the viewpoint of improving low-temperature fixability.
The THF-insoluble matter in (Ab) is preferably 1 to 70%. The lower limit is more preferably 2%, particularly preferably 5%, and the upper limit is more preferably 60%, particularly preferably 50%. Inclusion of the THF-insoluble content in the above range is preferable from the viewpoint of improving hot offset resistance.

The polyester resin for toner of the present invention may contain other polyester resins as long as the properties of the polyester resin (A) are not impaired. Examples of other resins include polyester resins other than any one of (A1) to (A3) having Mn of 1,000 to 1,000,000, particularly 1,000 to 9,500. When (A) is a nonlinear polyester resin (Ab), as the other resin used in combination, a linear polyester resin other than (Aa) is preferable.
The content of (A) in the polyester resin is usually 20 to 100%, preferably 25 to 100%. More preferably, it is 30 to 90%. When it is 20% or more, the characteristics of the present invention are sufficiently exhibited.

The polyester resin composition for toner according to the fourth aspect of the invention is a toner comprising the polyester resin for toner (A) and a modified body (w1) in which at least a part of the wax (w) is modified with a vinyl monomer (m). It consists of additive (B).
Examples of the wax (w) used as the raw material for (B) include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and mixtures thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.
From the viewpoints of filming on a carrier and the like and releasability, Mn of the polyolefin wax is preferably 400 to 40000, more preferably 1000 to 30000, and particularly 1500 to 2000.

  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.

  Among these, preferred are polyolefin wax, natural wax, and mixtures thereof, more preferably heat-reduced polyolefin, and particularly preferably heat-reduced polyethylene and heat-reduced polypropylene.

The softening point of the wax (w) is preferably 50 to 170 ° C. The lower limit is more preferably 80 ° C., further preferably 90 ° C., particularly 100 ° C., and the upper limit is more preferably 160 ° C., particularly 155 ° C. When the softening point is 50 ° C. or higher, the fluidity of the toner is good, and when it is 170 ° C. or lower, a sufficient release effect can be obtained.
The softening point is measured by the method specified in JIS K 2207-1996.

From the viewpoint of fixing properties of the toner, the melt viscosity of (w) is usually 2 to 10000 mPa · s, preferably 3 to 7000 mPa · s, particularly 5 to 4500 mPa · s at 160 ° C.
From the viewpoint of developing properties of the toner, the penetration of (w) is usually 5.0 or less, preferably 3.5 or less, particularly 1.0 or less.
The penetration is measured by a method defined in JIS K 2207-1996.

Examples of the vinyl monomer (m) include the following monomers (a) to (f) and combinations thereof.
(A) Carboxyl group-containing vinyl monomer:
(A-1) C3-C20 unsaturated monocarboxylic acid: (meth) acrylic acid, crotonic acid, cinnamic acid and the like;
(A-2) C4-C30 unsaturated dicarboxylic acid and ester-forming derivative thereof [acid anhydride and mono- or dialkyl (alkyl having 1 to 18 carbon atoms) ester]: maleic acid, fumaric acid, itaconic acid, Citraconic acid and anhydrides thereof, and mono- or dialkyl (alkyl having 1 to 18 carbon atoms) esters (such as methyl ester and ethyl ester);

(A-3) C3-C30 unsaturated carboxylic acid alkyl (C1-C24) ester: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (Meth) acrylate and ethyl-α-ethoxy (meth) acrylate, etc .;

(A-4) C3-C30 unsaturated carboxylic acid polyvalent (2-3) alcohol ester: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, 1,6 hexanediol diacrylate, polyethylene glycol di (meth) acrylate, etc .;
(A-5) Esters of unsaturated alcohol [vinyl, isopropenyl, etc.] and mono- or polycarboxylic acid having 1 to 12 carbon atoms: vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate , Isopropenyl acetate, methyl-4-vinyl benzoate, vinyl methoxyacetate and vinyl benzoate.

(B) Hydroxyl group-containing vinyl monomer:
(B-1) a hydroxyalkyl (meth) acrylate having 5 to 16 carbon atoms, such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
(B-2) C2-C12 alkenol, for example (meth) allyl alcohol, 1-buten-3-ol and 2-buten-1-ol;
(B-3) Alkene diols having 4 to 12 carbon atoms, such as 2-butene-1,4-diol;
(B-4) C3-C30 alkenyl ethers such as 2-hydroxyethylpropenyl ether and sucrose allyl ether.

(C) Vinyl hydrocarbon:
(C-1) Aromatic vinyl-based hydrocarbons (8 to 20 carbon atoms) including styrene: Hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted styrene, such as α-methylstyrene, Vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, and trivinylbenzene; and vinylnaphthalene.
(C-2) Aliphatic vinyl hydrocarbons: alkenes having 2 to 20 carbon atoms, such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins An alkadiene having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and 1,7-octadiene;
(C-3) Alicyclic vinyl hydrocarbons: mono and dicycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene and ethylidenebicycloheptene; terpenes such as pinene, limonene and indene.

(D) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate and the like.
(E) Nitrile group-containing vinyl monomers: (meth) acrylonitrile and the like.
(F) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, N-aminoethyl (meth) acrylamide , (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone and the like.

  Among these, preferred are styrene and a combination of styrene and another monomer [preferably (a) and (b), particularly (a-3) and (b-1)].

The modified product (w1) is obtained by modifying the wax (w) with the vinyl monomer (m). In the toner additive (B) used in the present invention, the modified wax (m) grafted with (m) is used. In addition to w1), unreacted (w) and / or (m) (co) polymers may be included.
From the viewpoint of toner fluidity, the weight ratio of (w) to (m) in the production of (w1) is preferably (1-30): (70-99), particularly (2-27): ( 83-98).

The Tg of (w1) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, particularly 55 to 75 ° C. When the Tg is in the range of 40 ° C. to 90 ° C., the heat resistant storage stability and the low temperature fixability are good.
Mn of (w1) is preferably 2000 to 10000, particularly 2500 to 9000. When Mn is in the range of 2000 to 10,000, the toner has good durability and pulverization.

The toner additive (B) comprising (w1) is prepared by, for example, dissolving or dispersing wax (w) in a solvent (for example, toluene or xylene) and heating to 100 ° C. to 200 ° C. It is obtained by dropping together with an initiator (benzoyl peroxide, ditertiary butyl peroxide, tertiary butyl peroxide benzoate, etc.) and polymerizing, and then distilling off the solvent.
The amount of peroxide initiator is usually 0.2 to 10%, preferably 0.5 to 5%, based on the total weight of (w) and (m).

The resin composition for toner of the fourth invention comprises a polyester resin (A) and a toner additive (B). The weight ratio of (A) and (B) is preferably (25-99.9): (0.1-75), more preferably (50-99) in order to control the particle size of the wax in the toner. : (1-50), particularly preferably (75-98: 2-25).
In addition to (A) and (B), the polyester resin composition for a toner of the present invention may contain other resin, a release agent described later, and the like as necessary. In the present invention, the toner additive (B) has a function as a compatibilizer for improving the compatibility between the polyester resin and the release agent.

  In order to obtain the polyester resin composition for toner according to the fourth aspect of the invention, the toner additive (B) and the polyester resin (A) may be powder mixed, a twin screw extruder, or heated and stirred. It may be melt-mixed in a compounding pot or the like, and the toner additive (B) may be produced in the presence of the polyester resin (A).

  The toner composition of the fifth invention comprises a polyester resin (A) for toner of the present invention that serves as a binder resin, a colorant, and, if necessary, a release agent, a charge control agent, a fluidizing agent and the like. Contains additives.

  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, Paranitaniline 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 polyester resin 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.

The release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof.
Specific examples thereof are the same as those in the wax (w) described above.

  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 fifth invention is preferably 30 to 97%, more preferably 40 to 95%, particularly preferably 45 to 92% of the polyester resin of the present invention based on the toner weight; Is preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; among the additives, the release agent is 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%, 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, then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the particle size (D50) is preferably made into fine particles of 5 to 20 μm, and then mixed with a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  The toner composition of the present invention is electrically mixed with carrier particles such as ferrite coated on the surface with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as necessary. Used as a latent image developer. The weight ratio of toner to carrier particles is 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.
Further, by using the toner composition of the present invention, in a wide temperature range where the difference between the hot offset occurrence temperature and the minimum fixing temperature when fixing an unfixed image with a fixing machine is 95 ° C. or more (particularly 100 ° C. or more). It is easy to fix.

