JP2023143700A - Toner and two-component developer - Google Patents

Abstract

To provide toner excellent in the low-temperature fixability, image heat resistance and curling resistance.SOLUTION: A toner includes a toner particle containing a binder resin and a crystalline polyester. In differential scanning calorimetry (DSC) of the toner, after such processes that (i) the toner is heated to 180°C at a rate of 10°C/min, then (ii) cooled from 180°C to 25°C at a rate of 10°C/min and (iii) successively cooled from 25°C to 15°C at a rate of 3°C/min, and heated again to 180°C at a rate of 10°C/min, an exothermic amount P1 of a peak derived from the crystalline polyester existing at 40°C or higher and 80°C or lower in the cooling process at a rate of 10°C/min of the toner is 1.00 J/g or less, an exothermic amount P2 of a crystallization peak derived from the crystalline polyester existing in the cooling process at a rate of 3°C/min of the toner is 0.10 J/g or more, and when a sum of endothermic amount of the endothermic peaks existing at 40°C or higher observed in the second heating process of DSC of the toner is P3 (J/g), and a sum of exothermic amount of the exothermic peaks existing at 40°C or higher observed in the cooling process at a rate of 10°C/min of the toner is P4 (J/g), the following formula (1) is satisfied. The formula (1): 2.0≤P3-P4≤10.0.SELECTED DRAWING: None

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, and the like, and a two-component developer using the toner.

In recent years, as electrophotographic full-color copiers have become widespread, there has been a demand for not only faster speeds and higher image quality, but also additional performance improvements such as energy-saving performance and support for a wide variety of media. There is.
Specifically, as a toner compatible with energy saving, there is a demand for a toner that can be fixed at a lower temperature and has excellent low-temperature fixing properties in order to reduce power consumption in the fixing process. Patent Document 1 proposes a toner that uses crystalline polyester as a binder resin as a toner with excellent low-temperature fixability.
Furthermore, coated paper, which is one of a wide variety of media, has high smoothness and a large load when stacked, so the contact area is large and the toner of the fixed image is transferred to the overlapping paper. It becomes easier to do. In other words, a toner with excellent image heat resistance is required as a toner compatible with a wide variety of media.
For example, Patent Document 2 proposes a toner with controlled crystalline sites and amorphous sites in crystalline polyester as a toner with excellent low-temperature fixability and image heat resistance.

Japanese Patent Application Publication No. 2004-046095 Japanese Patent Application Publication No. 2016-033648

The toner described in Patent Document 1 uses crystalline polyester. Crystalline polyester has sharp melting properties compared to amorphous polyester, and also works as a plasticizer for amorphous polyester, so it is an effective material for low-temperature fixing of toner. However, when the crystalline polyester is excessively compatible with the binder resin, image heat resistance deteriorates, and problems such as image sticking during storage at high temperatures may occur.
On the other hand, the toner described in Patent Document 2 has excellent low-temperature fixability and image heat resistance because it controls the crystalline sites and amorphous sites in crystalline polyester and is made to easily crystallize when cooled. It becomes. However, since crystalline polyester easily crystallizes, the paper may curl due to rapid volumetric shrinkage after fixing.
From the above, there are problems in satisfying all of the low-temperature fixability, image heat resistance, and curl resistance.
An object of the present invention is to provide a toner that solves the above problems. Specifically, the objective is to provide a toner with excellent low-temperature fixability, heat-resistant storage stability, and curl resistance.

The present invention provides a toner having toner particles containing a binder resin and a crystalline polyester,
In differential scanning calorimetry (DSC) of the toner, (i) the temperature was raised to 180°C at a rate of 10°C/min, (ii) the toner was cooled from 180°C to 25°C at a rate of 10°C/min, and ( iii) After that, when the toner is cooled from 25°C to 15°C at a rate of 3°C/min, and the toner is heated a second time to 180°C at a rate of 10°C/min,
In the cooling process of the toner at a speed of 10° C./min, the calorific value P1 of the peak derived from the crystalline polyester existing at 40° C. or higher and 80° C. or lower is 1.00 J/g or less;
The calorific value P2 of the crystallization peak derived from the crystalline polyester present during the cooling process of the toner at a rate of 3° C./min is 0.10 J/g or more,
P3 (J/g) of the sum of the endothermic amounts of the endothermic peaks present at 40°C or higher observed during the second temperature raising process of DSC of the toner, observed during the cooling process of the toner at a rate of 10°C/min. The present invention relates to a toner that satisfies the following formula (1), where P4 (J/g) is the sum of the calorific values of exothermic peaks existing at 40° C. or higher.
Formula (1) 2.0≦P3-P4≦10.0
The present invention also provides a two-component developer containing a toner and a magnetic carrier,
The present invention relates to a two-component developer in which the toner has the above structure.

According to the present invention, it is possible to provide a toner with excellent low-temperature fixability, heat-resistant storage stability, and curl resistance.

[Features of the present invention]
The present invention provides a toner having toner particles containing a binder resin and a crystalline polyester,
In differential scanning calorimetry (DSC) of the toner,
(i) After increasing the temperature to 180°C at a rate of 10°C/min,
(ii) cooling the toner from 180°C to 25°C at a rate of 10°C/min;
(iii) After that, when the toner is cooled from 25°C to 15°C at a rate of 3°C/min, and the toner is heated a second time to 180°C at a rate of 10°C/min,
In the cooling process of the toner at a speed of 10° C./min, the calorific value P1 of the peak derived from the crystalline polyester existing at 40° C. or higher and 80° C. or lower is 1.00 J/g or less;
The calorific value P2 of the crystallization peak derived from the crystalline polyester present during the cooling process of the toner at a rate of 3° C./min is 0.10 J/g or more,
P3 (J/g) of the sum of the endothermic amounts of the endothermic peaks present at 40°C or higher observed during the second temperature raising process of DSC of the toner, observed during the cooling process of the toner at a rate of 10°C/min. When the sum of the calorific values of the exothermic peaks existing at 40° C. or higher is P4 (J/g), the following formula (1) is satisfied.
Formula (1) 2.0≦P3-P4≦10.0

The present inventors consider the effects of using the toner of the present invention having such a configuration as follows.

The toner of the present invention contains a binder resin and a crystalline polyester. Here, "binder resin" refers to the sum of amorphous resin and crystalline resin. During fixing, the crystalline polyester becomes compatible with the amorphous resin, improving low-temperature fixability. If the image crystallizes rapidly during cooling thereafter, the image heat resistance is good, but there is a problem in curl resistance. This state can be understood by the peak calorific value P1 during cooling in differential scanning calorimetry (DSC), and if P1 is large, the curl resistance may deteriorate. In order to improve curl resistance while not deteriorating image heat resistance, rapid crystallization should not occur during cooling (P1 is small), and there should be a time limit for the image to be bonded when high temperature heat is applied. We thought that a system in which crystallization could occur was necessary.

Therefore, the present inventors verified various combinations of resins while controlling the compatibility between the amorphous resin and the crystalline resin. As a result, by setting P1, which is the crystallization peak during rapid cooling of the DSC, to 1.00 J/g or less, we have ensured low-temperature fixing performance and curl resistance, while maintaining the peak when cooling slowly afterwards. A certain P2 is observed to be 0.10 J/g or more, and the amount of crystals P3 observed in the subsequent temperature increase is 2.00 J compared to P4, which is the total amount crystallized during cooling, at the second temperature increase by DSC. It has been found that a toner with improved image heat resistance can be obtained by increasing the amount of heat resistance to /g or more. In particular, it is important that a slight peak appear when cooling slowly.

The toner of the present invention has P1 of 1.00 J/g or less, which can ensure curl resistance, but for even better curl resistance, it is preferable that P1 be 0.50 J/g or less.

Further, P3-P4 of the toner of the present invention is 2.0 or more and 10.0 or less, and by controlling it within this range, it is possible to achieve the optimum rate of crystal growth during standing. If P3-P4 is smaller than 2.0, the image heat resistance will deteriorate due to insufficient crystallization, and if P3-P4 is larger than 10.0, the amount of crystal precipitation will be excessive, resulting in insufficient image heat resistance. Not only the properties are not obtained, but also the curl resistance deteriorates.

The content of the crystalline polyester in the binder resin of the toner of the present invention is preferably 8.0% by mass or more and 15.0% by mass or less from the viewpoints of low-temperature fixability, image heat resistance, and curl resistance. When the amount is less than 8.0% by mass, low-temperature fixing properties tend to deteriorate and crystal growth becomes difficult, so that P2 and P3-P4 become too small, which tends to deteriorate image heat resistance. If it exceeds 15.0% by mass, P1 becomes too large, which not only tends to deteriorate curl resistance but also tends to deteriorate image heat resistance.

