CN116804833A

CN116804833A - Toner and two-component developer

Info

Publication number: CN116804833A
Application number: CN202310290534.1A
Authority: CN
Inventors: 满生健太; 梶原久辅; 井村茉贵; 吉田宜弘; 吉山浩平; 釜江健太郎; 西村悠; 大山一成; 菅原庸好; 千本裕也; 柴田隆穗
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2022-03-23
Filing date: 2023-03-23
Publication date: 2023-09-26

Abstract

The present invention relates to a toner and a two-component developer. The toner includes toner particles including a binder resin including crystalline polyester. In Differential Scanning Calorimetric (DSC), the toner is heated to 180℃at a rate of 10℃per minute, then cooled to 25℃at a rate of 10℃per minute, cooled from 25℃to 15℃in turn at a rate of 3℃per minute, and heated again to 180℃at a rate of 10℃per minute. As a result, the amount of heat release P1 when the toner is cooled from 80 to 40 ℃ is 1.00J/g or less, the amount of heat release P2 when the toner is cooled from 25 to 15 ℃ is 0.10J/g or more, the sum of heat absorption P3 (J/g) when the toner is heated again from 40 to 180 ℃ and the sum of heat release P4 (J/g) when the toner is cooled from 180 to 40 ℃ satisfy 2.0.ltoreq.P3-P4.ltoreq.10.0.

Description

Toner and two-component developer

Technical Field

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

Background

In recent years, as the use of electrophotographic full-color copying machines has become wider, not only higher speed and higher image quality have been demanded, but also improvement of additional properties such as energy saving properties and compatibility with a wide variety of media has been demanded.

Specifically, as a toner for energy saving, in order to reduce power consumption in the fixing step, a toner that can be fixed at a lower temperature and is excellent in low-temperature fixability is demanded.

In japanese patent application laid-open No.2004-046095, as a toner excellent in low-temperature fixability, a toner using crystalline polyester as a binder resin of the toner is proposed.

Further, thick coated paper, which is one of various media, has high smoothness and a large load at the time of stacking, so that the contact area is large, and toner fixing an image is easily transferred to the stacked paper. In other words, as a toner compatible with various media, a toner excellent in image heat resistance is required.

For example, japanese patent application laid-open No.2016-033648 proposes a toner which is excellent in low-temperature fixability and image heat resistance and which controls a crystalline portion and an amorphous portion of a crystalline polyester.

Disclosure of Invention

The toner described in Japanese patent application laid-open No.2004-046095 uses crystalline polyester. Crystalline polyesters have narrow melting properties as compared with amorphous polyesters, and also act as plasticizers for amorphous polyesters, and thus are effective materials for low-temperature fixing of toners. However, when the crystalline polyester is excessively compatible with the binder resin, the heat resistance of the image is deteriorated, and the image may adhere when stored at high temperature.

Meanwhile, the toner described in japanese patent application laid-open No.2016-033648 has controlled crystalline portions and amorphous portions in crystalline polyesters, and is easily crystallized upon cooling, thereby achieving excellent low-temperature fixability and image heat resistance. However, since crystalline polyesters are easily crystallized, the paper may curl due to rapid volume shrinkage after fixing.

For the above reasons, a toner satisfying all of low-temperature fixability, image heat resistance, and curl resistance (curl resistance) is required.

An object of the present invention is to provide a toner that solves the above-described problems. Specifically, an object of the present invention is to provide a toner excellent in all of low-temperature fixability, heat-resistant storage stability and curl resistance.

The present invention relates to a toner comprising:

toner particles comprising a binder resin comprising a crystalline polyester, wherein

When Differential Scanning Calorimetric (DSC) of the toner is sequentially subjected to: (i) a first temperature-raising process of raising the temperature of the toner from normal temperature to 180 ℃ at a rate of 10 ℃/min, (ii) a first cooling process of cooling the toner from 180 ℃ to 25 ℃ at a rate of 10 ℃/min, (iii) a second cooling process of subsequently cooling the toner from 25 ℃ to 15 ℃ at a rate of 3 ℃/min, and (iv) a second temperature-raising process of raising the temperature of the toner to 180 ℃ again at a rate of 10 ℃/min,

The exothermic amount P1 of exothermic peaks derived from crystalline polyester, which are observed in the first cooling process at 40 ℃ or higher and 80 ℃ or lower, is 1.00J/g or lower,

the exothermic amount P2 of exothermic peak derived from crystalline polyester observed in the second cooling process is 0.10J/g or more, and

when the sum of the endothermic amounts of the endothermic peaks existing at 40 ℃ or higher observed during the second temperature rising process is expressed as P3 (J/g), and the sum of the exothermic amounts of the exothermic peaks existing at 40 ℃ or higher observed during the first cooling process is expressed as P4 (J/g), P3-P4 satisfies the following formula (1):

the formula (1) is 2.0-P3-P4-10.0.

The present invention also relates to a two-component developer comprising: a toner; and a magnetic carrier, wherein the toner has the above-described structure.

Other features of the present invention will become apparent from the following description of exemplary embodiments.

Detailed Description

[ characteristic of the invention ]

The present invention is a toner comprising:

comprising a binder resin comprising a crystalline polyester,

wherein when Differential Scanning Calorimetric (DSC) of the toner is sequentially subjected to: (i) a first temperature-raising process of raising the temperature of the toner from normal temperature to 180 ℃ at a rate of 10 ℃/min, (ii) a first cooling process of cooling the toner from 180 ℃ to 25 ℃ at a rate of 10 ℃/min, (iii) a second cooling process of subsequently cooling the toner from 25 ℃ to 15 ℃ at a rate of 3 ℃/min, and (iv) a second temperature-raising process of raising the temperature of the toner to 180 ℃ again at a rate of 10 ℃/min,

when the sum of the heat absorption amounts of the endothermic peaks at 40 ℃ or higher observed during the second temperature rising process is represented as P3 (J/g) and the sum of the heat release amounts of the exothermic peaks at 40 ℃ or higher observed during the first cooling process is represented as P4 (J/g), P3-P4 satisfies the following formula (1):

the formula (1) is 2.0-P3-P4-10.0.

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

The toner of the present invention includes a binder resin containing crystalline polyester. Here, the "binder resin" refers to the sum of an amorphous resin and a crystalline resin. At the time of fixing, the crystalline polyester becomes compatible with the amorphous resin, thereby improving low-temperature fixability. Thereafter, if it is rapidly crystallized during cooling, the image heat resistance is good, but there is a problem of curl resistance. This state can be grasped by the exothermic amount P1 at the exothermic peak during cooling of differential scanning calorimetric measurement (DSC), and when P1 is large, the curl resistance is deteriorated. The present inventors considered that in order to improve curl resistance without deteriorating heat resistance of an image, a system is required in which the crystalline polyester does not rapidly crystallize (P1 small) upon rapid cooling, but crystallization of the crystalline polyester occurs within a time period until the image adheres upon slow further cooling.

Therefore, the present inventors examined the combination of all resins while controlling the compatibility between the amorphous resin and the crystalline resin. As a result, if P1 of the crystallization peak during rapid cooling of DSC is adjusted to 1.00J/g or less, the toner has low-temperature fixability and curl resistance; the toner has improved image heat resistance if P2 of the peak observed at the time of slow cooling thereafter is 0.10J/g or more, and the sum P3 of the endothermic amounts of the endothermic peaks observed in the subsequent second temperature rise is 2.00J/g or more greater than the total exothermic amount P4 of the exothermic peaks observed during cooling to 40 ℃. In particular, a minute peak occurring when cooling slowly after cooling rapidly is important for achieving the above at the same time.

In the toner of the present invention, P1 is 1.00J/g or less, curl resistance is ensured, and P1 is preferably 0.50J/g or less for even better curl resistance.

The toner of the present invention has a P3 to P4 of 2.0 to 10.0. By controlling P3-P4 within this range, the crystal growth rate upon standing can be optimized. If P3-P4 is less than 2.0, crystallization is insufficient, resulting in poor heat resistance of the image. Meanwhile, if P3-P4 is more than 10.0, the amount of precipitated crystals is excessive, and not only sufficient image heat resistance is not obtained, but also curl resistance is deteriorated.

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

The toner of the present invention preferably further comprises a hydrocarbon-based wax, and the difference T1-T2 between the melting point T1 (°c) of the hydrocarbon-based wax and the melting point T2 (°c) of the crystalline polyester in the toner preferably satisfies the following formula (2):

the formula (2) is 2-T1-T2-10.