The non-magnetic one-component toner of the sixth invention contains at least a polyester resin (A) [polyurethane resin (A1), (A2), or (A3) of the first to third inventions]] and a colorant.
In the polyester resin (A) used in the sixth invention, the softening point (sp) and the glass transition temperature (Tg) are further surrounded by a straight line represented by the following formulas (1) to (4) [ The one in the parallelogram in FIG. 1 is used. Preferably, it is in the range represented by the following formulas (1), (2), (3 ′), and (4 ′), more preferably the following formulas (1 ′), (2 ′), It is in the range represented by (3 ″) and (4 ′).
Formula (1) sp = 4Tg-110
Formula (2) sp = 4Tg-170
Formula (3) sp = 90
Formula (4) sp = 130
Formula (1 ') sp = 4Tg-114
Formula (2 ′) sp = 4Tg−166
Formula (3 ′) sp = 93
Formula (3 ″) sp = 95
Formula (4 ′) sp = 127

That is, sp of polyester resin (A) is 90-130 degreeC. The lower limit is preferably 93 ° C, more preferably 95 ° C, and the upper limit is preferably 127 ° C. The range of Tg is, for example, 50 to 65 ° C, preferably 51 to 64 ° C when sp is 90 ° C, and 60 to 75 ° C, preferably 61 to 74 ° C when sp is 130 ° C.
In this case, if the sp is lower than the above range, an offset phenomenon may occur during fixing. If the sp is higher than the above range, the fixing energy increases, and the color toner tends to decrease glossiness and transparency. Further, when Tg is lower than the above range, toner agglomerates and fixation may occur, and when it is higher than the above range, the fixing strength at the time of thermal fixing tends to decrease, so that sp and Tg are within the above range. Preferably there is. sp can be adjusted mainly by the molecular weight of the resin, and Mn is preferably 2000-20000, more preferably 3000-12000. Moreover, Tg can be adjusted mainly by selecting a monomer component constituting the resin. Specifically, Tg can be increased by using an aromatic polycarboxylic acid as a main component as a polycarboxylic acid component.

Unlike the softening point in the second invention, the sp of the polyester resin (A) is measured using a flow tester described in JIS K7210 and K6719. Specifically, using a flow tester (CFT-500, manufactured by Shimadzu Corporation), a sample of about 1 g was heated at a rate of temperature increase of 3 ° C./min. In while heating, applying a load of 30kg / cm ² by a plunger of surface area 1 cm ^2, hole diameter 1 mm, extruded from a die of length 10 mm. Thus, a plunger stroke-temperature curve is drawn, and when the height of the S-shaped curve is h, the temperature corresponding to h / 2 is the softening point.

The polyester resin (A) may be used in combination of two or more, and consists of the linear polyester resin (Aa) and the non-linear polyester resin (Ab) in terms of both low-temperature fixability, hot offset resistance and pulverization. Is preferred. (Aa) and (Ab) may be used in combination of two or more.
The weight ratio of (Aa) to (Ab) is preferably 10/90 to 80/20, more preferably 20/80 to 75/25, and particularly preferably 25/75 to 70/30.

The polyester resin used in the sixth invention preferably comprises only the resin (A), but may contain other polyester resins as long as the properties of the polyester resin are not impaired. Other resins include polyester resins other than (A) having Mn of 1,000 to 1,000,000. The content of other resins is preferably 10% or less, more preferably 5% or less.
When other resins are used in combination with (A), it is preferable that the whole polyester resin for toner of the present invention is within the range of the preferred physical properties (molecular weight, Tg, THF insoluble matter, etc.) of (A) described above. .

Examples of the colorant used in the nonmagnetic toner of the present invention include those described above.
The nonmagnetic toner of the present invention contains at least one fine particle additive (fluidizing agent) on the surface of the particles. These are mainly intended to improve the adhesiveness, cohesiveness, fluidity and the like of toner particles, and to improve the triboelectric chargeability and durability of the toner. Specific examples include organic and inorganic fine particles whose surface may have an average primary particle size of 0.001 to 5 μm, particularly preferably 0.002 to 3 μm, such as polyvinylidene fluoride and polytetrafluoroethylene. Fluorine-based resin powders, fatty acid metal salts such as zinc stearate and calcium stearate, resin beads mainly composed of polymethyl methacrylate and silicone resin, minerals such as talc and hydrotalcite, silicon oxide (colloidal silica) Etc.), metal oxides such as aluminum oxide, titanium oxide, zinc oxide and tin oxide.

  The non-magnetic toner of the sixth invention may contain one or more additives usually used for toner, such as the above-mentioned release agent and charge control agent, if necessary.

  The composition ratio of the non-magnetic toner of the present invention is preferably 30 to 97%, more preferably 40 to 95%, particularly preferably 45 to 92% of the polyester resin (A) based on the toner weight; Preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; Of the additives, the fine particle additive is preferably 0.01 to 10%, more preferably 0.05 to 5%, particularly preferably 0.1 to 4%; release agent is preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; charge control The agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%. The total content of additives (including fine particle 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 nonmagnetic toner of the present invention may be obtained by any conventionally known method such as the kneading and pulverization method, the emulsion phase inversion method, and the polymerization method.
The non-magnetic toner of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer or the like to be used as a recording material. As a method 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.

The measuring method of the property of the polyester resin obtained by the Example and comparative example of each invention of this application is shown next.
1. Hydroxyl value A method defined in JIS K1557 (1970 edition).
When the sample had a solvent-insoluble component accompanying crosslinking, the sample after melt kneading was used as a sample by the following method.
Kneading device: Labo plast mill MODEL30R150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 30 minutes at 130 ° C. and 70 rpm Acid value A method defined in JIS K0070 (1992 edition).
When the sample had a solvent-insoluble component accompanying crosslinking, the sample after melt kneading was used as a sample in the same manner as the hydroxyl value.
3. Softening point (hereinafter also referred to as Tm)
According to the softening point measurement method of the second invention described above.

<< Examples of the first to third inventions >>
[Examples 1-4, Comparative Examples 1-4]
Example 1
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 639 parts (24.5 mol) of 1,2-propylene glycol (hereinafter simply referred to as propylene glycol), bisphenol A · EO 2 mol adduct 180 Parts (1.6 mol), 653 parts (9.8 mol) dimethyl terephthalate, 10 parts (0.2 mol) adipic acid, and 3 parts tetrabutoxy titanate as a condensation catalyst, at 180 ° C. under a nitrogen stream And reacted for 8 hours while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point becomes 90 ° C. It was taken out at the time. The recovered propylene glycol was 263 parts (10.1 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-1).
In the linear polyester (Aa-1), Mn is 1500, Mp is 2500, the amount of the component having a molecular weight of 500 or less is 3.0%, the THF insoluble content is 0%, and the molar average cohesive energy of the polyol component (hereinafter referred to as En). ) Was 82 kJ, storage elastic modulus at 150 ° C. (hereinafter referred to as G ′) was 300, Tm was 90 ° C., loss tangent at 130 ° C. to 200 ° C. (hereinafter referred to as tan δ) was 5 to 11 (however, Since the temperature range exceeding 150 ° C. was too low to be measured, values in the range of 130 ° C. to 150 ° C. are also described for the following linear polyesters.
In addition, the number of moles in () is described to show the relative molar ratio of each raw material (the same applies to the following examples).
[Synthesis of nonlinear polyester]
In the same reaction vessel as above, 614 parts (23.8 moles) of propylene glycol, 156 parts (1.4 moles) of bisphenol A · EO 2 mole adduct, 627 parts (9.5 moles) of dimethyl terephthalate, adipine 25 parts (0.5 mol) of acid and 3 parts of tetrabutoxytitanate were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 288 parts (11.2 mol). Next, the mixture was cooled to 180 ° C., 98 parts (1.5 mol) of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. and normal pressure, and when the softening point reached 180 ° C. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as nonlinear polyester (Ab-1).
In the non-linear polyester (Ab-1), Mn is 4000, Mp is 8000, the amount of the component having a molecular weight of 500 or less is 1.3%, the THF insoluble content is 30%, En is 82 kJ, and G ′ is 3.6 × 10 ^5. , Tm was 180 ° C., and tan δ was 1.2 to 2.0.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-1) and 400 parts of non-linear polyester (Ab-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a polyester resin (1) for toner of the present invention.
The polyester resin for toner (1) had a Tg of 64 ° C., an Mn of 2200, an Mp of 3200, an amount of a component having a molecular weight of 500 or less, 2.3%, and a THF insoluble content of 13%.