The toner of the present invention further contains a hydrocarbon wax, and the difference between the melting point T1 (°C) of the hydrocarbon wax in the toner and the melting point T2 (°C) of the crystalline polyester is determined by the following formula (2). ) is preferably satisfied.
Formula (2) 2≦T1-T2≦10

Hydrocarbon wax has moderate compatibility with crystalline polyester, and has a melting point within the above range, so it can moderately promote crystallization and improve low-temperature fixing properties, image heat resistance, and curl resistance. It becomes easier to balance both. When T1-T2 is less than 2, crystallization of the crystalline polyester is promoted too much, and low-temperature fixability and curl resistance tend to deteriorate. When T1-T2 is larger than 10, crystallization becomes difficult and image heat resistance tends to deteriorate.

In the toner of the present invention, the binder resin contains amorphous resin A, amorphous resin B, and amorphous resin C, and the SP value of the amorphous resin A [(J/cm ³ ) ^0.5 ] SP1, SP value [(J/cm ³ ) ^0.5 ] of amorphous resin B is SP2, SP value [(J/cm ³ ) ^0.5 ] of amorphous resin C is SP3, and SP value of the above crystalline polyester. When [(J/cm ³ ) ^0.5 ] is SP4, it is preferable that the following formulas (3) to (5) are satisfied.
Formula (3) 2.00≦SP1-SP4≦2.90
Formula (4) 0.20≦SP2-SP1≦0.60
Formula (5) 0.20≦SP3-SP2≦0.60

By having a resin composition that satisfies these formulas, the compatibility of the crystalline polyester can be controlled and crystallization can be performed slowly without excessive crystallization. Amorphous resin A has an SP value closest to that of crystalline polyester, and this satisfies the relationship of formula (3), thereby improving low-temperature fixability. If SP1-SP4 is smaller than 2.00, they will be too compatible, resulting in P2 and P3-P4 becoming too small, and image heat resistance will tend to deteriorate. When SP1-SP4 is greater than 2.9, compatibility deteriorates and P1 becomes too large, which tends to deteriorate low-temperature fixability and curl resistance.

Amorphous resin B is a resin that has compatibility between amorphous resin A and amorphous resin C, and satisfies formula (4) to ensure the miscibility of amorphous resin A and amorphous resin C. This has the role of adjusting P2, which tends to increase P2. As a result, low-temperature fixability and image heat resistance are improved.

The amorphous resin C is a resin that is required not to make P1 too large while promoting the crystallization of the crystalline polyester, and therefore preferably satisfies the relationship of formula (5). When SP3-SP2 is smaller than 0.20, it becomes difficult to crystallize, the value of P2 and P3-P4 become small, and image heat resistance tends to deteriorate. When SP3-SP2 is larger than 0.60, P1 becomes too large due to excessive crystallization, and low-temperature fixability and curl resistance tend to deteriorate. Furthermore, when two types of amorphous resins are used as the binder resin without using amorphous resin C, P2 and P3-P4 become too small, and image heat resistance tends to deteriorate.

Note that the SP values of these resins can be controlled by the types and amounts of monomers of the amorphous resin and crystalline polyester. In particular, the amorphous resin C preferably has a polarity difference in its molecules, and preferably contains a hybrid resin of polyester and acrylic.

[Toner composition of the present invention]
Hereinafter, the structure of the toner of the present invention will be explained in detail.

<Amorphous resin>
As the amorphous resin used in the toner of the present invention, it is preferable to use three types of resins having different SP values. As for its structure, the resin with the smallest SP value is amorphous resin A, the resin with the next smallest SP value is amorphous resin B, and the resin with the largest SP value is amorphous resin C. The combination of resins used needs to be clearly distinguishable by GPC, and includes, for example, low molecular weight polyester, high molecular weight polyester, and hybrid resin that is a composite of polyester resin and acrylic resin. These materials have weight average molecular weights that differ by three times or more, or materials that have significantly different compositions such as polyester and hybrid resins.

For these, the following polymers or resins can be used.

For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers , styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin , acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron-indene resin, petroleum resin, composites of these Polymerized hybrid resins can be used.

Among these, from the viewpoint of low-temperature fixability, it is preferable to use polyester resin as the main component. The main component indicates that the content thereof is 50.0% by mass or more.

Monomers used in the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polycarboxylic acids (divalent or trivalent or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters. is used.

In order to produce a branched polymer, it is effective to partially crosslink within the molecules of the amorphous resin, and for this purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer for the polyester contains a trivalent or higher carboxylic acid, an acid anhydride thereof, or a lower alkyl ester thereof, and/or a trivalent or higher alcohol.

As the polyhydric alcohol monomer used in the polyester resin, the following monomers can be used.

Dihydric alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol and its derivatives represented by formula (A); diols represented by formula (B); mentioned

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
式（Ｂ）で示されるジオール類；

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)
Diols represented by formula (B);

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. Can be mentioned. Among these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

As the polycarboxylic acid monomer used in the polyester resin, the following monomers can be used.

Examples of divalent carboxylic acid components include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids and These lower alkyl esters are mentioned.

Among these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferably used.

Examples of trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra( (methylenecarboxyl)methane, 1,2,7,8-octane tetracarboxylic acid, pyromellitic acid, Empol trimer acid, acid anhydrides thereof, or lower alkyl esters thereof.

Among these, 1,2,4-benzenetricarboxylic acid, ie, trimellitic acid, or a derivative thereof is particularly preferably used because it is inexpensive and the reaction can be easily controlled. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

The method for producing polyester resin is not particularly limited, and any known method can be used. For example, the above-mentioned alcohol monomer and carboxylic acid monomer are simultaneously charged and polymerized through an esterification reaction or transesterification reaction and a condensation reaction to produce a polyester resin. Further, the polymerization temperature is not particularly limited, but is preferably in the range of 180°C or more and 290°C or less.

When polymerizing polyester, a polyester resin polymerized using a tin-based catalyst, which can use a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide, is more preferable.

It is preferable that the amorphous resin contains a hybrid resin that is a composite of a polyester resin and an acrylic resin. Containing a hybrid resin creates an intramolecular polarity difference, which can promote crystal growth of the crystalline polyester over time. The method for producing the hybrid resin is not particularly limited, but the following methods may be mentioned.
(i) A method of manufacturing by performing a transesterification reaction between a polyester component and a polymer containing a monomer component having an ester group such as an acrylic ester or a methacrylic ester.
(ii) A method of manufacturing by carrying out an esterification reaction between a polyester component and a polymer containing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid.
(iii) A method for producing by polymerizing monomer components constituting an acrylic copolymer region in the presence of a polyester region containing a monomer component having an unsaturated bond such as fumaric acid.

As mentioned above, the hybrid resin contains a monomer that can react with both sites in the monomer component that constitutes the acrylic copolymer site and/or in the monomer component that configures the polyester site, A preferred example is a method of producing by reacting them.

Among these methods, method (iii) is preferable because it can create a structure in which polyester resin is crosslinked with acrylic resin. This structure results in a structure in which acrylic resin is sandwiched between polyester resins. In this structure, the crosslinking site has an SP value that is compatible with crystalline polyester, and while the crosslinked polyester resin has a SP value that is different from that of crystalline polyester, it is structurally an ester that is compatible with crystalline polyester. It has a certain proportion of groups. This structure contributes to suppressing the rapid crystallization of crystalline polyester and promoting crystal growth over time, making it possible to achieve both low-temperature fixability, image heat resistance, and curl resistance. . When using this hybrid resin as one of three types of amorphous resins, it is important to design the resin so that its SP value as a whole is the highest among the three types of amorphous resins. Preferable from the viewpoint of crystal growth.

The crosslinking site is not limited to acrylic resins, and examples include copolymers of styrene components and acrylic acid and/or methacrylic acid components.

Examples of monomers used in the crosslinking site include the following.

Monomers used for the crosslinking site include styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-phenylstyrene, methyl methacrylate, ethyl methacrylate, and propyl methacrylate. , n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. α-methylene aliphatic monocarboxylic acid esters, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid esters such as stearyl acid, 2-chloroethyl acrylate, and phenyl acrylate are included. Among these, methyl methacrylate and ethyl methacrylate are preferably used.

When the amorphous resin contains amorphous resin A, amorphous resin B, and amorphous resin C, the content thereof is 10 parts by mass or more and 60 parts by mass or less in 100 parts by mass of the binder resin. It is preferable.

<Crystalline polyester>
Crystalline polyester is used for the toner particles. Crystalline polyester is a resin whose endothermic peak is observed in differential scanning calorimetry (DSC).

Crystalline polyester is obtained by polycondensation reaction of a monomer composition containing as main components an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. preferable.

As the polyhydric alcohol monomer used in the polyester unit of the crystalline polyester, the following polyhydric alcohol monomers can be used.

The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, deca Examples include methylene glycol and neopentyl glycol. Among these, linear aliphatic and α,ω-diols such as ethylene glycol and 1,4-butanediol are particularly preferred.

Of the alcohol component, preferably 50% by mass or more, more preferably 70% by mass or more is alcohol selected from aliphatic diols having 2 to 4 carbon atoms.