The hydrocarbon wax has a proper compatibility with the crystalline polyester. When the content thereof is within the above melting point range, crystallization of the crystalline polyester can be properly promoted, while low-temperature fixability, image heat resistance and curl resistance can be easily achieved. If T1-T2 is less than 2, crystallization of the crystalline polyester is excessively promoted, so that low-temperature fixability and curl resistance are liable to deteriorate. If T1-T2 is more than 10, the crystalline polyester becomes difficult to crystallize, so that the image heat resistance is liable to deteriorate.

In the toner of the present invention, the binder resin contains an amorphous resin A, an amorphous resin B and an amorphous resin C, and when the SP value of the amorphous resin A [ (J/cm) ³ ) ^0.5 ]SP value [ (J/cm) of amorphous resin B ] denoted as SP1 ³ ) ^0.5 ]SP value of amorphous resin C [ (J/cm) denoted as SP2 ³ ) ^0.5 ]When the SP value is SP3, the SP value [ (J/cm) of the crystalline polyester ³ ) ^0.5 ]When denoted as SP4, SP1, SP2, SP3, and SP4 preferably satisfy the following formulas (3) to (5):

the formula (3) is more than or equal to 2.00 and less than or equal to SP1-SP4 and less than or equal to 2.90

The formula (4) is more than or equal to 0.20 and less than or equal to 0.60 and SP2-SP1

The formula (5) is more than or equal to 0.20 and less than or equal to 0.60 and SP3-SP 2.

By setting the resin composition to satisfy these formulae, the compatibility of the crystalline polyester can be controlled, and crystallization can be performed slowly without causing excessive crystallization. The SP value of the amorphous resin a is closest to that of the crystalline polyester, and when it satisfies the relationship of the formula (3), the low-temperature fixability is improved. If SP1-SP4 is less than 2.00, the compatibility is too high, and P2 and P3-P4 will become too small, so that the image heat resistance tends to deteriorate. When SP1 to SP4 are more than 2.90, P1 becomes too large due to poor compatibility, so that low-temperature fixability and curl resistance are liable to deteriorate.

The amorphous resin B is a resin that improves the compatibility between the amorphous resin a and the amorphous resin C, and by satisfying the formula (4), has an effect of adjusting the miscibility of the amorphous resin a and the amorphous resin C, and thus, P2 tends to increase. This improves low-temperature fixability and image heat resistance.

The amorphous resin C is a resin that is required to promote crystallization of the crystalline polyester without excessively increasing P1, and therefore, it is preferable to satisfy the relationship of formula (5).

When SP3-SP2 is less than 0.20, crystallization becomes difficult, and the values of P2 and P3-P4 become small, and the heat resistance of the image tends to deteriorate. When SP3-SP2 is more than 0.60, crystallization is excessive, and thus, P1 becomes too large, so that low-temperature fixability and curl resistance are liable to deteriorate. Further, when two types of amorphous resins are used as the binder resin instead of the amorphous resin C, P2 and P3 to P4 become too small, so that the image heat resistance is liable to deteriorate.

The SP value of these resins can be controlled by controlling the types and amounts of monomers of the amorphous resin and the crystalline polyester. In particular, the amorphous resin C preferably has a polarity difference in its molecule, and preferably contains a polyester and an acrylic hybrid resin.

[ toner composition of the invention ]

The constitution of the toner of the present invention is described in detail below.

< amorphous resin >

As the amorphous resin used in the toner of the present invention, three resins having different SP values are preferably used. As a constitution thereof, the resin having the smallest SP value is an amorphous resin a, the resin having the next smallest SP value is an amorphous resin B, and the resin having the largest SP value is an amorphous resin C. For the combinations of resins used, they need to be clearly distinguished by GPC. For example, the amorphous resin a may be a low molecular weight polyester, the amorphous resin B may be a high molecular weight polyester, and the amorphous resin C may be a hybrid resin obtained by combining a polyester resin and an acrylic resin. They are combinations that differ by more than a factor of 3 in weight average molecular weight, or that differ significantly in composition, such as polyesters and hybrid resins.

As the amorphous resin, the following polymer or resin may be used.

For example, homopolymers of styrene such as polystyrene, parylene and polyvinyltoluene and substitution products thereof can be used; for example, styrene-based copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, styrene- α -methyl chloromethyl acrylic ester copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinylethyl ether copolymer, styrene-vinylmethyl ketone copolymer and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resins, natural resin modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, petroleum resins, and hybrid resins combining these.

Among them, from the viewpoint of low-temperature fixability, a polyester resin is preferably used as a main component. The main component represents that the content thereof is 50.0 mass% or more.

Monomers used in the polyester resin include polyhydric alcohols (di-or tri-or higher alcohols), polybasic carboxylic acids (di-or tri-or higher carboxylic acids) and anhydrides thereof or lower alkyl esters thereof.

Here, in order to prepare a branched polymer, it is effective to crosslink the molecular portion of the amorphous resin, and for this reason, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, the raw material monomer of the polyester preferably contains a tri-or higher carboxylic acid, an anhydride thereof or a lower alkyl ester thereof, and/or a tri-or higher alcohol.

The following monomers may be used as the polyol monomers used in the polyester resin.

Examples of the diol component 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, and hydrogenated bisphenol A, and bisphenols represented by formula (A) and derivatives thereof; and a diol represented by formula (B):

wherein R is ethylene or propylene, x and y are each integers of 0 or more, and the average value of x+y is 0 or more and 10 or less, and

A diol represented by formula (B):

wherein R' is-CH ₂ CH ₂ -、-CH ₂ -CH(CH ₃ ) -or-CH ₂ -C(CH ₃ ) ₂ -, and x 'and y' are each integers of 0 or more, and the average value of x '+y' is 0 or more and 10 or less.

Examples of the tri-or higher alcohol component include sorbitol, 1,2,3, 6-hexanetriol, 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 and 1,3, 5-trimethylol benzene. Among them, glycerol, trimethylolpropane and pentaerythritol are preferably used. These diols and tri-or higher alcohols may be used alone or in combination.

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

Examples of dicarboxylic 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-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and anhydrides and lower alkyl esters of these acids.

Among them, maleic acid, fumaric acid, terephthalic acid and n-dodecenyl succinic acid are preferably used.

Examples of tri-or higher carboxylic acids, anhydrides thereof and lower alkyl esters thereof include 1,2, 4-benzene tricarboxylic acid, 2,5, 7-naphthalene tricarboxylic acid, 1,2, 4-butane tricarboxylic acid, 1,2, 5-hexane tricarboxylic acid, 1, 3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2, 4-cyclohexane tricarboxylic acid, tetrakis (methylenecarboxymethane), 1,2,7, 8-octane tetracarboxylic acid, pyromellitic acid, empol trimer acid and anhydrides thereof or lower alkyl esters thereof.

Among them, 1,2, 4-trimellitic acid, that is, trimellitic acid or its derivatives are particularly preferably used because of being inexpensive and easy in reaction control. These dicarboxylic acids and tri-or higher carboxylic acids may be used singly or in combination.

The production method of the polyester is not particularly limited, and known methods may be used. For example, the above-mentioned alcohol monomer and carboxylic acid monomer are simultaneously added, subjected to an esterification reaction or a transesterification reaction and a condensation reaction, and then polymerized to produce a polyester resin. Further, the polymerization temperature is not particularly limited, but is preferably in the range of 180℃or more and 290℃or less.

Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide and germanium dioxide can be used for the polymerization of polyesters. Polyester resins polymerized using tin-based catalysts are more preferred.

The amorphous resin preferably contains a hybrid resin obtained by combining a polyester resin and an acrylic resin. The inclusion of the hybrid resin produces intramolecular polarity differences that can promote crystal growth of the crystalline polyester over time. The production method of the hybrid resin is not particularly limited, but includes the following:

(i) A production method by conducting a transesterification reaction between a polyester component and a polymer containing a monomer component having an ester group such as an acrylate or methacrylate;

(ii) A production method by conducting 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; and

(iii) A production method by polymerizing a monomer component constituting an acrylic copolymer portion in the presence of a polyester portion containing a monomer component having an unsaturated bond such as fumaric acid.

As a preferred example, the hybrid resin may be produced by including monomers capable of reacting with both parts in the monomer composition constituting the acrylic copolymer part and/or the monomer composition constituting the polyester part and reacting them.

Among them, the method (iii) is preferable because a structure in which a polyester resin is crosslinked with an acrylic resin can be formed. With this structure, the acrylic resin is sandwiched between the polyester resins. The structure has an SP value that the crosslinking moiety is easily compatible with the crystalline polyester, and the SP value of the polyester resin to be crosslinked is different from that of the crystalline polyester but has a certain proportion of ester groups compatible with the crystalline polyester structure.

This structure is thought to contribute to promoting the growth of crystals over time while suppressing the rapid crystallization of the crystalline polyester, so that low-temperature fixability, image heat resistance, and curl resistance can be achieved at the same time. When the hybrid resin is used as one of three amorphous resins, the SP value of the resin as a whole is preferably designed to be highest among the three amorphous resins from the viewpoint of crystal growth of the crystalline polyester.