Example 2
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 720 parts (23.8 moles) propylene glycol, 735 parts (9.5 moles) dimethyl terephthalate, 29 parts (0.5 moles) adipic acid, and tetrabutoxy titanate. 3 parts were added, reacted in the same manner as the linear polyester (Aa-1) of Example 1, and taken out when the softening point reached 94 ° C. The recovered propylene glycol was 235 parts (7.8 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-2).
In the linear polyester (Aa-2), Mn is 2700, Mp is 5800, the amount of the component having a molecular weight of 500 or less is 2.0%, THF insoluble matter is 0%, En is 73 kJ, G ′ is 300, Tm is 90 ° C. , Tan δ was 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 663 parts (22.5 mol) of propylene glycol, 677 parts (9.0 mol) of dimethyl terephthalate, 57 parts (1.0 mol) of adipic acid, and tetrabutoxy titanate. 3 parts were added and reacted in the same manner as the nonlinear polyester (Ab-1) of Example 1. The recovered propylene glycol was 251 parts (8.5 mol). Next, the mixture was cooled to 180 ° C., added with 112 parts (1.5 mol) of trimellitic anhydride, reacted in the same manner as (Ab-1), taken out when the softening point reached 180 ° C., cooled to room temperature, Grinded into particles. This is designated as nonlinear polyester (Ab-2).
In the non-linear polyester (Ab-2), Mn is 3900, Mp is 8000, the amount of the component having a molecular weight of 500 or less is 1.3%, THF insoluble matter is 29%, En is 73 kJ, and G ′ is 3.6 × 10 ^5. , Tm was 180 ° C., and tan δ was 1.2 to 2.1.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-2) and 400 parts of non-linear polyester (Ab-2) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin (2) for toner of the present invention.
The polyester resin (2) for toner had a Tg of 64 ° C., Mn of 3200, Mp of 6700, the amount of components having a molecular weight of 500 or less was 1.6%, and the THF-insoluble content was 13%.

Example 3
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 701 parts (18.8 moles) of propylene glycol, 716 parts (7.5 moles) of dimethyl terephthalate, 180 parts (2.5 moles) of adipic acid, and tetra 3 parts of butoxy titanate was added, reacted in the same manner as the linear polyester (Aa-1) of Example 1, and taken out when the softening point reached 150 ° C. The recovered propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-3).
In the linear polyester (Aa-3), Mn is 8000, Mp is 20000, the amount of the component having a molecular weight of 500 or less is 1.6%, THF insoluble content is 0%, En is 73 kJ, and G ′ is 1.6 × 10 ^6. , Tm was 150 ° C. and tan δ was 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 557 parts (17.5 moles) propylene glycol, 569 parts (7.0 moles) dimethyl terephthalate, 184 parts (3.0 moles) adipic acid, and tetrabutoxy titanate. 3 parts were added and reacted in the same manner as the nonlinear polyester (Ab-1) of Example 1. The recovered propylene glycol was 175 parts (5.5 mol). Next, the mixture was cooled to 180 ° C., 121 parts (1.5 mol) of trimellitic anhydride was added, reacted in the same manner as (Ab-1), taken out when the softening point reached 180 ° C., cooled to room temperature, Grinded into particles. This is designated as nonlinear polyester (Ab-3).
In the non-linear polyester (Ab-3), Mn is 8500, Mp is 23000, the amount of the component having a molecular weight of 500 or less is 0.9%, the THF insoluble content is 30%, En is 73 kJ, and G ′ is 3.6 × 10 ^5. , Tm was 180 ° C. and tan δ was 1.2 to 1.9.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-3) and 400 parts of non-linear polyester (Ab-3) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin (3) for toner of the present invention.
The polyester resin for toner (3) had a Tg of 62 ° C., an Mn of 8100, an Mp of 22000, an amount of a component having a molecular weight of 500 or less, 1.3%, and a THF insoluble content of 13%.

Example 4
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 540 parts (25.0 moles) of propylene glycol, 372 parts (4.0 moles) of adduct of bisphenol A and EO 2 moles, 551 parts (10.0 moles) of dimethyl terephthalate And 3 parts of tetrabutoxy titanate were added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 94 ° C. It was taken out at the time. The recovered propylene glycol was 281 parts (13.0 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-4).
In the linear polyester (Aa-4), Mn is 2700, Mp is 5800, the amount of components having a molecular weight of 500 or less is 2.5%, THF insoluble content is 0%, En is 96 kJ, G ′ is 300, Tm is 94 ° C. , Tan δ was 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 531 parts (24.3 moles) of propylene glycol, 330 parts (3.5 moles) of bisphenol A · EO2 mole adduct, 542 parts (9.7 moles) of dimethyl terephthalate. Then, 13 parts (0.3 mol) of adipic acid and 3 parts of tetrabutoxy titanate were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 301 parts (13.8 mol). Next, the mixture was cooled to 180 ° C., 83 parts (1.5 mol) of trimellitic anhydride was added, reacted for 2 hours under sealed atmospheric pressure, reacted at 220 ° C. and normal pressure, and when the softening point reached 180 ° C. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as nonlinear polyester (Ab-4).
In the non-linear polyester (Ab-4), Mn is 4000, Mp is 8000, the amount of the component having a molecular weight of 500 or less is 1.3%, THF insoluble matter is 31%, En is 96 kJ, and G ′ is 3.6 × 10 ^5. , Tm was 180 ° C., and tan δ was 1.1 to 1.4.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-4) and 400 parts of nonlinear polyester (Ab-4) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and pulverized to obtain a polyester resin (4) for toner of the present invention.
The polyester resin (4) for toner of the present invention had a Tg of 63 ° C., an Mn of 3200, an Mp of 6700, an amount of a component having a molecular weight of 500 or less, 1.9%, and a THF insoluble content of 14%.

Comparative Example 1
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 466 parts (9.0 moles) of bisphenol A · PO 2 mole adduct, 341 parts (7.0 moles) of bisphenol A · EO 2 mole adduct, 247 parts of terephthalic acid (10. 0 mol) and 3 parts of tetrabutoxy titanate were added and reacted at 230 ° C. under 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 reached 2, the mixture was cooled to 180 ° C., 74 parts (2.6 mol) of trimellitic anhydride was added, and the reaction was taken out after 2 hours of reaction under normal pressure and sealed. After cooling to room temperature, it was pulverized into particles. This is designated as linear polyester (Aa′-5).
In the linear polyester (Aa′-5), Mn is 1500, Mp is 2500, the amount of components having a molecular weight of 500 or less is 4.2%, THF insoluble matter is 0%, En is 166 kJ, G ′ is 300, Tm is 90 The ° C. and tan δ were 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 679 parts (10.8 moles) of bisphenol A · PO3 mole adduct, 47 parts (0.37 moles) of EO adduct of phenol novolac, 260 parts of terephthalic acid (10.0 moles) Mol) and 3 parts of tetrabutoxy titanate were added and reacted at 230 ° C. under a nitrogen stream for 7 hours while distilling off generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., added with 87 parts (2.9 mol) of trimellitic anhydride, and reacted for 2 hours under sealed at atmospheric pressure. The mixture was reacted at 220 ° C. and normal pressure, taken out when the softening point reached 180 ° C., cooled to room temperature, pulverized and granulated. This is designated as non-linear polyester (Ab′-5).
In the non-linear polyester (Ab′-5), Mn is 4200, Mp is 7400, the amount of components having a molecular weight of 500 or less is 3.2%, THF insoluble matter is 42%, En is 184 kJ, and G ′ is 5.0 × 10. ⁵ and Tm were 94 ° C. and tan δ was 0.3 to 0.7.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-5) and 400 parts of non-linear polyester (Ab′-5) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a comparative polyester resin for toner (1).
Comparative polyester resin for toner (1) had a Tg of 64 ° C., Mn of 2600, Mp of 4500, the amount of a component having a molecular weight of 500 or less was 3.8%, and the THF insoluble content was 16%.

Comparative Example 2
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 404 parts (7.0 moles) of bisphenol A · PO2 mole adduct, 380 parts (7.0 moles) of bisphenol A · EO2 mole adduct, 276 parts (10. 0 mol), and 3 parts of tetrabutoxy titanate were added and reacted at 230 ° C. under 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, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., 74 parts (2.3 mol) of trimellitic anhydride was added, and the reaction was performed for 2 hours under atmospheric pressure sealing. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as linear polyester (Aa′-6).
In the linear polyester (Aa′-6), Mn is 1900, Mp is 4200, the amount of components having a molecular weight of 500 or less is 4.0%, THF-insoluble content is 0%, En is 90 kJ, G ′ is 300, Tm is 90 The ° C. and tan δ were 5-11.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-6) and 400 parts of non-linear polyester (Ab′-5) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized by a pulverizer, and granulated to obtain a comparative polyester resin (2) for toner.
The Tg of the comparative polyester resin for toner (2) was 64 ° C., Mn was 2800, Mp was 5500, the amount of the component having a molecular weight of 500 or less was 3.7%, and the THF insoluble content was 17%.