In the present invention, polyhydric alcohol monomers other than the above polyhydric alcohols can also be used. Among the polyhydric alcohol monomers, dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Furthermore, among the polyhydric alcohol monomers, examples of polyhydric alcohol monomers having a valence of 3 or higher include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol; , 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and other fats. Examples include group alcohols.

Furthermore, monohydric alcohol may be used as the crystalline polyester. Examples of the monohydric alcohol include monoalcohols such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol, caprylic alcohol (decanol), and undecanol. , lauryl alcohol (dodecanol), tridecanol, myristyl alcohol (tetradecanol), pentadecanol, palmityl alcohol (hexadecanol), margaryl alcohol (heptadecanol), stearyl alcohol (octadecanol), nonadecanol, araki Examples include dicyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, 1-heptacosanol, montanyl alcohol, 1-nonacosanol, myricyl alcohol, and the like.

As the polycarboxylic acid monomer used in the polyester unit of the crystalline polyester, the following polycarboxylic acid monomers can be used.

The polyhydric carboxylic acid monomer is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, Examples include maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also include hydrolyzed acid anhydrides or lower alkyl esters of these acids. Of the above carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more, is a carboxylic acid selected from aliphatic dicarboxylic acids having 12 to 14 carbon atoms.

In the present invention, polyvalent carboxylic acids other than the above polyvalent carboxylic acid monomers can also be used. Among other polyvalent carboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; cyclohexanedicarboxylic acid; Examples include alicyclic carboxylic acids such as acids, and also include acid anhydrides and lower alkyl esters thereof. Among other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1, Aromatic carboxylic acids such as 2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 Examples include aliphatic carboxylic acids such as -methylenecarboxypropane, and derivatives thereof such as acid anhydrides and lower alkyl esters.

Furthermore, the crystalline polyester may contain a monovalent carboxylic acid. Examples of monovalent carboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, capric acid ( decanoic acid), undecylic acid, lauric acid (dodecanoic acid), tridecylic acid, myristylic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid , arachidic acid (icosanoic acid), henicosylic acid, behenic acid (docosanoic acid), tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and tricontanoic acid.

The content of the crystalline polyester is preferably 8 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the binder resin, from the viewpoint of low-temperature fixability, image heat resistance, and curl resistance. When the amount is less than 8 parts by mass, low-temperature fixability deteriorates and crystallization becomes difficult to proceed, so that image heat resistance also tends to deteriorate. When the amount is more than 15 parts by mass, not only image heat resistance deteriorates but also curl resistance tends to deteriorate due to excessive crystallization.

Crystalline polyester can be manufactured according to a normal polyester synthesis method. For example, a crystalline polyester can be obtained by subjecting the above-mentioned carboxylic acid monomer and alcohol monomer to an esterification reaction or transesterification reaction, and then carrying out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Obtainable. Thereafter, the above-mentioned aliphatic compound is further added and an esterification reaction is performed to obtain the desired crystalline polyester.

The above esterification or transesterification reaction can be carried out using a conventional esterification or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, if necessary.

Further, the above polycondensation reaction can be carried out using a known polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. . The polymerization temperature and the amount of catalyst are not particularly limited and may be determined as appropriate.

In esterification, transesterification, or polycondensation reactions, all monomers may be added at once to increase the strength of the resulting crystalline polyester, or divalent monomers may be reacted first to reduce low molecular weight components. After that, a method such as adding a monomer having a valence of 3 or more and causing a reaction may be used.

<Release agent>
It is preferable that the toner particles of the toner of the present invention contain a release agent. Examples of release agents that can be used in the toner of the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof Products: Waxes whose main component is fatty acid esters such as carnauba wax; Partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax.

Additionally, the following may be mentioned: Saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, seryl alcohol , saturated alcohols such as mericyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol. esters with alcohols such as , ceryl alcohol, and mericyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, and ethylene bislauric acid amide. acid amide, saturated fatty acid bisamides such as hexamethylene bis-stearamide; ethylene bis-oleic acid amide, hexamethylene bis-oleic acid amide, N,N' dioleyl adipate amide, N, N' dioleyl sebacic acid amide; unsaturated fatty acid amides such as m-xylene bisstearamide, aromatic bisamides such as N,N' distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts (generally called metal soaps); Waxes made by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; Fatty acids such as behenic acid monoglyceride Partial esterification product of polyhydric alcohol; methyl ester compound with hydroxyl group obtained by hydrogenation of vegetable oil.

Among these mold release agents, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferred from the viewpoint of promoting crystallization of the crystalline polyester.

The content of the mold release agent is preferably 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the binder resin. Here, the binder resin refers to the total of the crystalline polyester and the amorphous resin.

Further, in the endothermic curve during temperature rise measured by a differential scanning calorimeter (DSC) device, the peak temperature of the maximum endothermic peak of the wax is preferably 80° C. or more and 110° C. or less. The relationship between the melting point T1 (°C) of the wax in the toner and the melting point T2 (°C) of the crystalline polyester is preferably as follows.
2≦T1-T2≦10

With this relationship, crystallization of the crystalline polyester can be induced using the crystallization of the wax as a starting point, and the crystallization behavior of the crystalline polyester upon cooling can be controlled.

<Dispersant>
When the toner particles of the toner of the present invention contain a release agent, it is preferable to contain a dispersant in order to disperse the wax in the resin. Any known dispersant can be used as the dispersant, but when the wax contains a hydrocarbon wax, it is necessary to contain a polymer having a structure in which a vinyl resin component and a hydrocarbon compound have reacted. Preferred for dispersion. Among these, it is preferable to contain a graft polymer in which a vinyl monomer is graft-polymerized to a polyolefin.

When the polymer is contained, the compatibility between the wax and the resin is promoted, and adverse effects such as poor charging and member contamination due to poor wax dispersion are less likely to occur. Further, the content of the dispersant is preferably 1.0 parts by mass or more and 15.0 parts by mass or less based on 100 parts by mass of the binder resin. When the content is within this range, the polyolefin that tends to have a uniform dispersion state of wax in the amorphous resin is not particularly limited as long as it is an unsaturated hydrocarbon polymer or copolymer, and various polyolefins may be used. I can do it. In particular, polyethylene and polypropylene are preferably used. A plurality of these may be used.

Examples of monomers having a vinyl group include the following.

Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene Styrenic units such as styrene and its derivatives.

α-methylene aliphatic monocarboxylic acid esters containing an amino group such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl units containing an N atom such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; unsaturated acids such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Dibasic acid anhydride; methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconate half ester, ethyl citraconate half ester, butyl citraconate half ester, methyl itaconate half ester, alkenyl succinate Half esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester, mesaconate methyl half ester; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acrylic acid, methacrylic acid, croton acids, α,β-unsaturated acids such as cinnamic acid; α,β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic acid anhydride; anhydrides of the above α,β-unsaturated acids and lower fatty acids; Vinyl units containing a carboxy group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof, and monoesters thereof.

Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, 4-(1-hydroxy-1-methyl) Hexyl) A vinyl unit containing a hydroxyl group such as styrene.

Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate An ester unit consisting of an acrylic ester such as acrylic esters such as chloroethyl and phenyl acrylate.

Cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylate An ester unit consisting of a methacrylic acid ester such as α-methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. A plurality of these may be used.

The dispersant used in the present invention can be obtained by a known method such as the reaction between these polymers described above or the reaction between the monomer of one polymer and the other polymer.

<Colorant>
Colorants that can be contained in the toner of the present invention include the following.

Examples of the black colorant include carbon black, which is colored black using a yellow colorant, a magenta colorant, and a cyan colorant. Although a pigment may be used alone as a coloring agent, it is more preferable to use a dye and a pigment together to improve the clarity from the viewpoint of the image quality of a full-color image.

Examples of pigments for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of dyes for magenta toner include the following. C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Dispersed Red 9; C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of pigments for cyan toner include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6;C. I. Acid Blue 45, a copper phthalocyanine pigment in which the phthalocyanine skeleton is substituted with 1 to 5 phthalimidomethyl groups.

As a dye for cyan toner, C.I. I. There is Solvent Blue 70.

Examples of pigments for yellow toner include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C. I. Bat yellow 1, 3, 20.
As the dye for yellow toner, C. I. There is Solvent Yellow 162.

The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the binder resin.

<Charge control agent>
The toner of the present invention can also contain a charge control agent, if necessary. As the charge control agent contained in the toner, any known charge control agent can be used, but a metal compound of an aromatic carboxylic acid is particularly preferable because it is colorless, has a high charging speed of the toner, and can stably maintain a constant charge amount.

Examples of negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer-type compounds with sulfonic acid or carboxylic acid in the side chain, and sulfonate or sulfonic acid ester compounds in the side chain. Examples include polymeric compounds, polymeric compounds having carboxylates or carboxylic acid esters in their side chains, boron compounds, urea compounds, silicon compounds, and calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added is preferably 0.05 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin.