The crosslinking moiety is not limited to acrylic resins, and examples thereof include copolymers of a styrene component and an acrylic and/or methacrylic component.

Monomers used for the crosslinking moiety include the following.

Examples of the monomer for the crosslinking moiety include styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methoxystyrene and p-phenylstyrene, and acrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate. Among them, methyl methacrylate and ethyl methacrylate are preferably used.

When the amorphous resin contains the amorphous resin a, the amorphous resin B, and the amorphous resin C, their respective contents are preferably 10 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the binder resin.

< crystalline polyester >

The binder resin contained in the toner particles of the toner of the present invention contains crystalline polyester. Crystalline polyesters are resins in which an endothermic peak is observed in Differential Scanning Calorimetry (DSC).

The crystalline polyester is preferably obtained by subjecting a monomer composition containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components to polycondensation reaction.

As the polyol monomer used for the polyester unit of the crystalline polyester, the following polyol monomer may be used.

The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, examples of which include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 4-butadiene diol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Of these, linear aliphatic, α, ω -diols such as ethylene glycol and 1, 4-butanediol are particularly preferable.

Among the above-mentioned alcohol components, preferably 50 mass% or more, more preferably 70 mass% or more, is an alcohol selected from aliphatic diols having 2 to 4 carbon atoms.

In the present invention, a polyol monomer other than the above polyol may also be used. Among these polyol monomers, examples of the diol monomers include aromatic alcohols such as polyoxyethylenated bisphenol a and polyoxypropylene bisphenol a; and 1, 4-cyclohexanedimethanol. Further, among these polyol monomers, examples of the polyol monomer of three or more include aromatic alcohols such as 1,3, 5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2, 4-butanetriol, 1,2, 5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1, 2, 4-butanetriol, trimethylolethane and trimethylolpropane.

In addition, the crystalline polyester used may be a monohydric alcohol. Examples of the monohydric alcohol include monohydric alcohols such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol, and octanol (decanol), undecanol, lauryl alcohol (dodecanol), tridecyl alcohol, myristyl alcohol (tetradecanol), pentadecyl alcohol, palmityl alcohol (hexadecanol), heptadecyl alcohol (heptadecyl alcohol), stearyl alcohol (octadecyl alcohol), nonadecyl alcohol, arachidyl alcohol (eicosanol), heneicosyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, 1-heptadecyl alcohol, meng Danchun (montanyl alcohol), 1-icosayl alcohol, and triacontanol.

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

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

In the present invention, polycarboxylic acids other than the above polycarboxylic acid monomers may also be used. Among the other polycarboxylic acid monomers, examples of dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. Also included are anhydrides thereof or lower alkyl esters thereof. Further, among the other carboxylic acid monomers, examples of the tri-or higher carboxylic acid include aromatic carboxylic acids such as 1,2, 4-trimellitic acid (trimellitic acid), 2,5, 7-naphthalene tricarboxylic acid, 1,2, 4-naphthalene tricarboxylic acid, and pyromellitic acid, and aliphatic carboxylic acids such as 1,2, 4-butane tricarboxylic acid, 1,2, 5-hexane tricarboxylic acid, and 1, 3-dicarboxy-2-methyl-2-methylenecarboxypropane. Also included are derivatives such as anhydrides thereof or lower alkyl esters thereof.

In addition, the crystalline polyester may contain a monocarboxylic acid. Examples of monocarboxylic acids include benzoic acid, naphthalene carboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, caprylic acid, capric acid (capric acid)), undecanoic acid, lauric acid (dodecanoic acid), tridecanoic acid, myristic acid (tetradecanoic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid (heptadecanoic acid)), stearic acid (octadecanoic acid), nonadecanoic acid, arachic acid (eicosanoic acid), heneicosanoic acid, behenic acid (docosylic acid), tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic 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 viewpoints of low-temperature fixability, image heat resistance and curl resistance. If the content is less than 8 parts by mass, the low-temperature fixability is deteriorated, crystallization becomes difficult to proceed, and the image heat resistance is liable to be deteriorated. When the content is more than 15 parts by mass, not only the image heat resistance is deteriorated, but also the crystallization becomes excessive, so that the curl resistance is liable to be deteriorated.

The crystalline polyester can be produced according to a usual polyester synthesis method. For example, the crystalline polyester can be obtained by subjecting the above carboxylic acid monomer and alcohol monomer to an esterification reaction or transesterification reaction, and then performing a polycondensation reaction under reduced pressure or with the introduction of nitrogen gas according to a conventional method. Thereafter, the aliphatic compound is further added and an esterification reaction is performed, whereby a desired crystalline polyester can be obtained.

The above-mentioned esterification or transesterification reaction may be carried out using a usual esterification or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate, if necessary.

The polycondensation reaction may be carried out using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, and other known catalysts. The polymerization temperature and the catalyst amount are not particularly limited and may be appropriately determined.

In the esterification or transesterification reaction or polycondensation reaction, a method involving adding all the monomers at once to increase the strength of the resulting crystalline polyester may be employed, or a method involving first reacting a dibasic monomer, then adding a tribasic or higher monomer and reacting the tribasic or higher monomer to reduce the amount of the low molecular weight component may be employed.

< Release agent >

The toner particles of the toner of the present invention preferably contain a releasing agent. Examples of the release agent that can be used for the toner of the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystalline waxes, paraffin waxes, and fischer-tropsch waxes; hydrocarbon wax oxides such as oxidized polyethylene wax or block copolymers thereof; waxes containing fatty acid esters as a main component, such as carnauba wax; and fatty acid esters partially or totally deoxidized such as deoxidized carnauba wax.

The following is also included. Saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brasilenic acid, eleostearic acid and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, palmityl alcohol, ceryl alcohol, and melissa alcohol; polyols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, ceryl alcohol and melissa alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauramide and hexamethylene bisstearamide; unsaturated fatty acid amides such as ethylene bis-oleamide, hexamethylene bis-oleamide, N '-dioleyladipamide and N, N' -dioleylsebacamide; aromatic bisamides such as m-xylene bisstearamide and N, N' -distearyl isophthalic acid amide; aliphatic metal salts (commonly referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting a vinyl monomer such as styrene or acrylic acid to an aliphatic hydrocarbon-based wax; partial esters of fatty acids and polyols such as monoglyceride of behenic acid; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils.

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

The content of the 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 sum of crystalline polyester and amorphous resin.

In addition, in an endothermic curve during a temperature increase measured by a Differential Scanning Calorimeter (DSC), the peak temperature of the maximum endothermic peak of the wax is preferably 80 ℃ or more and 110 ℃ 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。

by this relationship, it is possible to induce crystallization of the crystalline polyester from the crystallization start of the wax, and control the crystallization behavior of the crystalline polyester during cooling.

< dispersant >

When the toner particles of the toner of the present invention contain a releasing agent, a dispersing agent is preferably contained to disperse the wax in the resin. The dispersant used may be known, and when a hydrocarbon-based wax is contained as the wax, in order to disperse the wax in the resin, it is preferable to contain a polymer having a structure in which a vinyl-based resin component and a hydrocarbon compound react with each other. Among them, a graft polymer obtained by graft polymerization of a vinyl monomer to a polyolefin is preferably contained.

When the polymer is contained, compatibility between the wax and the resin is promoted, and adverse effects such as poor charging due to poor dispersion of the wax and contamination of members are unlikely to occur. The content of the dispersant is preferably 1.0 part 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 the above range, the wax tends to be uniformly dispersed in the amorphous resin. The polyolefin is not particularly limited as long as it is a polymer or copolymer of unsaturated hydrocarbons, and various polyolefins may be used. In particular, polyethylene-based and polypropylene-based materials are preferably used. Two or more of these may be used.

Examples of the monomer having a vinyl group include the following.

For example, styrenes include styrene units such as styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3, 4-dichlorostyrene, p-ethylstyrene, 2, 4-dimethylstyrene, p-n-butylstyrene, p-t-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene and derivatives thereof.

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

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, and mesaconic acid; unsaturated dianhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenylsuccinic anhydride; half esters of unsaturated dibasic acids such as methyl half maleate, ethyl half maleate, butyl half maleate, methyl half citraconate, ethyl half citraconate, butyl half citraconate, methyl half itaconate, methyl half alkenylsuccinate, methyl half fumarate and methyl half mesaconate; unsaturated dibasic acid esters such as dimethyl maleate and dimethyl fumarate; α, β -unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; α, β -unsaturated anhydrides such as crotonic anhydride and cinnamic anhydride, and anhydrides of the above α, β -unsaturated acids and lower fatty acids; and vinyl units containing a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, anhydrides thereof, and monoesters thereof.