Comparative Example 3
[Synthesis of linear polyester]
In a reaction vessel similar to that in Example 1, 692 parts (25.0 mol) of propylene glycol, 707 parts (10.0 mol) of dimethyl terephthalate, and 3 parts of tetrabutoxy titanate as a condensation catalyst were added at 180 ° C. The reaction was carried out for 8 hours while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and the reaction was further performed for 1 hour under reduced pressure of 5 to 20 mmHg, and then taken out. The recovered propylene glycol was 166 parts (6.0 mol). Thereafter, it was cooled to room temperature, but it was not converted into a resin and was in the form of a paste. This is designated as linear polyester (Aa′-7).
The Mn of the linear polyester (Aa′-7) was 800, the Mp was 1200, and the THF insoluble content was 0%. Since (Aa′-7) was not resinized, it was not used for toner preparation.

Comparative Example 4
[Synthesis of linear polyester]
In a reaction vessel similar to that in Example 1, 722 parts (10.3 moles) of bisphenol A · EO 2 mole adduct, 356 parts (10.0 moles) of terephthalic acid and 3 parts of tetrabutoxy titanate as a condensation catalyst were added. The reaction was allowed to proceed for 5 hours while distilling off the water produced under a nitrogen stream at ° 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 25 parts (0.6 mol) of trimellitic anhydride, and reacted for 2 hours under sealed at atmospheric pressure. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as linear polyester (Aa′-8).
In the linear polyester (Aa′-8), Mn is 7000, Mp is 19000, the amount of components having a molecular weight of 500 or less is 3.3%, THF-insoluble content is 0%, En is 164 kJ, and G ′ is 1.0 × 10. ⁵ and Tm were 140 ° C. and tan δ at 130 to 200 ° C. was 0.8 to 4.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 693 parts (10.8 moles) of bisphenol A / PO3 mole adduct, 48 parts (0.37 moles) of EO adduct of phenol novolac, 239 parts of terephthalic acid (9.0 parts) Mol) and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react at 230 ° C. for 7 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., added with 89 parts (2.9 mol) of trimellitic anhydride, and reacted for 2 hours under sealed atmosphere. The mixture was reacted at 220 ° C. and normal pressure, taken out when the softening point reached 180 ° C., cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab′-8).
The non-linear polyester (Ab′-8) has an Mn of 8800, an Mp of 22000, an amount of a component having a molecular weight of 500 or less is 3.3%, an THF insoluble content is 42%, an En is 184 kJ, and a G ′ is 5.0 × 10. ⁵ and Tm were 180 ° C. and tan δ was 0.3 to 0.7.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-8) and 400 parts of non-linear polyester (Ab′-8) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature and then pulverized by a pulverizer to form particles, thereby obtaining a comparative polyester resin (4) for toner.
In the comparative polyester resin for toner (4), the Tg was 63 ° C., the Mn was 8000, the Mp was 21,000, the amount of the component having a molecular weight of 500 or less was 3.3%, and the THF insoluble content was 16%.

Examples (1) to (4) and Comparative Examples (1) to (2), (4)
Carbon black MA-100 [Mitsubishi Chemical Co., Ltd.] with respect to 100 parts of each of the polyester resins for toner (1) to (4) of the present invention and the polyester resins for comparison toner (1) to (2) and (4). 8 parts, 5 parts of carnauba wax, and 1 part of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] were added to form toner.
First, after pre-mixing 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 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 toners (1) to (4) of the present invention and the comparative toners (1) to ( 2) and (4) were obtained.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

[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 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 to the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
[3] Gloss development temperature (Gross)
In the same manner as the MFT, the developed unfixed image was evaluated for fixing using a fixing device of a commercially available color printer (LBP2160; manufactured by Canon). The fixing roll temperature at which the 60 ° gloss of the fixed image was 10% or more was defined as the gloss development temperature.
[4] Toner fluidity The quietness density of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the toner fluidity was judged according to the following criteria. Δ or more is the practical range.
Quiet density (g / 100ml) 36 or more: Toner fluidity ○
33 to less than 36: ○ △
30 to less than 33: △
27-30 or less: △ ×
Less than 27: ×
[5] Grindability A toner coarsely pulverized product (with 8.6 mesh pass to 30 mesh on) kneaded and cooled by a biaxial kneader is used as a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.] Was pulverized under the following conditions.
Crushing pressure: 0.5 MPa
Adjuster ring: 15mm
Size of louver: Medium Grinding time: 10 minutes Without classification, the volume average particle size was measured with Coulter Counter-TAII (manufactured by Coulter Electronics, USA), and used as a grindability test. In this measurement method, it can be said that the grindability is good when the volume average particle size is 12 μm or less.

[Examples 11 to 12, Comparative Examples 11 to 13]
Example 11
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 817 parts (22.6 moles) of propylene glycol, 831 parts (9.0 moles) of dimethyl terephthalate, 70 parts (1.0 moles) of adipic acid and tetracondensation as a condensation catalyst. 3 parts of butoxytitanate was added and reacted for 8 hours at 180 ° C. while distilling off methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off propylene glycol and water generated under a nitrogen stream, and further, the reaction was performed for 1 hour under a reduced pressure of 5 to 20 mmHg. When the softening point reaches 85 ° C., the mixture is cooled to 180 ° C., 37 parts (0.4 mol) of trimellitic anhydride is added, and after reacting for 2 hours under normal pressure sealing, the reaction is performed at 220 ° C. and normal pressure. It was taken out when the point reached 160 ° C. The recovered propylene glycol was 450 parts (12 moles). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (Ab-1).
Nonlinear polyester (Ab-11) has a Tg of 60 ° C., Mn of 5800, peak top molecular weight of 10,000, THF insoluble content of 3%, En of 73 kJ, G ′ of 1.6 × 10 ⁵ , Tm of 160 ° C., Tan δ was 1.2 to 2.5.
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 782 parts (22.7 moles) of 1,2-propylene glycol, 834 parts (9.5 moles) of dimethyl terephthalate, 33 parts (0.5 moles) of adipic acid and As a condensation catalyst, 3 parts of tetrabutoxy titanate was added and reacted for 8 hours while distilling off methanol produced at 180 ° C. under a nitrogen stream. Then, while gradually raising the temperature to 230 ° C., propylene glycol generated under a nitrogen stream and water were reacted for 4 hours while distilling off water, and further reacted under reduced pressure of 5 to 20 mmHg, and the softening point became 95 ° C. It cooled at the time. The recovered propylene glycol was 380 parts (11 mol). When the temperature reached 180 ° C., 17 parts of trimellitic anhydride was charged, held at 180 ° C. for 1.5 hours, and then taken out. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-11).
The linear polyester (Aa-11) had a Tg of 60 ° C., Mn of 2800, a peak top molecular weight of 5800, En of 73 kJ, G ′ of 140, Tm of 100 ° C., and tan δ of 4 to 20.
[Synthesis of polyester resin for toner]
400 parts of nonlinear polyester (Ab-11) and 600 parts of linear polyester (Aa-11) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin (11) for toner of the present invention.

Example 12
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 391 parts (22.3 mol) of propylene glycol, 358 parts (8.0 mol) of dimethyl terephthalate, 67 parts (2.0 mol) of adipic acid, and tetracondensation as a condensation catalyst. 3 parts of butoxy titanate was added and reacted for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off propylene glycol and water generated under a nitrogen stream. Next, 561 parts (7 moles) of bisphenol A propylene oxide 2 mole adduct, 56 parts of phenol novolak resin (core number 5.6) and ethylene oxide adduct (0.3 moles) were charged, and 230 ° C. and normal pressure for 4 hours. After the reaction, the reaction was performed under a reduced pressure of 5 to 20 mmHg, and the reaction was cooled when the softening point reached 90 ° C. When the temperature reached 180 ° C., 20 parts (0.45 mol) of trimellitic anhydride was charged, held at 180 ° C. for 1.5 hours, and then heated to 220 ° C. The reaction was appropriately performed by reducing the pressure at 5 to 20 mmHg, and the reaction was taken out when the softening point reached 135 ° C. The recovered propylene glycol was 314 parts (17.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (Ab-12).
Nonlinear polyester (Ab-12) has a Tg of 60 ° C., Mn of 4200, a peak top molecular weight of 7800, a THF-insoluble content of 3%, En of 97 kJ, G ′ of 1.36 × 10 ⁴ , Tm of 135 ° C., Tan δ was 1.2 to 1.9.
[Polyester resin for toner]
The nonlinear polyester (Ab-12) obtained by this synthesis was used as a polyester resin for toner (12).