<Inorganic fine particles>
The toner can also contain inorganic fine particles if necessary. The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica, titanium oxide, and aluminum oxide are preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

As an external additive for improving fluidity, inorganic fine powder having a specific surface area of 50 m ² /g or more and 400 m ² /g or less is preferable. In order to stabilize durability, an inorganic fine powder having a specific surface area of 10 m ² /g or more and 50 m ² /g or less is preferable. In order to simultaneously improve fluidity and stabilize durability, an inorganic fine powder having a specific surface area within the above range may be used in combination.

The external additive is preferably used in an amount of 0.10 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of toner particles. A known mixer such as a Henschel mixer can be used to mix the toner particles and the external additive.

[Developer]
The toner of the present invention can be used as a one-component developer, but in order to provide a stable image, it is preferable to mix it with a magnetic carrier and use it as a two-component developer.

When toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier at that time must be 2% by mass or more and 15% by mass or less, as the toner concentration in the two-component developer. is preferable, and more preferably 4% by mass or more and 13% by mass or less.

<Magnetic carrier>
Examples of magnetic carriers include iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, strontium and rare earths, alloy particles thereof, and oxide particles thereof; Magnetic materials such as ferrite and magnetite; magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state; Generally known carriers can be used, such as a filled magnetic carrier.

As the magnetic carrier, the above-mentioned magnetic material may be used directly, or a magnetic material formed by using the above-mentioned magnetic material as a core and coating the surface with a resin may be used. From the viewpoint of improving the chargeability of the toner, it is preferable to use a magnetic material formed by having the above-mentioned magnetic material as a core and coating the surface with a resin as the magnetic carrier.

The resin that coats the core is not particularly limited, and any known resin can be selected and used as long as it does not impair the toner properties, such as (meth)acrylic resin, silicone resin, urethane resin, polyethylene, polyethylene terephthalate, Resins such as polystyrene and phenol resins, copolymers and polymer mixtures containing them can be used. In particular, it is preferable to use (meth)acrylic resin or silicone resin from the viewpoint of charging characteristics and prevention of foreign matter adhesion to the carrier surface. In particular, (meth)acrylic resins having alicyclic hydrocarbon groups such as cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl, cyclobutyl, or cyclopropyl groups are used to This is a particularly preferred form because it makes the coating surface smooth and can suppress the adhesion of toner-derived components such as a binder resin, a mold release agent, and external additives.

〔Production method〕
The method for producing the toner particles of the present invention is not particularly limited, and known methods such as a pulverization method, suspension polymerization method, dissolution suspension method, emulsion aggregation method, and dispersion polymerization method can be used.

An example of a toner manufacturing procedure using a pulverization method will be described below.

In the raw material mixing step, predetermined amounts of materials constituting the toner particles, such as crystalline polyester, amorphous resin, and, if necessary, other components such as a release agent, a coloring agent, and a charge control agent, are weighed. Combine and mix. Examples of the mixing device include a double con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.), and the like.

Next, the mixed materials are melted and kneaded to disperse wax and the like in the binder resin. The kneading and discharge temperature can be appropriately adjusted depending on the binder resin and colorant used, but is generally preferably 100 to 180°C. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, as well as continuous-type kneaders can be used, and single-screw or twin-screw extruders are the mainstream because of their advantage in continuous production. ing. For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machinery Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin screw extruder (manufactured by K.C.K.) Co-kneader (manufactured by Busu Co., Ltd.), Kneedex (manufactured by Nippon Coke Industry Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like, and cooled with water or the like in a cooling step.

Next, the cooled resin composition is pulverized to a desired particle size in a pulverization step. In the pulverization process, after coarse pulverization is performed using a pulverizer such as a crusher, hammer mill, or feather mill, the grinding process is performed using a pulverizer such as a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nissin Engineering Co., Ltd.), or a turbo mill. (manufactured by Freund Turbo) or an air jet type pulverizer.

After that, if necessary, classification is performed using an inertial classification method Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), a centrifugal force classification method Turboplex (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), a faculty member (manufactured by Hosokawa Micron Corporation), etc. The particles are classified using a machine or a sieve to obtain classified products (toner particles).

The toner particles may be used as a toner as is, or if necessary, an external additive may be added to the surface of the toner particles. As a method for externally adding external additives, toner particles and various known external additives are blended in predetermined amounts, and a double con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid ( Examples include a method of stirring and mixing using a mixing device such as Nippon Coke Kogyo Co., Ltd.) or Nobilta (Hosokawa Micron Co., Ltd.) as an external additive.

[Method of measuring physical properties]
Next, methods for measuring each physical property related to the present invention will be described.

<Separation of each material from toner>
Separation of materials from toner is performed by utilizing differences in solubility in solvents and GPC. An example is shown below.
First separation: Dissolve the toner in methyl ethyl ketone (MEK) at 23°C. etc.).
Second separation: The insoluble components obtained in the first separation (crystalline polyester, wax added as necessary, wax dispersant, coloring agent, inorganic particles, etc.) are dissolved in MEK at 100°C, and the soluble components are dissolved in MEK at 100°C. (crystalline polyester, wax, wax dispersant) and insoluble components (colorant, inorganic particles) are separated.
Third separation: Dissolve the soluble components (crystalline polyester, wax, wax dispersant) obtained in the second separation in chloroform at 23°C to separate the soluble components (crystalline polyester) and insoluble components (wax, wax). Dispersant) is separated.
Fourth separation: When the amorphous resin is further separated, the soluble content obtained in the first separation is separated by GPC using molecular weight and polarity difference.

<Calculation of the content ratio of monomer units of amorphous resin and crystalline polyester>
The content of the constituent monomers in the resin is calculated by the following method using NMR.

Weigh 5 mg of the resin separated by the above method, dissolve it in heavy THF or heavy chloroform, perform ¹ H-NMR measurement, and calculate the composition ratio from the integral value of each peak. The specific equipment conditions are as follows.

(Measurement condition)
Measuring device JNM-ECA400 FT-NMR (JEOL)
Measurement nuclide: ^1H
Solvent: Heavy THF or heavy chloroform Measurement frequency: 400MHz
Pulse width: 5.0μs
Frequency range: 10500Hz
Accumulation count: 64 times Measurement temperature: Room temperature

<Measurement of glass transition temperature (Tg) of resin>
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

The temperature correction of the device detection part uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, approximately 3 mg of resin or toner is accurately weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference.
Temperature increase rate: 10℃/min
Measurement start temperature: 30℃
Measurement end temperature: 180℃

Measurement is carried out within the measurement range of 30 to 180°C at a temperature increase rate of 10°C/min. The temperature is raised once to 180°C, held for 10 minutes, then lowered to 30°C, and then raised again. In this second temperature raising process, a change in specific heat is obtained in the temperature range of 30 to 100°C. The intersection point between the line at the midpoint of the baseline before and after the specific heat change at this time and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

<Differential scanning calorimetry (DSC) measurement of toner>
The differential scanning calorimetry of the toner is performed using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

The temperature correction of the device detection part uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, approximately 3 mg of toner is accurately weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference.

After increasing the temperature from 20 to 180°C at a rate of 10°C/min, cooling to 25°C at a rate of 10°C/min, and cooling the toner from 25°C to 15°C at a rate of 3°C/min. Thereafter, the temperature is raised to 180° C. at a rate of 10° C./min for the second time.

P1 (J/g) is the calorific value of the peak derived from crystalline polyester that exists between 40°C and 80°C in the cooling process at a rate of 10°C/min, and the crystallinity that exists in the cooling process at a rate of 3°C/min. P2 (J/g) is the calorific value of the crystallization peak derived from polyester, P3 (J/g) is the sum of the endothermic amounts of the endothermic peaks present at 40°C or higher observed in the second heating process, and P3 (J/g) is the cooling process. P4 (J/g) is the sum of the calorific values of the exothermic peaks present at 40°C or higher observed in the process, and the melting point T1 of the wax and the melting point T2 of the crystalline polyester are determined from the endothermic peak observed in the second heating process. seek. If it is difficult to identify each peak by just measuring the toner, perform differential scanning calorimetry on the separated materials or when they are mixed with an amorphous resin to determine whether T1 or T2 is present in the toner. It is possible to identify which material belongs to the material.

<SP value calculation method>
Regarding the sp values of amorphous resin A, amorphous resin B, amorphous resin C, and crystalline polyester,
According to the calculation method proposed by Fedors, the evaporation energy (Δei ) (cal/mol) and molar volume (Δvi) (cm ³ /mol), and set 2.0455×(ΣΔei/ΣΔvi) ^0.5 as the SP value (J/cm ³ ) ^0.5 .

<Molecular weight measurement of amorphous resin by GPC>
The molecular weight distribution of the THF-soluble portion of the resin is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) for 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8% by mass. Using this sample solution, measurements are performed under the following conditions.
Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0ml/min
Oven temperature: 40.0℃
Sample injection amount: 0.10ml

When calculating the molecular weight of the sample, use standard polystyrene resin (for example, trade name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500'', manufactured by Tosoh Corporation).