Acrylic and methacrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and vinyl units containing a hydroxyl group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

Ester units composed of acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.

Ester units composed of methacrylic acid esters such as α -methylene aliphatic monocarboxylic acid esters, for example, cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. Two or more of these may be used.

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

< colorant >

Examples of the colorant that may be contained in the toner of the present invention include the following.

The black colorant includes carbon black; and those blackened with yellow, magenta and cyan colorants. As the colorant, a pigment may be used alone, but from the viewpoint of full-color image quality, it is more preferable to use a dye in combination with a pigment to improve sharpness.

Examples of the magenta toner pigment 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, and 282; c.i. pigment violet 19; and c.i. vat red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of magenta toner dyes include the following. For example c.i. solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109 and 121; c.i. disperse red 9; c.i. solvent violet 8, 13, 14, 21 and 27; and c.i. disperse violet 1 and like oil-soluble dyes, e.g. c.i. basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39 and 40; and c.i. basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

Examples of the cyan toner pigment include the following. C.i. pigment blue 2, 3, 15:2, 15:3, 15:4, 16, 17; c.i. vat blue 6; c.i. acid blue 45, and a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups.

Examples of cyan toner dyes include c.i. solvent blue 70.

Examples of the yellow toner pigment 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 and 185; and c.i. vat yellow 1, 3 and 20.

Examples of yellow toner dyes include c.i. 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 may further contain a charge control agent as needed. As the charge control agent contained in the toner, a known charge control agent can be used, and a metal compound of an aromatic carboxylic acid is particularly preferable because it is colorless, the charging speed of the toner is high, and a constant charge amount can be stably maintained.

Examples of the negative charge control agent include a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, and a polymeric compound having a sulfonic acid or carboxylic acid as a side chain, a high molecular weight compound having a sulfonate or sulfonate as a side chain, a polymeric compound having a carboxylate or carboxylate as a side chain, and a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymeric compounds having quaternary ammonium salts in 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 to be added is preferably 0.05 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the binder resin.

< inorganic Fine particles >

The toner may further contain inorganic fine particles as needed. The inorganic fine particles may be internally added 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, titania, and alumina are preferable. 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 flowability, the specific surface area was 50m ² Above/g and 400m ² Inorganic fine powder of/g or less is preferable. In order to stabilize the durability, the specific surface area is 10m ² Above/g and 50m ² Inorganic fine powder of/g or less is preferable. In order to improve fluidity and stabilize durability at the same time, inorganic fine powders having a specific surface area within the above-mentioned range may be used in combination.

The content of the external additive used is preferably 0.10 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the toner particles. The toner particles and the external additive may be mixed using a known mixer such as a Henschel mixer.

[ developer ]

The toner of the present invention can also be used as a one-component developer, but is preferably used as a two-component developer in combination with a magnetic carrier in order to provide a stable image.

When the toner is mixed with the magnetic carrier for use as a two-component developer, as the toner concentration in the two-component developer, the mixing ratio of the magnetic carrier in this case is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

< magnetic Carrier >

As the magnetic carrier, for example, iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, strontium, and rare earth, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite and magnetite; and a magnetic material-dispersed resin carrier (so-called resin carrier) comprising a magnetic material and a binder resin for holding the magnetic material in a dispersed state, and a known carrier such as a magnetic carrier in the form of ferrite or magnetite particles having pores filled with a resin.

As the magnetic carrier, any of the above-described magnetic materials may be used as it is, or a magnetic material obtained by coating the surface of any of the above-described magnetic materials as a core with a resin may be used. From the viewpoint of improving the chargeability of the toner, as the magnetic carrier, a magnetic material obtained by coating the surface of any one of the above-described magnetic materials as a core with a resin is preferably used.

The resin for coating the core is not particularly limited, and known resins may be selected and used as long as the characteristics of the above toner are not impaired. Resins such as (meth) acrylic resins, silicone resins, polyurethane resins, polyethylene terephthalate, polystyrene, and phenolic resins, or copolymers or polymer mixtures containing these resins can be used. In particular, from the viewpoints of chargeability and prevention of adhesion of foreign matter to the carrier surface, a (meth) acrylic resin or a silicone resin is preferably used. In particular, a (meth) acrylic resin having an alicyclic hydrocarbon group such as cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl, cyclobutyl, or cyclopropyl is a particularly preferable form because the surface of the resin coating layer (coated surface) that coats the surface of the magnetic material becomes smooth and the adhesion of components from the toner such as a binder resin, a release agent, and an external additive can be suppressed.

[ production method ]

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

An exemplary process of producing toner by the pulverization method will be described below.

In the raw material mixing step, as materials constituting the toner particles, for example, prescribed amounts of crystalline polyester and amorphous resin, and other components such as a release agent, a colorant, and a charge control agent are weighed, blended, and blended as necessary. Examples of the mixing device include a twin cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by NIPPON bike & ENGINEERING co., ltd.).

Next, the mixed materials are melt-kneaded to disperse wax or the like in the binder resin. The kneading and discharging temperatures may be appropriately adjusted depending on the binder resin and the colorant used, but are generally preferably 100 to 180 ℃. In the melt kneading step, a pressure kneader, a batch kneader such as a Banbury mixer, or a continuous kneader may be used, and single-screw or twin-screw extruders are the mainstream because of their superiority in continuous production. Examples include KTK-type twin screw extruders (manufactured by Kobe Steel, ltd.), TEM-type twin screw extruders (manufactured by Toshiba Machine co., ltd.), PCM kneaders (manufactured by IKEGAI corp., ltd.), twin screw extruders (manufactured by k.c. k.co., ltd.), co-kneaders (manufactured by Buss), and Kneadex (manufactured by NIPPON co ke & ENGINEERING co., ltd.). 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 into a desired particle size in a pulverizing step. The pulverizing step is coarse-pulverizing with a pulverizer such as a crusher, a hammer mill, or a feather mill, and then further fine-pulverizing with a pulverizer such as a krypton system (manufactured by Kawasaki Heavy Industries ltd.), a super rotor (manufactured by Nisshin Engineering inc.), a turbo mill (manufactured by Freund-Turbo Corporation), or an air jet type fine pulverizer.

Then, classification is performed using a classifier or a sieving machine such as an inertial classification type Elbow-Jet (manufactured by nitetsu minigco., ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), or a faultey (manufactured by Hosokawa Micron Corporation) as necessary to obtain a classified product (toner particles).

The toner particles may be used directly as toner, or the toner may be obtained by adding an external additive to the surface of the toner particles as needed. Examples of the method of externally adding the external additive include a method of blending toner particles and various known external additives in prescribed amounts, and stirring and mixing using a mixing device such as a twin cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., ltd.) or Nobilta (manufactured by Hosokawa Micron Corporation) as the external additive.

[ method of measuring physical Properties ]

Next, a measurement method of each physical property related to the present invention is described.

< separation of materials from toner >

The material is separated from the toner using the difference in solubility in the solvent and GPC.

Examples are shown below.

First separation: the toner was dissolved in Methyl Ethyl Ketone (MEK) at 23 ℃ to separate soluble substances (amorphous resins) and insoluble substances (crystalline polyesters, and optionally added waxes, wax dispersants, colorants, inorganic particles, and the like).

And (3) separating for the second time: the insoluble matters (crystalline polyester and optionally added wax, wax dispersant, colorant, inorganic particles, etc.) obtained in the first separation were dissolved in MEK at 100 ℃ to separate the soluble matters (crystalline polyester, wax, and wax dispersant) and the insoluble matters (colorant and inorganic particles).

Third separation: the soluble matters (crystalline polyester, wax and wax dispersant) obtained in the second separation were dissolved in chloroform at 23 ℃ to separate the soluble matters (crystalline polyester) and insoluble matters (wax and wax dispersant).

Fourth separation: if the amorphous resin is further separated, the soluble substance obtained in the first separation is separated by GPC using a molecular weight and polarity difference.

< calculation of the content ratio of monomer Unit in amorphous resin and crystalline polyester >

The content of the constituent monomers in the resin was calculated by the following method using NMR.

Weighing 5mg of the resin separated by the method, dissolving in deuterated THF or deuterated chloroform, and performing ¹ H-NMR measurement, the composition ratio was calculated from the integral value of each peak. Specific device conditions are as follows.

(measurement conditions)

Measuring device: JNM-ECA400 FT-NMR (JEOL)

Measuring core: ¹ H

solvent: deuterated THF or deuterated chloroform

Measuring frequency: 400MHz

Pulse width: 5.0 mu s

Frequency range: 10500Hz

Cumulative number of times: 64 times

Measuring temperature: room temperature

< measurement of glass transition temperature (Tg) of resin >

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

The melting points of indium and zinc are used to correct the temperature of the device detector and the heat of fusion of indium is used to correct the heat.