Comparative Example 11
[Synthesis of nonlinear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 552 parts (2.5 mol) of propylene oxide 2-mole adduct of bisphenol A and 184 parts (8 mol) of ethylene oxide 2-mole adduct of bisphenol A Then, 287 parts (8.2 mol) of terephthalic acid and 3 parts of dibutyltin oxide were added, and dehydration esterification was performed at 230 ° C. under a nitrogen stream. When distillate water ceased to come out, the pressure was reduced and esterification proceeded until the acid value reached 1.0. Thereafter, the temperature was set to 220 ° C., and 49 parts (1.2 mol) of trimellitic anhydride was added and held for 1 hour. Then, it was made to react suitably under reduced pressure of 5-20 mmHg, and when the softening point became 115 degreeC, it took out from the reaction tank, and nonlinear polyester (Ab'-13) was obtained. Polyester (Ab′-13) has a Tg of 60 ° C., Mn of 3200, peak top molecular weight of 5800, THF insoluble content of 0%, En of 165 kJ, G ′ of 5.8 × 10 ³ , Tm of 115 ° C. tan δ was 1.1 to 5.2.
[Polyester resin for toner]
The nonlinear polyester (Ab′-13) obtained by this synthesis was used as a comparative polyester resin for toner (11).

Comparative Example 12
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 138 parts (2.2 mol) of bisphenol A propylene oxide 2 mol adduct, 616 parts (8.5 mol) of bisphenol A propylene oxide 2 mol adduct, 224 parts of terephthalic acid (7 0.5 mol) and 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 230 ° C. under a nitrogen stream for 7 hours while distilling off the produced water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value reached 1, it was cooled to 180 ° C., 87 parts (2.5 mol) of trimellitic anhydride was added, and after 2 hours of reaction under atmospheric pressure sealing, The reaction was carried out at 220 ° C., normal pressure, and appropriately from 5 to 20 mmHg, and the mixture was taken out when the softening point reached 185 ° C., cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab′-14).
Non-linear polyester (Ab′-14) had Mn of 6000, Mp of 10,000, En of 183 kJ, G ′ of 5.0 × 10 ⁵ , Tm of 185 ° C., and tan δ of 0.1 to 0.4.
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 552 parts (10.0 mol) of bisphenol A propylene oxide 2 mol adduct, 208 parts (4.0 mol) of bisphenol A ethylene oxide 2 mol adduct, 263 parts of terephthalic acid (10 0.0 mol) and 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 230 ° C. in a nitrogen stream while distilling off the water produced. Next, when the acid value reached 1.5, the mixture was cooled to 180 ° C., 34 parts of trimellitic anhydride was added, the reaction was taken out for 2 hours under normal pressure sealing, the mixture was taken out, cooled to room temperature, pulverized and granulated. This is designated as linear polyester (Aa′-14).
The Mn of the linear polyester (Aa′-14) was 2800, Mp was 5200, En was 166 kJ, G ′ was 1.4 × 10 ² , Tm was 100 ° C., and tan δ was 3 to 15.
[Creation of polyester resin for toner]
400 parts of nonlinear polyester (Ab′-14) and 600 parts of linear polyester (Aa′-14) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a comparative polyester resin for toner (12).

Comparative Example 13
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 137 parts (2.2 mol) of bisphenol A propylene oxide 2 mol adduct, 612 parts (8.5 mol) of bisphenol A propylene oxide 2 mol adduct, 267 parts of terephthalic acid (9 mol) 0.0 mol) and 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 230 ° C. under a nitrogen stream for 7 hours while distilling off the produced water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value reached 1, it was cooled to 180 ° C., 52 parts (1.5 mol) of trimellitic anhydride was added, and after reaction for 2 hours under normal pressure sealing, The reaction was carried out at 220 ° C., normal pressure, and appropriately from 5 to 20 mmHg, and the mixture was taken out when the softening point reached 160 ° C., cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab′-15).
Mn of the non-linear polyester (Ab′-15) was 11000, Mp was 240000, En was 183 kJ, G ′ was 2.4 × 10 ⁵ , Tm was 160 ° C., and tan δ was 0.5 to 0.9.
[Creation of polyester resin for toner]
400 parts of nonlinear polyester (Ab′-15) and 600 parts of linear polyester (Aa′-14) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a comparative polyester resin (13) for toner.

Examples (11) to (12) and Comparative Examples (11) to (13)
8 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 5 parts of carnauba wax with respect to 100 parts of polyester resins (11) to (12) and toner polyester resins (11) to (13) of comparative toner of the present invention. Was added to the toner by the following method.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) in a sample mill, and the toners (11) to (12) of the present invention and comparative toners (11) to (11) ( 13) was obtained.
The evaluation results evaluated by the evaluation method are shown in Table 2.

[Examples 21 to 24, Comparative Examples 21 to 22]
Example 21
In the same reaction vessel as in Example 1, 127 parts of propylene glycol, 454 parts of dimethyl terephthalate, 38 parts of adipic acid, 452 parts of bisphenol A propylene oxide 2-mol adduct, phenol novolak resin (average degree of polymerization 5.6) 2.3 parts of EO adduct and 3 parts of tetrabutoxytitanate as a condensation catalyst were allowed to react at 180 ° C. for 12 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under reduced pressure of 5 to 20 mmHg. When the softening point reaches 98 ° C. Cooled down. When the temperature reached 180 ° C., 17 parts of trimellitic anhydride was added, stirred for 1 hour, reacted, and then taken out. The polyester resin [21] taken out had Mn of 3600, Mp of 8000, Tg of 60 ° C., En of 114 kJ, G ′ of 140, Tm of 102 ° C., and tan δ of 6 to 11.

Example 22
In a reaction vessel similar to that in Example 1, 347 parts of propylene glycol, 317 parts of dimethyl terephthalate, 60 parts of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst are produced at 180 ° C. in a nitrogen stream. The reaction was allowed to proceed for 8 hours while removing methanol. Next, 596 parts of bisphenol A propylene oxide 2 mol adduct and 2.3 parts of EO adduct of phenol novolac resin (average polymerization degree 5.6) were added, and the mixture was generated in a nitrogen stream while gradually raising the temperature to 230 ° C. The reaction was carried out for 4 hours while distilling off propylene glycol and water, and further the reaction was carried out under reduced pressure of 5 to 20 mmHg, and the mixture was cooled when the softening point reached 98 ° C. The recovered propylene glycol was 295 parts. When the temperature reached 180 ° C., 17 parts of trimellitic anhydride was added, stirred for 1 hour, and taken out after reaction. The polyester resin [22] taken out had Mn of 3700, Mp of 7900, Tg of 60 ° C., En of 140 kJ, G ′ of 150, Tm of 102 ° C., and tan δ of 5 to 11.

Example 23
In the same reaction vessel as in Example 1, 380 parts of propylene glycol, 46 parts of an EO adduct of phenol novolak resin (average polymerization degree 5.6), 351 parts of dimethyl terephthalate, 28 parts of adipic acid, and a condensation catalyst 3 parts of tetrabutoxy titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg. It was taken out at the time. The recovered propylene glycol was 190 parts. The extracted polyester resin [23] has Mn of 3700, Mp of 11000, Tg of 65 ° C., En of 73 kJ, G ′ of 8.7 × 10 ³ , Tm of 142 ° C., and tan δ of 1.6 to 1.8. there were.

Comparative Example 21
In a reaction vessel similar to Example 1, 453 parts of ethylene glycol diester terephthalate, 36 parts of adipic acid, and 3 parts of dibutyltin oxide as a condensation catalyst were added, 596 parts of bisphenol A propylene oxide 2 mol adduct, 0 trimellitic acid 0 .9 parts, gradually increasing the temperature to 230 ° C., reacting for 7 hours while distilling off ethylene glycol and water in a nitrogen stream, and further reacting under reduced pressure of 1 to 20 mmHg, with a softening point of 98 It cooled when it became ° C. The recovered ethylene glycol was 239 parts. When the temperature reached 180 ° C., 17 parts of trimellitic anhydride was added, stirred for 1 hour, and taken out after reaction. The comparative polyester resin [21 ′] taken out had Mn of 4200, Mp of 8100, Tg of 58 ° C., En of 167 kJ, G ′ of 140, Tm of 101 ° C., and tan δ of 4 to 11.