<Molecular weight measurement of crystalline polyester by GPC>
First, the crystalline polyester is dissolved in o-dichlorobenzene at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8% by mass. Using this sample solution, measurements are performed under the following conditions.
Equipment: HLC-8121GPC/HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H HT (7.8mm I.D x 30cm) 2 series (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135℃
Solvent: o-dichlorobenzene (0.05% ionol added)
Flow rate: 1.0ml/min
Sample: Inject 0.4ml of 0.1% sample

Measurement is performed under the above conditions, and a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used to calculate the molecular weight of the sample. Furthermore, it is calculated by converting it into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

<Method for measuring the softening point of amorphous resin>
The softening point of the resin is measured using a constant load extrusion type capillary rheometer "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature.

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D" is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time the outflow starts (this is set as X. X = (Smax - Smin) / 2). The temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

The measurement sample was obtained by compression molding about 1.0 g of resin at about 10 MPa for about 60 seconds using a tablet molding and compression machine (for example, NT-100H, manufactured by NP Systems, Inc.) in an environment of 25 ° C. A cylinder with a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 50℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

<Measurement of melting point of mold release agent>
The temperature correction of the device detection part uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat. Specifically, approximately 2 mg of the sample was accurately weighed, placed in an aluminum pan, and using an empty aluminum pan as a reference, the temperature was increased at a heating rate of 10 within the measurement temperature range of 30 to 200°C. Measurements are made in °C/min. In the measurement, the temperature is raised to 200°C, then lowered to 30°C, and then raised again. The peak temperature of the maximum endothermic peak in the DSC curve in the temperature range of 30 to 200° C. during this second temperature raising process is defined as the melting point. Note that there is no holding time after raising the temperature to 200°C, and as soon as the temperature reaches 200°C, the temperature is lowered to 30°C.

<Method for measuring weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles was measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube using the pore electrical resistance method. Using the included dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measured data, measurements were taken with 25,000 effective measurement channels, and the measured data was Analyze and calculate.

The electrolytic aqueous solution used in the measurement can be one in which special grade sodium chloride is dissolved in ion-exchanged water to have a concentration of about 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter).

Note that, before performing measurement and analysis, the dedicated software is set as follows.

In the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count in control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter). Set the value obtained using By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

On the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) Approximately 200 ml of the above electrolyte aqueous solution is placed in a 250 ml round-bottom glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 revolutions/second. Then, use the analysis software's ``aperture flush'' function to remove dirt and air bubbles from inside the aperture tube.
(2) Pour about 30 ml of the above electrolytic aqueous solution into a 100 ml glass flat-bottomed beaker, and add "Contaminon N" as a dispersant (precision measurement of pH 7 consisting of nonionic surfactant, anionic surfactant, and organic builder). Approximately 0.3 ml of a diluted solution prepared by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning utensils (manufactured by Wako Pure Chemical Industries, Ltd.) by 3 times by mass with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and are installed in the water tank of an ultrasonic dispersion device "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is poured into the water tank, and approximately 2 ml of the contaminon N is added to the water tank.
(4) Set the beaker of (2) above in the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. Incidentally, during the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10° C. or more and 40° C. or less.
(6) Using a pipette, drop the aqueous electrolyte solution of (5) in which toner is dispersed into the round bottom beaker of (1) placed in the sample stand, and adjust the measured concentration to approximately 5%. . Then, the measurement is continued until the number of particles to be measured reaches 50,000.
(7) Analyze the measurement data using the dedicated software attached to the device and calculate the weight average particle diameter (D4). In addition, when the graph/volume % is set in the dedicated software, the "average diameter" on the analysis/volume statistics (arithmetic mean) screen is the weight average particle diameter (D4).

<Method for measuring acid value>
The acid value is the mass [mg] of potassium hydroxide required to neutralize the acid contained in 1 g of sample. That is, the mass [mg] of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of a sample is referred to as the acid value.

In the present invention, the acid value was measured according to JIS K 0070-1992. Specifically, it was measured according to the following procedure.

(1) Preparation of reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water was added to make 100 mL to obtain a phenolphthalein solution.

7 g of special grade potassium hydroxide was dissolved in 5 mL of water, and ethyl alcohol (95% by volume) was added to make 1 L. The sample was placed in an alkali-resistant container and left for 3 days to avoid contact with carbon dioxide gas. After standing, it was filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution is as follows: Take 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, add a few drops of the above phenolphthalein solution, titrate with the above potassium hydroxide solution, and calculate the amount of potassium hydroxide required for neutralization. It was determined from the amount of solution. The above 0.1 mol/L hydrochloric acid was prepared according to JIS K 8001-1998.

(2) Operation (A) Main test 2.0 g of the sample was placed in a 200 mL Erlenmeyer flask, accurately weighed, 100 mL of a mixed solution of toluene/ethanol (2:1) was added, and the sample was dissolved over 5 hours. Next, several drops of the above phenolphthalein solution were added as an indicator, and titration was carried out using the above potassium hydroxide solution. The end point of the titration is when the indicator remains pale red for 30 seconds.

(B) Blank test Titration was performed in the same manner as above, except that no sample was added (that is, only a mixed solution of toluene/ethanol (2:1) was used).

(3) Calculation of acid value The obtained results were substituted into the following formula to calculate the acid value.
AV=[(B-A)×f×5.61]/S

In the above formula, AV represents the acid value [mgKOH/g], A represents the amount of potassium hydroxide solution added in the blank test [mL], and B represents the amount of potassium hydroxide solution added in the main test [mL]. , f indicates the factor of the potassium hydroxide solution, and S indicates the mass [g] of the sample.

In the present invention, when amorphous resin B and amorphous resin B' were used in combination, 1 g of the mixed sample was used to measure the acid value.

<Method for measuring hydroxyl value>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to hydroxyl groups when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

(1) Preparation of reagent Place 25 g of special grade acetic anhydride in a 100 ml volumetric flask, add pyridine to bring the total volume to 100 ml, and shake thoroughly to obtain an acetylation reagent. The obtained acetylation reagent is stored in an amber bottle to prevent it from coming into contact with moisture, carbon dioxide, etc.

Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.

Dissolve 35 g of special grade potassium hydroxide in 20 ml of water, and add ethyl alcohol (95 vol%) to make 1 liter. After leaving it in an alkali-resistant container for 3 days to avoid contact with carbon dioxide gas, filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined by placing 25 ml of 0.5 mol/l hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. Determine from the amount of potassium solution. The 0.5 mol/l hydrochloric acid prepared according to JIS K 8001-1998 is used.

(2) Procedure (A) Main test 1.0 g of the sample is accurately weighed into a 200 ml round bottom flask, and 5.0 ml of the above acetylation reagent is accurately added to it using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it.

Place a small funnel on the mouth of the flask, and heat the flask by immersing the bottom of the flask about 1 cm into a glycerin bath at about 97°C. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with cardboard with round holes.

After 1 hour, remove the flask from the glycerin bath and allow to cool. After cooling, add 1 ml of water from the funnel and shake to hydrolyze acetic anhydride. For more complete hydrolysis, the flask is heated again in the glycerin bath for 10 minutes. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.

Add several drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The end point of the titration is when the indicator remains pale red for about 30 seconds.

(B) Blank test Perform titration in the same manner as above, except that no sample is used.

(3) Substitute the obtained results into the following formula to calculate the hydroxyl value.
A=[{(B-C)×28.05×f}/S]+D
Here, A: hydroxyl value (mgKOH/g), B: amount of potassium hydroxide solution added in blank test (ml), C: amount of potassium hydroxide solution added in main test (ml), f: potassium hydroxide Solution factor, S: sample (g), D: acid value (mgKOH/g) of the sample.

<Measurement of BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles was measured according to JIS Z8830 (2001). The specific measurement method is as follows.

As the measuring device, "Automatic Specific Surface Area/Pore Distribution Measuring Device TriStar 3000 (manufactured by Shimadzu Corporation)" was used, which employs a constant volume gas adsorption method as the measuring method. Setting of measurement conditions and analysis of measurement data are performed using the dedicated software "TriStar3000 Version 4.00" attached to this device, and a vacuum pump, nitrogen gas piping, and helium gas piping are connected to the device. The value calculated by the BET multi-point method using nitrogen gas as the adsorption gas was defined as the BET specific surface area of the inorganic fine particles in the present invention.

Note that the BET specific surface area was calculated as follows.

First, nitrogen gas was adsorbed onto inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell at that time and the nitrogen adsorption amount Va (mol·g ⁻¹ ) of the external additive were measured. The horizontal axis is the relative pressure Pr, which is the value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, and the vertical axis is the nitrogen adsorption amount Va (mol・g ^-1 ). An adsorption isotherm was obtained. Next, the monomolecular layer adsorption amount Vm (mol·g ⁻¹ ), which is the adsorption amount necessary to form a monomolecular layer on the surface of the external additive, was determined by applying the following BET formula.
Pr/Va(1-Pr)=1/(Vm×C)+(C-1)×Pr/(Vm×C)
(Here, C is a BET parameter, which is a variable that changes depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET formula is interpreted as a straight line with a slope of (C-1)/(Vm×C) and an intercept of 1/(Vm×C), where the X-axis is Pr and the Y-axis is Pr/Va (1-Pr). (This straight line is called a BET plot).
Slope of straight line = (C-1)/(Vm×C)
Intercept of straight line = 1/(Vm×C)

By plotting the measured value of Pr and the measured value of Pr/Va (1-Pr) on a graph and drawing a straight line using the method of least squares, the slope and intercept of the straight line can be calculated. By solving the simultaneous equations of the slope and intercept using these values, Vm and C can be calculated.