Specifically, about 3mg of the resin or toner was precisely weighed, placed in an aluminum pan, and measured using an empty aluminum pan as a reference under the following conditions:

rate of temperature rise: 10 ℃/min

Measuring the initial temperature: 30 DEG C

Measuring the end temperature: 180 DEG C

The temperature was measured at a temperature rising rate of 10 deg.c/min in a measurement range of 30 deg.c to 180 deg.c. The temperature was once raised to 180 ℃ for 10 minutes, then lowered to 30 ℃ and then raised again. In this second temperature increase process, a change in specific heat is obtained in a temperature range of 30 to 100 ℃. The intersection point of the differential thermal curve with a line between the intermediate points of the baselines before and after the occurrence of the change in specific heat is defined as the glass transition temperature (Tg) of the resin.

< differential scanning calorimetric measurement (DSC) of toner >

Differential scanning calorimeter measurement of the toner was performed using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

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

The temperature was increased from 20 ℃ to 180 ℃ at a rate of 10 ℃/min, then cooled to 25 ℃ at a rate of 10 ℃/min, and the toner was cooled from 25 ℃ to 15 ℃ at a rate of 3 ℃/min. Thereafter, the temperature was raised to 180℃at a rate of 10℃per minute for the second time.

The exothermic amount of the peak derived from the crystalline polyester existing at 40 ℃ or higher and 80 ℃ or lower upon cooling at a rate of 10 ℃/min is represented as P1 (J/g), the exothermic amount of the peak derived from the crystalline polyester existing during cooling at a rate of 3 ℃/min is represented as P2 (J/g), the sum of the exothermic amounts of the endothermic peaks existing at 40 ℃ or higher observed during the second temperature rising is represented as P3 (J/g), the sum of the exothermic amounts of the exothermic peaks existing at 40 ℃ or higher observed during the cooling step is represented as P4 (J/g), and the endothermic peak observed during the second temperature rising is used to determine the melting point T1 of the wax and the melting point T2 of the crystalline polyester. If it is difficult to identify the peaks by measuring only the toner, differential scanning calorimetric measurement may be performed on the separated materials alone or mixed with the amorphous resin to identify which material T1 and T2 in the toner belong to.

< SP value calculation method >

The evaporation energy (. DELTA.ei) (cal/mol) and the molar volume (. DELTA.vi) (cm) of atoms or groups of atoms in the molecular structure were determined for SP values of the amorphous resin A, the amorphous resin B, the amorphous resin C and the crystalline polyester by the calculation method proposed by Fedors using the tables given in "Polym.Eng.Sci.,14 (2), 147-154 (1974)" ³ Per mol), 2.0455 × (ΣΔei/ΣΔvi) ^0.5 As SP value (J/cm) ³ ) ^0.5 。

< measurement of molecular weight of amorphous resin by GPC >

The molecular weight distribution of THF-soluble matter of the resin was measured by Gel Permeation Chromatography (GPC) as follows.

First, the toner was dissolved in Tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution was then filtered through a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) having a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution was adjusted so that the concentration of THF-soluble components was about 0.8 mass%. The sample solution was used for measurement under the following conditions:

the device comprises: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)

Column: 7 columns, 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 DEG C

Sample injection volume: 0.10mL

Molecular weight calibration curves prepared using standard polystyrene resins (e.g., trade names "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, and A-500", manufactured by Tosoh Corporation ") were used to calculate the molecular weights of the samples.

< measurement of molecular weight of crystalline polyester by GPC >

First, the crystalline polyester was dissolved in o-dichlorobenzene at room temperature for 24 hours. The resulting solution was then filtered through a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) having a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution was adjusted so that the concentration of THF-soluble components was about 0.8 mass%. The sample solution was used for measurement under the following conditions:

the device comprises: HLC-8121GPC/HT (manufactured by Tosoh Corporation)

Column: 2-column, TSKgel GMHHR-HHT (7.8 mm I.D.times.30 cm) (manufactured by Tosoh Corporation)

A detector: RI for high temperature

Temperature: 135 DEG C

Solvent: o-dichlorobenzene (0.05% ionol added)

Flow rate: 1.0mL/min

Sample: 0.4mL of 0.1% sample was injected

Measurements were made under the above conditions and molecular weight of the samples were calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples. Furthermore, it is calculated by converting into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

< method for measuring softening Point of amorphous resin >

The softening point of the resin was measured using a constant load extrusion capillary rheometer "Flow Property Evaluation Device FlowTester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. The device applies a certain load from above the measuring sample through the piston, heats and melts the measuring sample filled in the charging barrel, and extrudes the melted measuring sample through the die head at the bottom of the charging barrel, so that a flow curve showing the relation between the lowering amount of the piston and the temperature at the moment can be obtained.

In the present invention, the softening point is the "melting temperature of 1/2 method" described in the handbook attached to "Flow Property Evaluation Device FlowTester CFT-500D". Note that the melting temperature of the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston-down amount Smax at the end of outflow and the piston-down amount Smin at the beginning of outflow is obtained (set to X, x= (Smax-Smin)/2). When the piston drop is X in the flow curve, the temperature of the flow curve is the melting temperature of the 1/2 method.

The measured sample was about 1.0g of resin, and was compressed and molded at about 10MPa for about 60 seconds in an environment of 25 ℃ using a tablet press (e.g., NT-100H, manufactured by NPa systemco., ltd.) to form a cylindrical shape having a diameter of about 8 mm.

The measurement conditions of CFT-500D were as follows:

test mode: wen Shengfa

Starting temperature: 50 DEG C

Final temperature: 200 DEG C

Measurement interval: 1.0 DEG C

Rate of temperature rise: 4.0 ℃/min

Piston cross-sectional area: 1.000cm ²

Test load (piston load): 10.0kgf (0.9807 MPa)

Preheating time: 300 seconds

Diameter of die hole: 1.0mm

Die length: 1.0mm

< measurement of melting Point of Release agent >

The melting points of indium and zinc are used to correct the temperature of the device detector and the heat of fusion of indium is used to correct the heat. Specifically, about 2mg of the sample was precisely weighed and placed in an aluminum pan, and an empty aluminum pan was used as a reference to measure at a temperature rising rate of 10 ℃/min in a measurement temperature range of 30 ℃ to 200 ℃. Note that in the measurement, the temperature was once raised to 200 ℃, then lowered to 30 ℃, and then raised again. The peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ℃ during the second temperature elevation is defined as the melting point. There was no retention time after the temperature was increased to 200 ℃, and once the temperature reached 200 ℃, the temperature was reduced to 30 ℃.

< method for measuring weight average particle diameter (D4) of toner particles >

The weight average particle diameter (D4) of the toner particles was calculated by analyzing measurement data obtained by measurement of 25000 effective measurement channels using a precision particle size distribution measuring apparatus "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, inc.) equipped with a 100 μm mouth tube, and an accompanying dedicated software "Beckman Coulter Multisizer 3version 3.51" (manufactured by Beckman Coulter, inc.) for setting measurement conditions and analyzing measurement data.

As the aqueous electrolyte solution used for measurement, for example, "Isoton II" (manufactured by Beckman Coulter, inc.) or the like, extra sodium chloride dissolved in ion-exchanged water at a concentration of about 1 mass% can be used.

Note that the dedicated software is configured as follows before measurement and analysis are performed.

In a "standard change measurement method (SOM) screen" of the dedicated software, the total count value in the control mode was set to 50000 particles, the number of measurements was set to 1, and the Kd value was set to a value obtained using "standard particle 10.0 μm" (manufactured by Beckman Coulter, inc.). The threshold and noise level are automatically set by pressing the threshold/noise level measurement button. Further, the current was set to 1600 μa, the gain was set to 2, the electrolyte was set to ISOTON II, and the flushing of the oral tube after the measurement was checked.

In the "pulse-particle diameter conversion setting screen" of the dedicated software, the interval is set to logarithmic particle diameter, the particle diameter elements are set to 256 particle diameter elements, and the particle diameter range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.

(1) About 200mL of the aqueous electrolyte solution was placed in a 250mL round bottom glass beaker dedicated to Multisizer 3, which was placed on a sample holder with a stirring bar counter-clockwise at 24 revolutions per second. Then, the "orotracheal rinsing" function of the analysis software is used to remove dirt and bubbles from the inside of the orocanal.