Example 24, Comparative Example 22
To 100 parts of each of the polyester resins [21] to [23] and the comparative polyester resin [21 ′] of the present invention, 8 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 5 parts of carnauba wax are added, and the toner is prepared by the following method. Turned into.
First, after pre-mixing 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 pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) in a sample mill to obtain toners (21) to (23) of the present invention and a comparative toner (21). It was.

  Table 3 shows the evaluation results evaluated by the evaluation method. However, the image density was evaluated for fixing in the same manner as the MFT, and the image density was measured using a Macbeth densitometer.

<< Example according to the fourth invention >>
[Production Examples 31-33, Comparative Production Examples 31-32]
Production Example 31 (Polyester resin)
[Synthesis of linear polyester]
The linear polyester (Aa-1) of Example 1 is synthesized to obtain a linear polyester (Aa-31).
[Synthesis of nonlinear polyester]
The nonlinear polyester (Ab-1) of Example 1 is synthesized to obtain a nonlinear polyester (Ab-31).

Production Example 32 (Polyester resin)
[Synthesis of linear polyester]
The linear polyester (Aa-2) of Example 2 is synthesized into a linear polyester (Aa-32).
[Synthesis of nonlinear polyester]
The nonlinear polyester (Ab-2) of Example 2 is synthesized to obtain a nonlinear polyester (Ab-32).

Production Example 33 (Additive for Toner)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene, 480 parts of heat-reduced low molecular weight polypropylene (Viscol 440P manufactured by Sanyo Chemical Industries, Ltd .: softening point 153 ° C.), heat-reduced low molecular weight polyethylene ( Sanyo Kasei Kogyo Co., Ltd. Sunwax LEL-400: Softening point 128 ° C.) 120 parts are added and dissolved sufficiently, and after substitution with nitrogen, styrene 1992 parts, acrylonitrile 168 parts, monobutyl maleate 240 parts, di-t-butyl par A mixed solution of 78 parts of oxyhexahydroterephthalate and 455 parts of xylene was added dropwise at 175 ° C. over 3 hours for polymerization, and the temperature was further maintained for 30 minutes. Next, the solvent was removed to obtain a toner additive (B-1) comprising a wax modified product.
Mn of (B-1) was 2950, the weight average molecular weight was 10900, and the acid value was 20.9 mgKOH / g.

Comparative Production Example 31 (Polyester resin)
[Synthesis of linear polyester]
The linear polyester (Aa′-6) of Comparative Example 2 is synthesized and used as a comparative linear polyester (Aa′-31).
[Synthesis of nonlinear polyester]
The nonlinear polyester (Ab′-5) of Comparative Example 1 is synthesized and used as a comparative nonlinear polyester (Ab′-31).

Comparative Production Example 32
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 1200 parts of xylene were placed, and after substitution with nitrogen, 1992 parts of styrene, 168 parts of acrylonitrile, 240 parts of monobutyl maleate, 78 parts of di-t-butylperoxyhexahydroterephthalate A mixed solution of 455 parts of xylene was added dropwise at 175 ° C. over 3 hours for polymerization, and the temperature was further maintained at this temperature for 30 minutes. Subsequently, the solvent was removed to obtain a comparative toner additive (B′-1).
Mn of (B′-1) was 2900, the weight average molecular weight was 9800, and the acid value was 25.8.

[Examples 31-32 and Comparative Examples 31-32]
Example 31
[Preparation of polyester resin composition for toner]
580 parts of linear polyester (Aa-31), 400 parts of non-linear polyester (Ab-31) and 20 parts of additive (B-1) for toner are melted in a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. Mixed. The molten resin was cooled to room temperature, pulverized with a pulverizer, and pulverized to obtain a toner resin composition (31) of the present invention.
The resin composition for toner (31) had a Tg of 64 ° C., an Mn of 2200, an Mp of 3200, and a THF-insoluble content of 13%.

Example 32
[Preparation of polyester resin composition for toner]
580 parts of linear polyester (Aa-32), 400 parts of non-linear polyester (Ab-32) and 20 parts of toner additive (B-1) were melt-mixed in a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. did. The molten resin was cooled to room temperature, pulverized with a pulverizer, and pulverized to obtain a toner resin composition (32) of the present invention.
The resin composition for toner (32) had a Tg of 64 ° C., an Mn of 3200, an Mp of 6700, and a THF-insoluble content of 13%.

Comparative Example 31
[Preparation of polyester resin composition for toner]
580 parts of linear polyester (Aa'-31), 400 parts of non-linear polyester (Ab'-31) and 20 parts of additive (B-1) for toner in a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes Melt mixed. The molten resin was cooled to room temperature, pulverized with a pulverizer, and pulverized to obtain a comparative resin composition for toner (31).
The comparative resin composition for toner (31) had a Tg of 64 ° C., an Mn of 3200, an Mp of 6700, and a THF-insoluble content of 13%.

Comparative Example 32
[Preparation of polyester resin composition for toner]
580 parts of linear polyester (Aa-32) and 400 parts of non-linear polyester (Ab-32) and 20 parts of additive for toner (B′-1) were compared with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. And melt mixed. The molten resin was cooled to room temperature, then pulverized with a pulverizer, and granulated to obtain a comparative resin composition for toner (32).
The comparative resin composition for toner (32) had a Tg of 64 ° C., an Mn of 3200, an Mp of 6700, and a THF-insoluble content of 13%.

Evaluation examples (31) to (32) and comparative evaluation examples (31) to (32)
Carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] with respect to 100 parts of each of the resin compositions for toner (31) to (32) of the present invention and the resin composition parts for comparative toner (31) to (32). 8 parts, 5 parts of carnauba wax and 1 part of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] were added to form a toner by the following method.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toners (31) to (32) of the present invention and comparative toners (31) to (31) ( 32) was obtained.
Table 4 shows the evaluation results evaluated by the following evaluation methods.

[Evaluation methods]
[1] Minimum fixing temperature (MFT)
According to the method.
[2] Hot offset generation temperature (HOT)
According to the method.
[3] Toner fluidity According to the above method.
[4] Image Stability Using a commercially available printer (LP-1300), the prepared toner was filled and solid images were continuously printed. The 5000th image was visually judged according to the following criteria.
No unevenness and white streaks: ○
Some white streaks but no unevenness: △
There are white streaks, unevenness: ×

<< Example according to the sixth invention >>
[Production Examples 41 to 43, Comparative Production Examples 41 to 44]
Production Example 41
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 792 parts (22.8 moles) of propylene glycol, 868 parts (9.8 moles) of dimethyl terephthalate, 13 parts (0.2 moles) of adipic acid, and a condensation catalyst 3 parts of tetrabutoxy titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is performed under a reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is 80. When it became 0 degreeC, it cooled to 180 degreeC, 26 parts (0.3 mol) of trimellitic anhydride was added, and it took out after reaction for 2 hours under normal pressure sealing. The recovered propylene glycol was 410 parts (11.8 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-41).
Tg of linear polyester (Aa-41) is 56 ° C., Mn is 2200, Mp is 4000, THF insoluble content is 0%, En is 73 kJ, G ′ is 2.0 × 10 ² , Tm is 82 ° C., tan δ is 4-12.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 810 parts (22.4 mol) of propylene glycol, 774 parts (8.4 mol) of dimethyl terephthalate, 111 parts (1.6 mol) of adipic acid, and a condensation catalyst 3 parts of tetrabutoxy titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 427 parts (11.8 mol). Next, it is cooled to 180 ° C., 18 parts (0.2 mol) of trimellitic anhydride is added, and after reacting for 2 hours under atmospheric pressure sealing, the reaction is performed at 220 ° C. under reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is When the temperature reached 125 ° C., the product was taken out, cooled to room temperature, and pulverized into particles. This is designated as nonlinear polyester (Ab-41).
Nonlinear polyester (Ab-41) has a Tg of 55 ° C., Mn of 7000, Mp of 16000, THF insoluble content of 3%, En of 73 kJ, G ′ of 6.8 × 10 ² , Tm of 125 ° C., tan δ of 2.8-4.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-41) and 400 parts of nonlinear polyester (Ab-41) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin for toner (A-41) of the present invention.
The polyester resin for toner (A-41) had a Tg of 55 ° C., an Sp of 98 ° C., an Mn of 4500, an Mp of 5000, and a THF insoluble content of 2%. As shown in FIG. 1, Tg and Sp were within the range surrounded by the formulas (1) to (4).