Furthermore, the BET specific surface area S (m ² /g) of the inorganic fine particles is calculated from the Vm calculated above and the molecular occupied cross section of nitrogen molecules (0.162 nm ² ) based on the following formula.
S=Vm×N×0.162× ^10-18
(Here, N is Avogadro's number (mol ^-1 ).)

Measurements using this device were carried out in accordance with the "TriStar3000 Instruction Manual V4.0" attached to the device, and specifically, the measurements were performed using the following procedure.

The tare of a dedicated glass sample cell (stem diameter: 3/8 inch, volume: approximately 5 ml), which had been thoroughly washed and dried, was accurately weighed. Then, approximately 0.1 g of external additive was placed into this sample cell using a funnel.

The sample cell containing the inorganic fine particles was set in a "pretreatment device VacuPrep 061 (manufactured by Shimadzu Corporation)" connected to a vacuum pump and nitrogen gas piping, and vacuum degassing was continued at 23° C. for about 10 hours. Incidentally, during vacuum deaeration, the air was gradually degassed while adjusting the valve so that inorganic fine particles would not be sucked into the vacuum pump. The pressure inside the cell gradually decreased as the gas was degassed, and finally reached about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas was gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell was removed from the pretreatment device. Then, the mass of this sample cell was accurately weighed, and the accurate mass of the external additive was calculated from the difference from the tare weight. At this time, the sample cell was covered with a rubber stopper during the weighing so that the external additive in the sample cell would not be contaminated by moisture in the atmosphere.

Next, a dedicated "isothermal jacket" was attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a special filler rod was inserted into this sample cell, and the sample cell was set in the analysis port of the apparatus. Note that the isothermal jacket is a cylindrical member whose inner surface is made of a porous material and whose outer surface is made of an impermeable material, and is capable of sucking up liquid nitrogen to a certain level by capillary action.

Subsequently, the free space of the sample cell including the connecting device was measured. The free space was determined by measuring the volume of the sample cell using helium gas at 23°C, then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen, also using helium gas. It was calculated by converting from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is separately automatically measured using a Po tube built into the apparatus.

Next, after performing vacuum degassing in the sample cell, the sample cell was cooled with liquid nitrogen while continuing vacuum degassing. Thereafter, nitrogen gas was introduced stepwise into the sample cell to cause the toner to adsorb nitrogen molecules. At this time, the adsorption isotherm was obtained by measuring the equilibrium pressure P (Pa) at any time, and this adsorption isotherm was converted into a BET plot. Note that the relative pressure Pr points at which data were collected were set to a total of six points: 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line was drawn using the least squares method on the obtained measurement data, and Vm was calculated from the slope and intercept of the straight line. Furthermore, using this value of Vm, the BET specific surface area of the inorganic fine particles was calculated as described above.

[Configuration included in the embodiment of the present invention]
The disclosure of this embodiment includes the following configurations.
(Structure 1) A toner having toner particles containing a binder resin and a crystalline polyester,
In differential scanning calorimetry (DSC) of the toner, (i) the temperature was raised to 180°C at a rate of 10°C/min, (ii) the toner was cooled from 180°C to 25°C at a rate of 10°C/min, and ( iii) After that, when the toner is cooled from 25°C to 15°C at a rate of 3°C/min, and the toner is heated a second time to 180°C at a rate of 10°C/min,
In the cooling process of the toner at a speed of 10° C./min, the calorific value P1 of the peak derived from the crystalline polyester existing at 40° C. or higher and 80° C. or lower is 1.00 J/g or less;
The calorific value P2 of the crystallization peak derived from the crystalline polyester present during the cooling process of the toner at a rate of 3° C./min is 0.10 J/g or more,
P3 (J/g) of the sum of the endothermic amounts of the endothermic peaks present at 40°C or higher observed during the second temperature raising process of DSC of the toner, observed during the cooling process of the toner at a rate of 10°C/min. A toner that satisfies the following formula (1), where P4 (J/g) is the sum of the calorific values of exothermic peaks existing at 40° C. or higher.
Formula (1) 2.0≦P3-P4≦10.0
(Structure 2) According to Structure 1, in the cooling process of the toner at a rate of 10°C/min, the calorific value P1 of the peak derived from the crystalline polyester existing at 40°C or more and 80°C or less is 0.50 J/g or less. toner.
(Structure 3) The toner according to Structure 1 or 2, wherein the ratio of the crystalline polyester to the binder resin in the toner is 8.0% by mass or more and 15.0% by mass or less.
(Structure 4) The toner contains a hydrocarbon wax, and the difference between the melting point T1 (°C) of the hydrocarbon wax and the melting point T2 (°C) of the crystalline polyester in the toner is expressed by the following formula (2). ) The toner according to any one of configurations 1 to 3, which satisfies the following.
Formula (2) 2≦T1-T2≦10
(Structure 5) The binder resin contains amorphous resin A, amorphous resin B, and amorphous resin C, and the SP value [(J/cm ³ ) ^0.5 ] of the amorphous resin A is SP1. , the SP value [(J/cm ³ ) ^0.5 ] of the amorphous resin B is SP2, the SP value [(J/cm ³ ) ^0.5 ] of the amorphous resin C is SP3, and the SP value [( J/cm ³ ) ^0.5 ] is SP4, the toner according to any one of configurations 1 to 4, which satisfies the following formulas (3) to (5).
Formula (3) 2.00≦SP1-SP4≦2.90
Formula (4) 0.20≦SP2-SP1≦0.60
Formula (5) 0.20≦SP3-SP2≦0.60
(Structure 6) A two-component developer containing a toner and a magnetic carrier,
A two-component developer, wherein the toner is the toner according to any one of configurations 1 to 5.

The present invention will be explained below with reference to Examples. However, the description regarding this example does not limit the technical scope of the present invention.

<Production example of amorphous resin A1>
・Bisphenol A propylene oxide adduct (average number of added moles: 2.2 mol)
:69.7 parts by mass (52.0 mol%)
・Terephthalic acid: 17.5 parts by mass (28.0 mol%)
・Adipic acid: 5.5 parts by mass (10.0 mol%)
- Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200°C.

Furthermore, the pressure inside the reaction tank was lowered to 8.3 kPa and maintained for 1 hour, then cooled to 160° C. and returned to atmospheric pressure.

・Trimellitic anhydride: 7.2 parts by mass (10.0 mol%)
After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, the temperature was maintained at 200°C, and the reaction was allowed to occur. After confirming that the softening point had reached the temperature shown in Table 1, the temperature was lowered and the reaction was carried out. The process was stopped to obtain amorphous polyester resin A1. The physical properties are shown in Table 1.

<Production examples of amorphous resins A2 to A4>
In the production example of amorphous resin A1, the reaction was carried out in the same manner except that the monomers used were changed as shown in Table 1, and amorphous resins A2 to A4 were obtained. Table 1 shows the composition and physical properties of the obtained amorphous resins A2 to A4.

表１中の略号は以下の通りである。
ＢＰＡ－ＰＯ（２．２）：ビスフェノールＡのプロピレンオキサイド付加物（平均付加モル数２．２ｍｏｌ）
ＢＰＡ－ＰＯ（２．５）：ビスフェノールＡのプロピレンオキサイド付加物（平均付加モル数２．５ｍｏｌ）

The abbreviations in Table 1 are as follows.
BPA-PO (2.2): propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol)
BPA-PO (2.5): propylene oxide adduct of bisphenol A (average number of moles added: 2.5 mol)

<Production example of amorphous resin B1>
・Bisphenol A propylene oxide adduct (average number of added moles: 2.2 mol)
:73.2 parts by mass (56.0 mol%)
・Terephthalic acid: 26.6 parts by mass (43.7 mol%)
・Trimellitic anhydride: 0.2 parts by mass (0.3 mol%)
- Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 3 hours while stirring at a temperature of 200°C. After that, the pressure in the reaction tank was lowered to 8.3 kPa, the temperature was maintained at 200°C, and the reaction was allowed to proceed. After confirming that the softening point had reached the temperature shown in Table 2, the temperature was lowered to stop the reaction. Resin B1 was obtained. The physical properties are shown in Table 2.

<Production examples of amorphous resins B2 and B3>
In the production example of amorphous resin B1, the reaction was carried out in the same manner except that the monomers used were changed as shown in Table 2, and amorphous resins B2 and B3 were obtained. Table 2 shows the composition and physical properties of the obtained amorphous resins B2 to B3.