(2) About 30ml of the aqueous electrolyte solution was placed in a 100ml flat bottom glass beaker, and about 0.3ml of a diluted solution obtained by diluting "Containon N" by 3 times by mass with deionized water (10% by mass aqueous solution of a neutral detergent having a pH of 7 for washing a precision measuring instrument, made of a nonionic surfactant, an anionic surfactant and an organic builder, manufactured by Wako Pure Chemical Industries, ltd.) was added thereto as a dispersant.

(3) 2 oscillators having an oscillation frequency of 50kHz were placed in 180 degrees of phase shift, and a prescribed amount of ion-exchanged water was placed in a water bath of an ultrasonic wave dispersing apparatus "Ultrasonic Dispension System Tetora150" (manufactured by Nikkaki BIOS Co.Ltd.) having an electric output of 120W, and about 2ml of Containon N was added to the water bath.

(4) Placing the beaker of (2) in a beaker-holding hole of an ultrasonic dispersion device to operate the ultrasonic dispersion device. Then, the height position of the beaker was adjusted to maximize the resonance state of the liquid level of the electrolyte aqueous solution in the beaker.

(5) While the aqueous electrolyte solution in the beaker in (4) above was irradiated with ultrasonic waves, about 10mg of toner was added little by little to the aqueous electrolyte solution and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. Note that in ultrasonic dispersion, the water temperature in the water bath is appropriately adjusted to 10 ℃ or higher and 40 ℃ or lower.

(6) To a round-bottom glass beaker of (1) provided in a sample holder, an aqueous electrolyte solution of the above-mentioned (5) in which a toner was dispersed was dropped using a pipette, and the measured concentration was adjusted to about 5%. The measurement was then continued until the number of measurement particles reached 50000.

(7) The measurement data were analyzed by dedicated software attached to the apparatus, and the weight average particle diameter was calculated (D4). Note that when the graph/volume% is set on the dedicated software, the "average diameter" on the analysis/volume statistics (arithmetic average) screen is the weight average particle diameter (D4).

< method for measuring acid value >

The acid number is the mass of potassium hydroxide required to neutralize the acid contained in 1g of the sample [ mg ]. That is, the mass [ mg ] of potassium hydroxide required for neutralizing free fatty acids, resin acids, and the like contained in 1g of the sample is referred to as an acid value.

In the present invention, the acid value was measured in accordance with JIS K0070-1992. Specifically, the measurement was performed according to the following procedure.

(1) Preparation of reagents

1.0g of phenolphthalein was dissolved in 90ml of ethanol (95 vol%) and ion-exchanged water was added thereto to a volume of 100ml, to obtain a phenolphthalein solution.

7g of extra potassium hydroxide was dissolved in 5mL of water, to which ethanol (95 vol%) was added to a volume of 1 liter. Placing in alkali-resistant container, standing for 3 days, and not contacting with carbon dioxide gas, etc. After standing, filtering to obtain potassium hydroxide solution. The resulting potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined as follows. 25ml of 0.1mol/L hydrochloric acid was placed in an conical flask, a few drops of the above phenolphthalein solution were added, titration was performed with the above potassium hydroxide solution, and the amount of potassium hydroxide solution required for neutralization was used to determine the factor.

The above-mentioned 0.1mol/L hydrochloric acid used was prepared in accordance with JIS K8001-1998.

(2) Operation of

(A) Main experiment

2.0g of the sample was placed in a 200mL Erlenmeyer flask and accurately weighed, 100mL of a toluene/ethanol (2:1) mixed solution was added thereto, and the sample was dissolved in 5 hours. Then, a plurality of drops of the phenolphthalein solution was added as an indicator, and titration was performed using the potassium hydroxide solution. The endpoint of the titration was a pale red color of the indicator for 30 seconds.

(B) Blank experiment

The same titration as described above was performed except that no sample was added (i.e., only toluene/ethanol (2:1) mixed solution was used).

(3) Calculation of acid value

The acid value was calculated by substituting the obtained result into the following formula.

AV＝[(B-A)×F×5.61]/S

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

Note that when the amorphous resin B and the amorphous resin B' are mixed and used in the present invention, 1g of the mixed sample is used to measure the acid value.

< method for measuring hydroxyl value >

The hydroxyl number is the mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl groups when 1g of the sample is acetylated. The hydroxyl value of the binder resin was measured according to JIS K0070-1992, more specifically, it was measured according to the following procedure.

(1) Preparation of reagents

25g of superfine acetic anhydride was placed in a 100mL volumetric flask, pyridine was added thereto to a total volume of 100mL, and the mixture was sufficiently shaken to obtain an acetylation reagent. The obtained acetylating agent is stored in a brown bottle without contact with moisture, carbon dioxide gas, or the like.

1.0g of phenolphthalein was dissolved in 90ml of ethanol (95 vol%) and ion-exchanged water was added thereto to a volume of 100ml to obtain a phenolphthalein solution.

35g of extra potassium hydroxide was dissolved in 20ml of water, and ethanol (95 vol%) was added thereto to a volume of 1 liter. Standing in alkali-resistant container for 3 days without contact with carbon dioxide gas, etc., and filtering to obtain potassium hydroxide solution. The resulting potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined as follows. 25ml of 0.5mol/L hydrochloric acid was placed in an conical flask, a few drops of phenolphthalein solution were added, titration was performed with potassium hydroxide solution, and the amount of potassium hydroxide solution required for neutralization was used to determine the factor. The 0.5mol/L hydrochloric acid used was prepared in accordance with JIS K8001-1998.

(2) Operation of

(A) Main experiment

1.0g of the sample was weighed exactly in a 200ml round bottom flask, to which 5.0ml of acetylating reagent was added exactly using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of extra-grade toluene is added to dissolve it.

The small funnel was placed on the flask mouth, and the bottom of the flask was immersed in a glycerin bath at about 97 ℃ at a depth of about 1cm and heated. At this time, in order to prevent the temperature of the neck portion of the flask from rising due to the bath heat, the bottom portion of the neck portion of the flask is preferably covered with a piece of cardboard having a circular hole.

After 1 hour, the flask was removed from the glycerol bath and allowed to cool. After cooling, 1ml of water was added through the funnel and shaken to hydrolyze the acetic anhydride. For more complete hydrolysis, the flask was again heated in a glycerol bath for 10 minutes. After cooling, the walls of the funnel and flask were washed with 5ml ethanol.

Several drops of phenolphthalein solution were added as an indicator and titration was performed using potassium hydroxide solution. Note that the endpoint of the titration is a pale red color of the indicator for about 30 seconds.

(B) Blank experiment

The same titration as described above was performed except that no sample was used.

(3) Substituting the obtained result into the following formula to calculate a hydroxyl value:

A＝[{(B-C)×28.05×f}/S]+D，

wherein A: hydroxyl number (mg KOH/g), B: amount of potassium hydroxide solution added (ml) in blank experiments, C: amount of potassium hydroxide solution added in main experiment (ml), f: factor of potassium hydroxide solution, S: sample (g), and D: acid value of sample (mg KOH/g).

< measurement of BET specific surface area of inorganic Fine particles >

The BET specific surface area of the inorganic fine particles was measured in accordance with JIS Z8830 (2001). The specific measurement method is as follows.

The measurement apparatus used was "automatic specific surface area and porosity analyzer Tristar 3000 (manufactured by Shimadzu Corporation)" using a constant volume gas adsorption method as a measurement method. The setting of the measurement conditions and the analysis of the measurement data were performed using the dedicated software "Tristar 3000 version 4.00" attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe were connected to the apparatus. The value calculated by the BET multipoint method using nitrogen as the adsorption gas is defined as the BET specific surface area of the inorganic fine particles in the present invention.

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

First, nitrogen gas was adsorbed to the inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell and nitrogen adsorption of the external additive at this time were measuredQuantity Va (mol. G) ^-1 ). The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is obtained as the horizontal axis, and the nitrogen adsorption amount Va (mol. G ^-1 ) Adsorption isotherms were taken as the vertical axis. Next, the monolayer adsorption amount Vm (mol. G) which is the adsorption amount required for forming a monolayer on the surface of the external additive was obtained by applying the following BET formula ^-1 )：

Pr/Va(1-Pr)＝1/(Vm×C)+(C-1)×Pr/(Vm×C)。

(wherein C is a BET parameter which is a variable that varies depending on the type of the measurement sample, the type of the adsorbed gas, and the adsorption temperature).

If the X-axis is Pr and the Y-axis is Pr/Va (1-Pr), the BET formula can be interpreted as a straight line with a slope of (C-1)/(Vm C) and an intercept of 1/(Vm C) (this straight line is called the BET plot).