Production Example 42
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 803 parts (22.6 moles) of propylene glycol, 816 parts (9.0 moles) of dimethyl terephthalate, 68 parts (1.0 moles) of adipic acid, and a condensation catalyst 3 parts of tetrabutoxy titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is 93. When it became 0 degreeC, it cooled to 180 degreeC, 26 parts (0.3 mol) of trimellitic anhydrides were added, and it took out after reaction for 2 hours under normal pressure sealing. The recovered propylene glycol was 427 parts (12.0 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-42).
Tg of linear polyester (Aa-42) is 55 ° C., Mn is 3000, Mp is 5800, THF insoluble content is 0%, En is 73 kJ, G ′ is 2.2 × 10 ² , Tm is 95 ° C., tan δ is 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 780 parts of propylene glycol (22.6 moles), 793 parts of dimethyl terephthalate (9.0 moles), 66 parts of adipic acid (1.0 moles), and a condensation catalyst 3 parts of tetrabutoxy titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 397 parts (11.5 mol). Next, it is cooled to 180 ° C., 44 parts (0.5 mol) of trimellitic anhydride is added, and after reacting for 2 hours under atmospheric pressure sealing, it is reacted under reduced pressure of 220 ° C. and 5-20 mmHg, and the softening point (Tm) is When it reached 145 ° C., it was taken out, cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab-42).
Nonlinear polyester (Ab-42) has a Tg of 66 ° C., Mn of 6800, Mp of 10500, THF insoluble content of 2%, En of 73 kJ, G ′ of 2.0 × 10 ³ , Tm of 145 ° C., and tan δ of It was 1.5 to 1.9.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-42) and 400 parts of nonlinear polyester (Ab-42) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin for toner (A-42) of the present invention.
The polyester resin for toner (A-42) had Tg of 60 ° C., Sp of 110 ° C., Mn of 5000, Mp of 6500, and THF insoluble content of 1%. As shown in FIG. 1, Tg and Sp were within the range surrounded by the formulas (1) to (4).

Production Example 43
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 634 parts (22.7 mol) of propylene glycol, 256 parts (2.0 mol) of bisphenol A · PO2 mol adduct, 658 parts (9.2 mol) of dimethyl terephthalate. Then, 43 parts (0.8 mol) of adipic acid and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is 93. When it became 0 degreeC, it cooled to 180 degreeC, 26 parts (0.4 mol) of trimellitic anhydride was added, and it took out after reaction for 2 hours under normal pressure sealing. The recovered propylene glycol was 390 parts (13.9 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa-43).
Tg of linear polyester (Aa-43) is 65 ° C., Mn is 3300, Mp is 6200, THF insoluble content is 0%, En is 90 kJ, G ′ is 2.2 × 10 ² , Tm is 95 ° C., tan δ is 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 582 parts (22.7 moles) of propylene glycol, 326 parts (2.4 moles) of bisphenol A / PO3 mole adduct, 603 parts (9.2 moles) of dimethyl terephthalate Then, 39 parts (0.8 mol) of adipic acid and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 360 parts (14.0 mol). Next, the mixture was cooled to 180 ° C., 23 parts (0.4 mol) of trimellitic anhydride was added, and after reacting for 2 hours under normal pressure sealing, the reaction was performed at 220 ° C. under reduced pressure of 5 to 20 mmHg, and the softening point (Tm) was When it reached 160 ° C., it was taken out, cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab-43).
Nonlinear polyester (Ab-43) has a Tg of 65 ° C., Mn of 7000, Mp of 13,200, THF insoluble content of 3%, En of 97 kJ, G ′ of 9.5 × 10 ³ , Tm of 160 ° C., tan δ of It was 1.2 to 2.2.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa-43) and 400 parts of nonlinear polyester (Ab-43) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin for toner (A-43) of the present invention.
The polyester resin for toner (A-43) had a Tg of 65 ° C., an Sp of 125 ° C., an Mn of 5100, an Mp of 6500, and a THF-insoluble content of 2%. As shown in FIG. 1, Tg and Sp were within the range surrounded by the formulas (1) to (4).

Comparative Production Example 41
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 642 parts (11.9 mol) of bisphenol A · PO 2 mol adduct, 131 parts (2.1 mol) of bisphenol A · PO 3 mol adduct, 257 parts of terephthalic acid (10. 0 mol), and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react 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 26 parts (0.9 mol) of trimellitic anhydride, and reacted for 2 hours under sealed atmosphere. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as linear polyester (Aa′-41).
Linear polyester (Aa′-41) has a Tg of 55 ° C., Mn of 2000, Mp of 4000, THF insoluble content of 0%, En of 170 kJ, G ′ of 2.0 × 10 ² , Tm of 82 ° C., tan δ Was 4-12.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 777 parts (12.5 moles) of bisphenol A · PO3 mole adduct, 171 parts (6.7 moles) of terephthalic acid, 59 parts (2.0 moles) of trimellitic anhydride Then, 3 parts of tetrabutoxy titanate was added as a condensation catalyst, and the reaction was carried out for 7 hours at 230 ° C. under a stream of nitrogen while distilling off the generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., 60 parts (3.3 mol) of fumaric acid was added, and after reacting at normal pressure for 4 hours, The reaction was conducted under a reduced pressure of 20 mmHg, and the mixture was taken out when the softening point (Tm) reached 115 ° C., cooled to room temperature, pulverized and granulated. This is designated as nonlinear polyester (Ab′-41).
Nonlinear polyester (Ab′-41) has a Tg of 56 ° C., Mn of 6500, Mp of 9500, THF insoluble content of 5%, En of 184 kJ, G ′ of 6.8 × 10 ² , Tm of 125 ° C., tan δ Was 0.7 to 1.1.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-41) and 400 parts of non-linear polyester (Ab′-41) were melt-mixed using a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a comparative polyester resin for toner (A′-41).
The comparative polyester resin for toner (A′-41) had a Tg of 56 ° C., an Sp of 96 ° C., an Mn of 4000, an Mp of 5000, and a THF insoluble content of 3%. As shown in FIG. 1, Tg and Sp were within the range surrounded by the formulas (1) to (4).

Comparative Production Example 42
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 490 parts (8.4 moles) of bisphenol A · PO2 mole adduct, 266 parts (4.0 moles) of bisphenol A · PO3 mole adduct, 278 parts of terephthalic acid (10. 0 mol) and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react for 5 hours while distilling off the water produced at 230 ° C. 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., added with 26 parts (0.8 mol) of trimellitic anhydride, and reacted for 2 hours under sealed atmosphere. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as linear polyester (Aa′-42).
Tg of linear polyester (Aa′-42) is 65 ° C., Mn is 3000, Mp is 5900, THF insoluble content is 0%, En is 172 kJ, G ′ is 2.3 × 10 ² , Tm is 95 ° C., tan δ Was 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 210 parts (4.2 moles) of bisphenol A · PO2 mole adduct, 567 parts (9.8 moles) of bisphenol A · PO3 mole adduct, 159 parts of terephthalic acid (6. 7 mol), 56 parts of fumaric acid (3.3 mol)) and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 210 ° C. under a nitrogen stream for 7 hours while distilling off the produced water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., 74 parts (2.7 mol) of trimellitic anhydride was added, and the reaction was performed for 2 hours under atmospheric pressure sealing. The reaction was carried out under reduced pressure of 220 ° C. and 5 to 20 mmHg, and when the softening point (Tm) reached 160 ° C., the mixture was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (Ab′-42).
Nonlinear polyester (Ab′-42) has a Tg of 67 ° C., Mn of 4000, Mp of 7500, THF insoluble content of 45%, En of 179 kJ, G ′ of 1.2 × 10 ⁴ , Tm of 160 ° C., tan δ Was 0.5 to 0.8.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-42) and 400 parts of nonlinear polyester (Ab′-42) were melt-mixed using a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, then pulverized by a pulverizer, and granulated to obtain a comparative polyester resin for toner (A′-42).
The comparative polyester resin for toner (A′-42) had a Tg of 66 ° C., an Sp of 125 ° C., an Mn of 3500, an Mp of 6000, and a THF insoluble content of 23%. As shown in FIG. 1, Tg and Sp were within the range surrounded by the formulas (1) to (4).