表２中の略号は以下の通りである。
ＢＰＡ－ＰＯ（２．２）：ビスフェノールＡのプロピレンオキサイド付加物（平均付加モル数２．２ｍｏｌ）

The abbreviations in Table 2 are as follows.
BPA-PO (2.2): propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol)

<Production example of amorphous resin C1>
・Bisphenol A propylene oxide adduct (average number of added moles: 2.2 mol)
: 39.8 parts by mass (26.4 mol%)
・Bisphenol A ethylene oxide adduct (average number of moles added: 2.2 mol)
:24.2 parts by mass (17.6 mol%)
・Ethylene glycol: 1.9 parts by mass (7.5 mol%)
・Fumaric acid: 0.2 parts by mass (0.5 mol%)
・Terephthalic acid: 30.9 parts by mass (44.0 mol%)
・Myristic acid: 2.4 parts by mass (2.5 mol%)
- Tin (II) 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and reaction was carried out for 4 hours while stirring at a temperature of 200°C.

Furthermore, the pressure inside the reaction tank was lowered to 8.3 kPa and maintained for 1 hour, then cooled to 160 psi and returned to atmospheric pressure.

Thereafter, 0.5 parts by mass of dicumyl peroxide was added, and then 0.6 parts by mass (1.5 mol%) of methyl methacrylate was added dropwise over 1 hour with stirring. After that, the pressure in the reaction tank was lowered to 8.3 kPa, the temperature was maintained at 200°C, and the reaction was allowed to proceed. After confirming that the softening point had reached the temperature shown in Table 3, the temperature was lowered to stop the reaction. A crystalline resin C1 was obtained. The physical properties are shown in Table 3.

<Production examples of amorphous resins C2 to C4>
In the production example of amorphous resin C1, the reaction was carried out in the same manner except that the monomers used were changed as shown in Table 3, and amorphous resins C2 to C4 were obtained. Table 3 shows the composition and physical properties of the obtained amorphous resins C2 to C4.

表３中の略号は以下の通りである。
ＢＰＡ－ＰＯ（２．２）：ビスフェノールＡのプロピレンオキサイド付加物（平均付加モル数２．２ｍｏｌ）
ＢＰＡ－ＥＯ：ビスフェノールＡのエチレンオキサイド付加物（平均付加モル数２．２ｍｏｌ）

The abbreviations in Table 3 are as follows.
BPA-PO (2.2): propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol)
BPA-EO: ethylene oxide adduct of bisphenol A (average number of added moles: 2.2 mol)

<Production example of crystalline polyester D1>
・Ethylene glycol: 17.8 parts by mass (49.0 mol%)
・Tetradecanedioic acid: 71.9 parts by mass (46.0 mol%)
・Behenic acid: 10.3 parts by mass (5.0 mol%)
- Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. After purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out at a temperature of 140° C. for 3 hours while stirring.

Thereafter, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200° C., thereby obtaining crystalline polyester D1, which is a crystalline resin. The physical properties are shown in Table 4.

<Production examples of crystalline polyesters D2 to D7>
In the production example of crystalline polyester D1, the reaction was carried out in the same manner except that the monomers used were changed as shown in Table 4, and crystalline polyesters D2 to D7 were obtained. Table 4 shows the composition and physical properties of the crystalline polyesters D2 to D7 obtained.

<Releasing agent 1, 2>
The mold release agent used in the present invention is Fischer-Tropsch wax, of which the peak temperature of the maximum endothermic peak of mold release agent 1 is 90°C and the acid value is 0, and the peak temperature of the maximum endothermic peak of mold release agent 2 is 90°C. The temperature was 87°C and the acid value was 0.

<Production example of wax dispersant E>
・Low molecular weight polypropylene (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.):
10.0 parts by mass (0.02 mol; 2.4 mol% based on the total number of moles of constituent monomers)
- Xylene: 25.0 parts by mass The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised to 175° C. while stirring.

·styrene:
68.0 parts by mass (0.65 mol; 76.4 mol% based on the total number of moles of constituent monomers)
・Cyclohexyl methacrylate:
5.0 parts by mass (0.03 mol; 3.5 mol% based on the total number of moles of constituent monomers)
・Butyl acrylate:
12.0 parts by mass (0.09 mol; 11.0 mol% based on the total number of moles of constituent monomers)
・Methacrylic acid:
5.0 parts by mass (0.06 mol; 6.8 mol% based on the total number of moles of constituent monomers)
- Xylene: 10.0 parts by mass - Di-t-butylperoxyhexahydroterephthalate: 0.5 parts by mass Thereafter, the above materials were added dropwise over 3 hours, and the mixture was further stirred for 30 minutes. Next, the solvent was distilled off to obtain a wax dispersant E having a structure in which a vinyl resin component and a hydrocarbon compound reacted. The obtained wax dispersant E had a peak molecular weight Mp of 6000 and a softening point of 125°C.

<Toner 1 manufacturing example>
- Amorphous resin A1 25 parts by mass - Amorphous resin B1 20 parts by mass - Amorphous resin C1 45 parts by mass - Crystalline polyester D1 10 parts by mass - Wax dispersant E 5 parts by mass - Release agent 1 5 parts by mass Department/C. I. Pigment Blue 15:3 7 parts by mass The above materials were mixed using a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 5 min, and the temperature was set at 130°C. The mixture was kneaded using a twin-screw kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.). The obtained kneaded product was cooled and coarsely ground to 1 mm or less using a hammer mill to obtain a coarsely ground product. The obtained coarse material was pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.

The weight average particle diameter (D4) of the toner particles 1 was measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) and found to be 6.5 μm.

To 100 parts by mass of the obtained toner particles 1, 1.0 parts by mass of hydrophobic silica (BET: 200 m ² /g) surface-treated with hexamethyldisilazane and titanium oxide fine particles (BET) surface-treated with isobutyltrimethoxysilane were added. :80m ² /g) were mixed in a Henschel mixer (model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min to obtain toner 1. .

<Production example of toners 2 to 24>
In the production example of Toner 1, except that the amorphous resin A, the amorphous resin B, the amorphous resin C, the crystalline polyester D, the release agent, and the parts by mass thereof were changed as shown in Table 5. Toners 2 to 24 were obtained in the same manner. Note that T2 could not be confirmed for toner 20, toner 23, and toner 24.

<Production example of magnetic core particle 1>
・Process 1 (weighing/mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg(OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 parts by mass The ferrite raw materials were weighed so that the above materials had the above composition ratios. Thereafter, the mixture was ground and mixed for 5 hours using a dry vibration mill using stainless steel beads with a diameter of 1/8 inch.

・Process 2 (temporary firing process):
The obtained pulverized material was made into pellets of approximately 1 mm square using a roller compactor. Coarse powder was removed from the pellets using a vibrating sieve with an opening of 3 mm, then fine powder was removed using a vibrating sieve with an opening of 0.5 mm, and then the pellets were heated in a nitrogen atmosphere (oxygen concentration 0. 01% by volume) at a temperature of 1000° C. for 4 hours to produce calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO)a(MgO)b( _SrO )c( _Fe2O3 )d
In the above formula, a=0.257, b=0.117, c=0.007, d=0.393

・Process 3 (pulverization process):
After crushing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was ground for 4 hours in a wet ball mill using alumina beads with a diameter of 1/16 inch to obtain a ferrite slurry (finely ground product of calcined ferrite).

・Process 4 (granulation process):
To the ferrite slurry, 1.0 parts by mass of ammonium polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to 100 parts by mass of calcined ferrite, and the mixture was dried with a spray dryer (manufacturer: Okawara Kakoki). It was granulated into spherical particles. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

・Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300°C in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then fired at a temperature of 1150°C for 4 hours. Thereafter, the temperature was lowered to 60° C. over a period of 4 hours, the temperature was returned to the atmosphere from the nitrogen atmosphere, and the sample was taken out at a temperature of 40° C. or lower.

・Process 6 (sorting process):
After crushing the agglomerated particles, the low-magnetic particles are cut by magnetic separation, and coarse particles are removed by sieving with a sieve with an opening of 250 μm. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8 parts by mass Methyl methacrylate monomer 0.2 parts by mass Methyl methacrylate macromonomer 8.4 parts by mass (macromonomer with a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3 parts by mass Methyl ethyl ketone 31.3 parts by mass Azobisisobutyronitrile 2.0 parts by mass Among the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were mixed in a reflux condenser and a thermometer. , into a four-neck separable flask equipped with a nitrogen inlet tube and a stirring device, introduce nitrogen gas to create a sufficient nitrogen atmosphere, heat to 80°C, and add azobisisobutyronitrile. The mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate the copolymer, and the precipitate was filtered off and dried under vacuum to obtain coated resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3 parts by mass Toluene 66.4 parts by mass Carbon black (Regal 330; manufactured by Cabot Corporation) 0.3 parts by mass (primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75ml/100g)
was dispersed in a paint shaker for 1 hour using zirconia beads with a diameter of 0.5 mm. The obtained dispersion liquid was filtered through a 5.0 μm membrane filter to obtain coating resin solution 1.