Straight line slope= (C-1)/(vm×c)

Straight line intercept=1/(vm×c)

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

Furthermore, using the calculated Vm and the cross-sectional area occupied by the nitrogen molecules (0.162 nm ² ) The BET specific surface area S (m) of the inorganic fine particles was calculated according to the following formula ² /g)：

S＝Vm×N×0.162×10 ^-18 。

(wherein N is the Avogaldro number (mol) ^-1 )。)

The measurement using the apparatus was performed according to "Tristar 3000 instruction manual V4.0" attached to the apparatus, specifically, the following procedure.

The well-washed and dried dedicated glass sample cell (rod diameter 3/8 inch, volume about 5 ml) was weighed accurately. Then, about 0.1g of the external additive was placed in the sample cell with a funnel.

The sample cell containing the inorganic fine particles was set in a "pretreatment device VacPrep 061 (manufactured by Shimadzu Corporation)" to which a vacuum pump and a nitrogen pipe were connected, and vacuum degassing was continued at 23 ℃ for about 10 hours. During vacuum degassing, the valve is gradually degassed so that inorganic fine particles are not sucked into the vacuum pump. The pressure in the cell gradually decreased with degassing, eventually reaching about 0.4Pa (about 3 mTorr). After the vacuum degassing was completed, nitrogen gas was gradually injected to restore the inside of the sample cell to atmospheric pressure, and the sample cell was taken out of the pretreatment device. The mass of the cell was then accurately weighed and the exact mass of the external additive was calculated from the difference from the tare. Note that at this time, the sample cell is covered with a rubber stopper at the time of weighing so that the external additive in the sample cell is not contaminated with moisture or the like in the atmosphere.

Next, a dedicated "isothermal jacket" was attached to the stem of the sample cell containing inorganic fine particles. A special filling rod is then inserted into the cuvette and the cuvette is placed in the analysis port of the device. Note that the isothermal sheath is a cylindrical member with a porous inner surface and an impermeable outer surface capable of drawing liquid nitrogen to a level by capillary action.

Then, the free space of the sample cell containing the connecting device is measured. Free space is calculated as follows. The volume of the cell was measured at 23 ℃ using helium, and after cooling the cell with liquid nitrogen, the volume of the cell was likewise measured using helium. The free space is calculated by scaling the difference between these volumes. Further, the saturated vapor pressure Po (Pa) of nitrogen gas was measured separately and automatically using a Po tube built into the apparatus.

Next, the inside of the sample cell was vacuum degassed, and then the sample cell was cooled with liquid nitrogen while continuing vacuum degassing. Thereafter, nitrogen gas was gradually introduced into the sample cell, and the toner was allowed to adsorb nitrogen molecules. At this time, since the adsorption isotherm can be obtained by measuring the equilibrium pressure P (Pa) at any time, the adsorption isotherm is converted into a BET map. Note that the points of the relative pressure Pr of the data collection were set to 6 points in total of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn on the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, the BET specific surface area of the inorganic fine particles was calculated as described above using the Vm value.

[ constitution included in the embodiment of the present invention ]

The disclosure of the embodiments includes the following constitution.

(constitution 1) A toner comprising:

toner particles comprising a binder resin and a crystalline polyester, wherein

When Differential Scanning Calorimetric (DSC) of the toner undergoes: (i) heating to 180 ℃ at a rate of 10 ℃/min, (ii) then cooling the toner from 180 ℃ to 25 ℃ at a rate of 10 ℃/min, (iii) subsequently cooling the toner from 25 ℃ to 15 ℃ at a rate of 3 ℃/min, and (iv) when the temperature of the toner is again increased to 180 ℃ at a rate of 10 ℃/min,

in the process of cooling the toner at a rate of 10 ℃/min, the exothermic amount P1 of a peak derived from crystalline polyester existing at 40 ℃ or higher and 80 ℃ or lower is 1.00J/g or lower,

an exothermic amount P2 of a crystallization peak derived from the crystalline polyester, which is present during cooling of the toner at a rate of 3 ℃/min, is 0.10J/g or more, and

when the sum of the endothermic amounts of the endothermic peaks existing at 40 ℃ or higher observed during the second temperature increase in the DSC of the toner is expressed as P3 (J/g), and the sum of the exothermic amounts of the exothermic peaks existing at 40 ℃ or higher observed during the cooling of the toner at a rate of 10 ℃/min is expressed as P4 (J/g), the following formula (1) is satisfied:

The formula (1) is 2.0-P3-P4-10.0.

(constitution 2) the toner according to constitution 1, wherein the exothermic amount P1 of a peak derived from the crystalline polyester existing at 40 ℃ or more and 80 ℃ or less is 0.50J/g or less in the process of cooling the toner at a rate of 10 ℃/min.

(constitution 3) the toner according to constitution 1 or 2, wherein the ratio of the crystalline polyester to the binder resin is 8.0% by mass or more and 15.0% by mass or less.

(constitution 4) the toner according to any one of constitution 1 to 3, wherein the toner contains a hydrocarbon-based wax, and a difference between a melting point T1 (°c) of the hydrocarbon-based wax in the toner and a melting point T2 (°c) of the crystalline polyester satisfies the following formula (2):

the formula (2) is 2-T1-T2-10.

(constitution 5) the toner according to any one of constitution 1 to 4, wherein the binder resin comprises an amorphous resin A, an amorphous resin B and an amorphous resin C, when the SP value of the amorphous resin A [ (J/cm) ³ ) ^0.5 ]SP value [ (J/cm) of amorphous resin B ] denoted as SP1 ³ ) ^0.5 ]SP value of amorphous resin C [ (J/cm) denoted as SP2 ³ ) ^0.5 ]Expressed as SP3, and when the crystalline polyester has SP value [ (J/cm) ³ ) ^0.5 ]When denoted as SP4, the formulas (3) to (5) are satisfied:

(constitution 6) a two-component developer comprising: a toner and a magnetic carrier, wherein the toner is the toner according to any one of constitutions 1 to 5.

Examples (example)

The present invention will be described below with reference to examples and the like. Note that the description of these embodiments does not limit the technical scope of the present invention.

< production example of amorphous resin A1 >

Bisphenol a propylene oxide adduct (average number of moles added 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%)

Tetrabutyl titanate (esterification catalyst): 0.5 part by mass

The above materials were weighed into a reactor equipped with a condenser, a stirrer, a nitrogen introduction tube and a thermocouple.

Then, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed at a temperature of 200℃for 2 hours while stirring.

In addition, the pressure in the reactor was reduced to 8.3kPa and maintained for 1 hour, then cooled to 160 ℃ and returned to atmospheric pressure.

Trimellitic anhydride: 7.2 parts by mass (10.0 mol%)

After that, the above-mentioned materials were added, the pressure in the reactor was reduced to 8.3kPa, and the reaction was allowed to proceed while maintaining the temperature at 200 ℃, confirming that the softening point reached the temperature shown in table 1. Then, the temperature was lowered to stop the reaction, to obtain an amorphous polyester resin A1. Table 1 shows the physical properties thereof.

< production example of amorphous resins A2 to A4 >

Amorphous resins A2 to A4 were obtained in the same manner as in the production example of the amorphous resin A1 except that the monomers used were changed as shown in table 1. Table 1 shows the composition and physical properties of the resulting amorphous resins A2 to A4.

TABLE 1

Abbreviations in table 1 are as follows:

BPA-PO (2.2): propylene oxide adducts of bisphenol A (average number of moles added 2.2 mol)

BPA-PO (2.5): propylene oxide adducts 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 moles added 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 part by mass (0.3 mol%)

Tetrabutyl titanate (esterification catalyst): 0.5 part by mass

The above materials were weighed into a reactor equipped with a condenser, stirrer, nitrogen inlet tube and thermocouple.

Then, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed at a temperature of 200℃for 3 hours while stirring. Thereafter, the pressure in the reactor was reduced to 8.3kPa, the reaction was performed while maintaining the temperature at 200℃and it was confirmed that the softening point reached the temperature shown in Table 2. Then, the temperature was lowered to stop the reaction, to obtain amorphous resin B1. Table 2 shows its physical properties.

< production examples of amorphous resins B2 and B3 >

Amorphous resins B2 and B3 were obtained in the same manner as in the production example of the amorphous resin B1, except that the monomers used were changed as shown in table 2. Table 2 shows the composition and physical properties of the resulting amorphous resins B2 and B3.

TABLE 2

Abbreviations in table 2 are as follows:

< production example of amorphous resin C1 >

Bisphenol a propylene oxide adduct (average number of moles added 2.2 mol): 39.8 parts by mass (26.4 mol%)

Bisphenol a ethylene oxide adducts (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 part 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 2-ethylhexanoate (II): 0.5 part by mass

Then, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed at a temperature of 200℃for 4 hours while stirring.