Comparative Production Example 43
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 385 parts (22.6 mol) of propylene glycol, 156 parts (2.0 mol) of bisphenol A · PO2 mol adduct, 451 parts of bisphenol A · PO3 mol adduct (5. 0 mol), 391 parts (9.0 mol) of dimethyl terephthalate, 33 parts (1.0 mol) of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst, and produced at 180 ° C. under a nitrogen stream. The reaction was allowed to proceed for 8 hours while distilling off the methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is performed under a reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is 93. When it became 0 degreeC, it cooled to 180 degreeC, 26 parts (0.6 mol) of trimellitic anhydrides were added, and it took out after reaction for 2 hours under normal pressure sealing. The recovered propylene glycol was 304 parts (17.9 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa′-43).
Linear polyester (Aa′-43) has a Tg of 52 ° C., Mn of 2900, Mp of 5800, THF insoluble content of 0%, En of 136 kJ, G ′ of 2.3 × 10 ² , Tm of 95 ° C., tan δ Was 5-11.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 132 parts (8.0 moles) of propylene glycol, 653 parts (7.5 moles) of bisphenol A / PO3 mole adduct, 140 parts (3.3 moles) of dimethyl terephthalate. Then, 83 parts (2.0 mol) of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 61 parts (3.7 mol). Next, the mixture was cooled to 180 ° C., 167 parts (6.7 mol) of fumaric acid was added, reacted at normal pressure for 4 hours, and then reacted under reduced pressure of 5 to 20 mmHg, when the softening point (Tm) reached 130 ° C. And cooled to room temperature, pulverized into particles. This is designated as nonlinear polyester (Ab′-43).
Nonlinear polyester (Ab′-43) has a Tg of 52 ° C., Mn of 6500, Mp of 10,000, THF insoluble content of 5%, En of 143 kJ, G ′ of 1.8 × 10 ³ , Tm of 130 ° C., tan δ Was 0.7 to 1.1.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-43) and 400 parts of non-linear polyester (Ab′-43) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin (A′-43) for toner of the present invention.
The polyester resin for toner (A′-43) had Tg of 52 ° C., Sp of 108 ° C., Mn of 4500, Mp of 6500, and THF insoluble content of 3%. As shown in FIG. 1, Tg and Sp were out of the range surrounded by the formulas (1) to (4).

Comparative Production Example 44
[Synthesis of linear polyester]
In the same reaction vessel as in Example 1, 329 parts (22.9 mol) of propylene glycol, 395 parts (6.0 mol) of bisphenol A · PO2 mol adduct, 304 parts (4. 0 mol), 363 parts (9.9 mol) of dimethyl terephthalate, 3 parts (0.1 mol) of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst, and produced at 180 ° C. under a nitrogen stream. The reaction was allowed to proceed for 8 hours while distilling off the methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point (Tm) is 95. When it became 0 degreeC, it cooled to 180 degreeC, 26 parts (0.7 mol) of trimellitic anhydrides were added, and it took out after reaction for 2 hours under normal pressure sealing. The recovered propylene glycol was 299 parts (20.8 mol). The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (Aa′-44).
Linear polyester (Aa′-44) has a Tg of 77 ° C., Mn of 3000, Mp of 6000, THF insoluble content of 0%, En of 156 kJ, G ′ of 2.4 × 10 ² , Tm of 97 ° C., tan δ Was 2-8.
[Synthesis of nonlinear polyester]
In the same reaction vessel as in Example 1, 330 parts (22.6 moles) of propylene glycol, 656 parts (9.8 moles) of bisphenol A · PO2 mole adduct, 373 parts (10.0 moles) of dimethyl terephthalate And 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 297 parts (20.3 mol). Next, it is cooled to 180 ° C., 74 parts (2.0 mol) of trimellitic anhydride is added, and after reacting for 2 hours under normal pressure sealing, the reaction is carried out under reduced pressure of 230 ° C. and 5-20 mmHg, and the softening point (Tm) is When the temperature reached 132 ° C., the product was taken out, cooled to room temperature, and pulverized into particles. This is designated as nonlinear polyester (Ab′-44).
Nonlinear polyester (Ab′-44) has a Tg of 77 ° C., Mn of 6600, Mp of 9800, THF insoluble content of 5%, En of 149 kJ, G ′ of 1.9 × 10 ³ , Tm of 132 ° C., tan δ Was 0.7 to 1.1.
[Creation of polyester resin for toner]
600 parts of linear polyester (Aa′-44) and 400 parts of nonlinear polyester (Ab′-44) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and granulated to obtain a polyester resin for toner (A′-44) of the present invention.
The polyester resin for toner (A′-44) had a Tg of 77 ° C., an Sp of 110 ° C., an Mn of 4200, an Mp of 6600, and a THF-insoluble content of 3%. As shown in FIG. 1, Tg and Sp were out of the range surrounded by the formulas (1) to (4).

[Examples 41 to 43, Comparative Examples 41 to 44]
To 100 parts of polyester resins for toner (A-41) to (A-43) and comparative polyester resins for toner (A′-41) to (A′-44), yellow pigment [toner manufactured by Clariant Co., Ltd. 4 parts of yellow HG VP2155], 5 parts of carnauba wax, and 1 part of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] were added to form toner.
First, after pre-mixing 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 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 toners (41) to (43) of the present invention and the comparative toners (41) to (41) 44) was obtained.
Table 5 shows the evaluation results evaluated by the following evaluation methods.

[Evaluation methods]
[1] Minimum fixing temperature (MFT)
According to the method.
[2] Hot offset generation temperature (HOT)
According to the method.
[3] Color Tone In the same manner as in the above MFT, the image was fixed on an OHP film at a fixing roll temperature of 170 ° C., a fixed image was transferred through an overhead projector, and the color tone was visually determined.
Judgment criteria ○: Vivid light yellow
Δ: Bright yellow
X: Slightly dull yellow [4] Grindability According to the above method.

The toner composition of the present invention using the polyester resin for toner of the present invention has an excellent balance of low-temperature fixability, hot offset resistance and pulverization, and is useful as an electrostatic image developing toner, particularly a color toner.
The toner of the sixth invention is useful as a toner for developing electrostatic images because of its excellent balance of low-temperature fixability, hot offset resistance, and pulverization properties, and particularly useful as a color toner in terms of gloss and transparency. It is.

Claims (8)

  In the polyester resin for toner obtained by polycondensation of a polyol component and a polycarboxylic acid component, the polycarboxylic acid component is 80-100 mol% of terephthalic acid, isophthalic acid, and / or their lower alkyl (carbon of alkyl group). Number: 1-4) It consists of ester (a), and a polyol component is 20-100 mol% aliphatic diol (80-100 mol% of the aliphatic diol is 1,2-propylene glycol) (b) The total of the polyol component and the polycarboxylic acid component is 0.1 to 20 mol% is a trihydric or higher polyhydric alcohol and / or a trivalent or higher polycarboxylic acid (c), and has a softening point of 95 to 95. 160 ° C., glass transition temperature (Tg) of 45 to 75 ° C., linear polyester resin (Aa) and nonlinear polyester resin (Ab), Polyester resin for a toner which is characterized by comprising a non-linear polyester resin (Ab) (A3).   The polyester resin for toner according to claim 1, wherein (A3) is a polyester resin having a number average molecular weight of 1000 to 9500 in a tetrahydrofuran-soluble component.   (A3) is a combination of a linear polyester resin (Aa) and a non-linear polyester resin (Ab), or (A3) is a non-linear polyester resin (Ab), and the number average molecular weight is other than (Aa) of 1000 to 9500 The polyester resin for toner according to claim 1, which is used in combination with a linear polyester resin.   The toner according to claim 1, wherein (A3) is a resin obtained by polycondensation in the presence of a polymerization catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel, and aluminum. Polyester resin.   The polyester resin for toner according to any one of claims 1 to 4, wherein the THF-insoluble matter in (A3) is 1 to 70% by weight.   A toner resin (B) comprising the polyester resin for toner according to any one of claims 1 to 5 and a modified body (w1) in which at least a part of the wax (w) is modified with a vinyl monomer (m). A polyester resin composition for toner.   The polyester resin for toner according to any one of claims 1 to 5 and a colorant, or one selected from the polyester resin for toner, a colorant, a release agent, a charge control agent, and a fluidizing agent. A toner composition comprising the above additives. In the non-magnetic one-component toner used in the image forming method for developing the latent image by supplying the toner to the latent image carrier, the toner is a polyester resin for toner (A3) according to any one of claims 1 to 5, And (A3) when the glass transition temperature (Tg) is a variable on the x-axis and the softening point (sp) is a variable on the y-axis plotted on the xy coordinates, the following formulas (1) to (4) A non-magnetic one-component toner having physical properties within a range surrounded by a straight line represented by the formula (1) and containing one or more fine particle additives on the surface of the toner particles.
Formula (1) sp = 4Tg-110
Formula (2) sp = 4Tg-170
Formula (3) sp = 90
Formula (4) sp = 130