<Manufacturing example of magnetic carrier 1>
(Resin coating process):
Coating resin solution 1 was put into a vacuum degassing type kneader maintained at room temperature in an amount of 2.5 parts by mass as a resin component based on 100 parts by mass of magnetic core particles 1. After the addition, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and after a certain amount of the solvent (80% by mass) had evaporated, the temperature was raised to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier was separated into low-magnetic products by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified with an air classifier to obtain a magnetic carrier with a 50% particle size (D50) of 38.2 μm based on volume distribution. I got 1.

<Example of manufacturing two-component developer and replenishment developer>
Toners 1 to 24 and magnetic carrier 1 were mixed with a V-type mixer (V-10 model: Tokuju Seisakusho Co., Ltd.) at a rotation time of 5 min at 0.5 s ^-1 so that the toner concentration was 8.0% by mass. , two-component developers 1 to 24 were obtained.

In addition, toners 1 to 24 and magnetic carrier 1 were mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at a rotation time of 0.5 s ^-1 and a rotation time of 5 min so that the toner concentration was 95.0% by mass. By mixing, replenishment developers 1 to 24 listed in Table 6 were obtained.

[Example 1]
<Evaluation>
Using the two-component developer 1 and replenishment developer 1, the following low-temperature fixability evaluation, image heat resistance evaluation, and curl resistance evaluation were performed.

A full color copying machine imagePress C800 manufactured by Canon Inc. was modified so that fixing temperature and process speed could be set freely. A two-component developer of cyan toner is put into the developing device of each color, a replenishment developer container containing replenishment developer of cyan toner is set in each color unit, an image is formed, and durability tests are carried out. We conducted an evaluation.

Evaluation was performed based on the following evaluation method, and the results are shown in Table 6.

[Rating 1. Low temperature fixability evaluation]
The image was taken in single color mode under normal temperature and humidity environment (temperature 23℃, relative humidity 50% to 60%), adjusted so that the amount of toner applied on the paper was 1.2mg/cm ² , print ratio 25%, undetermined. I outputted it on my arrival. Copy paper GF-C081 (A4, basis weight 81.4 g/m ² , sold by Canon Marketing Japan Inc.) was used as the evaluation paper.

Then, in a low-temperature, low-humidity environment (temperature 15°C, relative humidity 10% or less), the process speed was set to 450 mm/sec, and the fixing temperature was increased sequentially by 2.5°C from 120°C to the lower limit temperature at which no offset occurs. was defined as the fixable temperature.

(Evaluation criteria for fixing temperature)
A: Less than 150℃ (Excellent)
B: 150°C or higher and lower than 155°C (Good)
C: 155°C or higher and lower than 160°C (This is the level at which the effects of the present invention are obtained.)
D: 160°C or higher (not permissible according to the present invention)

[2. Image heat resistance evaluation]
Coated paper: Image coat gloss 128 (128.0g/m ² )
(Sold by Canon Marketing Japan Inc.)
Toner loading amount: 1.20mg/cm ²
Evaluation image: Place a 100cm ² (10cm x 10cm) image in the center of the above A4 paper Fixation test environment: Low temperature and low humidity environment (temperature 15℃, humidity 10%RH)
Process speed: 450mm/sec
Fixing temperature: Low temperature fixing evaluation temperature +10℃
Using the above image forming apparatus, output one fixed image under the above conditions, stack a paper stack (CS-680 (sold by Canon Marketing Japan Inc.); 500 sheets) on top of the fixed image, and then combine the output and the paper stack. was placed in a constant temperature bath set at 30° C. and 80% RH, and left for 1 hour. Thereafter, the temperature of the constant temperature bath was reset to the following evaluation conditions, and then left for 10 hours. Next, the printed product and the sheet of paper on top of it were taken out of the thermostatic bath, allowed to cool for 1 hour, and then the two sheets were peeled off. At that time, it was evaluated whether the images were adhered.

(Evaluation criteria)
A1: The output product peels off easily under constant temperature oven temperature of 65°C. (Very good)
A2: A load is felt when peeling off the printed product at a constant temperature oven temperature of 65°C, but no uneven gloss appears on the image. (Very good)
B1: The output product peels off easily under constant temperature bath conditions of 60°C. (Are better)
B2: Constant temperature bath condition: A load is felt when peeling off the printed product at a temperature of 60° C., but uneven gloss of the image does not appear. (Are better)
C: Printed products do not adhere to each other under constant temperature oven temperature of 55°C. (This is a level that poses no problem in the present invention)
D: The printed products adhere to each other at a temperature of 55° C. in a constant temperature oven, and if they are strongly peeled off, the printed products will be torn. (Not permissible in this invention)

[Evaluation 3: Curl resistance evaluation]
Using the above image forming apparatus, PB PAPER (66.0 g/m ² , letter, sold by Canon Marketing Japan Inc.) was used as evaluation paper in a high temperature and high humidity environment (temperature 35°C, humidity 85% RH). We conducted an evaluation.

In single-sided continuous printing mode, 100 sheets were printed in succession, with a leading edge margin of 3 mm, a trailing edge margin of 3 mm, and left and right margins of 3 mm each, and a full-surface solid image of 1.20 mg/cm ² was output.

Under the same environment, after stacking 100 sheets with the solid image side facing upward after image output, place a 210 mm x 30 mm weight of 100 g on the rear edge of the paper, along the line between the 210 mm side and the rear edge of the paper. I posted them together. Then, measure the height of the trailing edge of the paper and the height of the leading edge of the paper, subtract the height of the trailing edge from the height of the leading edge, and then divide by the height of the trailing edge. The height ratio (%) was determined by multiplying by 100. The larger the height ratio, the more curls are generated, and the evaluation was made based on the following criteria.

(Evaluation criteria)
A: The height ratio is less than 6%.
B: The height ratio is 6% or more and less than 11%.
C: The height ratio is 11% or more and less than 16%.
D: Height ratio is 16% or more.

[Examples 2 to 18 and Comparative Examples 1 to 6]
Evaluation was performed in the same manner as in Example 1, except that the two-component developer used in the evaluation was changed to the two-component developer listed in Table 6. The evaluation results are shown in Table 6.

Claims (6)

A toner having toner particles containing a binder resin and a crystalline polyester,
In differential scanning calorimetry (DSC) of the toner, (i) the temperature was raised to 180°C at a rate of 10°C/min, (ii) the toner was cooled from 180°C to 25°C at a rate of 10°C/min, and ( iii) After that, when the toner is cooled from 25°C to 15°C at a rate of 3°C/min, and the toner is heated a second time to 180°C at a rate of 10°C/min,
In the cooling process of the toner at a speed of 10° C./min, the calorific value P1 of the peak derived from the crystalline polyester existing at 40° C. or higher and 80° C. or lower is 1.00 J/g or less;
The calorific value P2 of the crystallization peak derived from the crystalline polyester present during the cooling process of the toner at a rate of 3° C./min is 0.10 J/g or more,
P3 (J/g) of the sum of the endothermic amounts of the endothermic peaks present at 40°C or higher observed during the second temperature raising process of DSC of the toner, observed during the cooling process of the toner at a rate of 10°C/min. A toner that satisfies the following formula (1), where P4 (J/g) is the sum of the calorific values of exothermic peaks existing at 40° C. or higher.
Formula (1) 2.0≦P3-P4≦10.0 The toner according to claim 1, wherein in a cooling process of the toner at a rate of 10° C./min, a peak calorific value P1 derived from the crystalline polyester present at a temperature of 40° C. or more and 80° C. or less is 0.50 J/g or less. 3. The toner according to claim 1, wherein the ratio of the crystalline polyester to the binder resin in the toner is 8.0% by mass or more and 15.0% by mass or less. A claim in which the toner contains a hydrocarbon wax, and the difference between the melting point T1 (°C) of the hydrocarbon wax and the melting point T2 (°C) of the crystalline polyester in the toner satisfies the following formula (2): The toner according to item 1 or 2.
Formula (2) 2≦T1-T2≦10 The binder resin contains an amorphous resin A, an amorphous resin B, and an amorphous resin C, and the SP value [(J/cm ³ ) ^0.5 ] of the amorphous resin A is SP1, and the amorphous resin The SP value [(J/cm ³ ) ^0.5 ] of resin B is SP2, the SP value [(J/cm ³ ) ^0.5 ] of the amorphous resin C is SP3, and the SP value [(J/cm ^{3 )} of the crystalline polyester is ) ^0.5 ] is SP4, the toner according to claim 1 or 2, which satisfies the following formulas (3) to (5).
Formula (3) 2.00≦SP1-SP4≦2.90
Formula (4) 0.20≦SP2-SP1≦0.60
Formula (5) 0.20≦SP3-SP2≦0.60 A two-component developer containing a toner and a magnetic carrier,
A two-component developer, wherein the toner is the toner according to claim 1 or 2.