Then, after 0.5 part by mass of dicumyl peroxide was added, 0.6 part by mass (1.5 mol%) of methyl methacrylate was added dropwise over 1 hour while stirring. Thereafter, the pressure in the reactor was reduced to 8.3kPa, the reaction was performed while maintaining the temperature at 200℃and it was confirmed that the softening point reached the temperature shown in Table 3. Then, the temperature was lowered to stop the reaction, to obtain amorphous resin C1. Table 3 shows its physical properties.

< production examples of amorphous resins C2 to C4 >

Amorphous resins C2 to C4 were obtained in the same manner as in the production example of the amorphous resin C1, except that the monomers used were changed as shown in table 3. Table 3 shows the composition and physical properties of the resulting amorphous resins C2 to C4.

TABLE 3

Abbreviations in table 3 are as follows.

BPA-EO: ethylene oxide adducts of bisphenol A (average number of moles added 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 (II): 0.5 part by mass

After the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed at a temperature of 140℃for 3 hours while stirring.

Thereafter, the pressure in the reactor was reduced to 8.3kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200℃to obtain a crystalline polyester D1 as a crystalline resin. Table 4 shows its physical properties.

< production examples of crystalline polyesters D2 to D7 >

Crystalline polyesters D2 to D7 were obtained in the same manner as in the production example of crystalline polyester D1 except that the monomers used were changed as shown in table 4. Table 4 shows the composition and physical properties of the resulting crystalline polyesters D2 to D7.

TABLE 4

< mold release Agents 1 and 2>

The mold release agent used in the present invention is a Fischer-Tropsch wax. Wherein, the peak temperature of the maximum endothermic peak of the release agent 1 is 90 ℃ and the acid value thereof is 0, and the peak temperature of the maximum endothermic peak of the release agent 2 is 87 ℃ and the acid value thereof is 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; 2.4mol% based on the total mol of constituent monomers)

Xylene: 25.0 parts by mass

Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised to 175 ℃ while stirring.

Styrene: 68.0 parts by mass (0.65 mol; 76.4mol% based on the total mol of constituent monomers)

Cyclohexyl methacrylate: 5.0 parts by mass (0.03 mol; 3.5mol% based on the total mol of constituent monomers)

Butyl acrylate: 12.0 parts by mass (0.09 mol; 11.0mol% based on the total mol of constituent monomers)

Methacrylic acid: 5.0 parts by mass (0.06 mol; 6.8mol% based on the total moles of monomers)

Xylene: 10.0 parts by mass

Di-t-butylperoxy-hexahydroterephthalate: 0.5 part by mass

Then, the above materials were added dropwise over 3 hours, and the mixture was further stirred for 30 minutes. Then, the solvent was distilled off to obtain a wax dispersant E having a structure in which the vinyl resin component and the hydrocarbon compound reacted. The peak molecular weight Mp of the wax dispersant E obtained was 6000 and the softening point was 125 ℃.

< production example of toner 1 >

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 E5 parts by mass

15 parts by mass of a release agent

C.I. pigment blue 15:3.7 parts by mass

Using a Henschel mixer (model FM-75, manufactured by Mitsui Kozan) at a rotation speed of 20s ^-1 The above materials were mixed with a rotation time of 5 minutes, and then the mixture was kneaded using a twin screw kneader (model PCM-30, manufactured by Ikegai corp.). The obtained kneaded product was cooled and coarsely pulverized to 1mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo). Further, 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 diameter distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, inc.) and found to be 6.5 μm.

Using a Henschel mixer (model FM-75, manufactured by Mitsui Muike Kakoki) at a rotation speed of 30s ^-1 The rotation time was 10 minutes, and 1.0 parts by mass of hexamethyldisilazane was mixed with 100 parts by mass of the resultant toner particles 1 at the surfaceHydrophobic silica (BET: 200 m) ² Per g) and 1.0 part by mass of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80m ² /g), toner 1 was obtained.

< production example of toners 2 to 24 >

Toners 2 to 24 were obtained in the same manner as 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. Note that T2 cannot be confirmed for toner 20, toner 23, and toner 24.

[ Table 5-1]

[ Table 5-2]

< production example of magnetic core particle 1 >

Step 1 (weighing/mixing step):

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.

Ferrite raw materials were weighed to obtain the above composition ratio. Thereafter, stainless steel shot particles having a diameter of 1/8 inch were crushed and mixed in a dry vibratory mill for 5 hours.

Step 2 (precalcination step):

the crushed product thus obtained was made into particles of about 1mm square by means of a roll press. The pellets were passed through a vibrating screen having an opening of 3mm to remove coarse powder, then through a vibrating screen having an opening of 0.5mm to remove fine powder, and then calcined in a nitrogen atmosphere (oxygen concentration: 0.01 vol%) using a burner type firing furnace at a temperature of 1000 ℃ for 4 hours to produce pre-calcined ferrite. The composition of the resulting pre-calcined ferrite was as follows:

(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d

In the above formula, a=0.257, b=0.117, c=0.007, and d=0.393.

Step 3 (pulverizing step):

crushing to about 0.3mm using a crusher, then adding 30 parts by mass of water to 100 parts by mass of the pre-calcined ferrite using zirconia beads having a diameter of 1/8 inch, and crushing for 1 hour using a wet ball mill. The slurry was pulverized in a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (finely pulverized pre-calcined ferrite).

Step 4 (granulation step):

to the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added based on 100 parts by mass of the pre-calcined ferrite, and the mixture was granulated into spherical particles with a spray dryer (manufacturer: ohkawara Kakohki co., ltd.). The resulting granules were subjected to particle size adjustment and then heated at 650 ℃ for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

Step 5 (calcination step):

to control the calcination atmosphere, the spherical particles were heated from room temperature to 1300 ℃ in 2 hours under a nitrogen atmosphere (oxygen concentration 1.00 vol%) in an electric furnace, and then calcined at 1150 ℃ for 4 hours. Then, the temperature was lowered to 60℃over 4 hours, the nitrogen atmosphere was restored to air, and the spherical particles were taken out at a temperature of 40℃or lower.

Step 6 (screening step):

after the aggregated particles were pulverized, magnetic separation was performed to cut the low magnetic force product, and the resultant was sieved with a sieve having an opening of 250 μm to remove coarse particles, to obtain magnetic core particles 1 having a 50% particle diameter (D50) of 37.0 μm based on the volume distribution.

< preparation of coating resin 1 >

26.8 parts by mass of cyclohexyl methacrylate monomer

Methyl methacrylate monomer 0.2 parts by mass

8.4 parts by mass of methyl methacrylate macromonomer (macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000)

Toluene 31.3 parts by mass

Methyl ethyl ketone 31.3 parts by mass

2.0 parts by mass of azobisisobutyronitrile

Of the above materials, cyclohexyl methacrylate, methyl methacrylate macromer, toluene and methyl ethyl ketone were charged into a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet and a stirrer, nitrogen was introduced thereinto to form a sufficient nitrogen atmosphere, and then heated to 80 ℃, azobisisobutyronitrile was added thereinto and refluxed for 5 hours to polymerize. Hexane was injected into the resultant reaction mixture to precipitate a copolymer, and the precipitate was separated by filtration and dried in vacuo to give a coating resin 1. 30 parts by mass of the obtained coating resin 1 was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content: 30 mass%).

< preparation of coating resin solution 1 >

33.3 parts by mass of a polymer solution 1 (resin solid content: 30%) was added

Toluene 66.4 parts by mass

0.3 part by mass of carbon black (Regal 330; manufactured by Cabot Corporation) (primary particle diameter 25nm, nitrogen adsorption specific surface area 94 m) ² /g, and DBP oil absorption 75ml/100 g)

Zirconia beads with a diameter of 0.5mm were used and dispersed for 1 hour with a paint shaker. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

< production example of magnetic Carrier 1 >

(resin coating step):

the coating resin solution 1 was added to a vacuum degassing kneader maintained at normal temperature so that the resin component was 2.5 parts by mass based on 100 parts by mass of the magnetic core particles 1. After the addition, the mixture was stirred at 30rpm for 15 minutes, after a certain amount or more of the solvent (80 mass%) had evaporated, the temperature was raised to 80℃while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic carrier was subjected to magnetic separation to separate a low magnetic force product, passed through a sieve having an opening of 70 μm, and then classified with an air classifier, to obtain a magnetic carrier 1 having a 50% particle diameter (D50) of 38.2 μm based on a volume distribution.

< production example of two-component developer and supplemental developer >

Toners 1 to 24 and the magnetic carrier 1 were mixed with a V-type mixer (V-10 type: tokuju co., ltd.) at 0.5s ^-1 The rotation time was 5 minutes to mix so that the toner concentration was 8.0 mass%, resulting in two-component developers 1 to 24.

Further, the toners 1 to 24 and the magnetic carrier 1 were mixed with a V-type mixer (V-10 type: tokuju Co., ltd.) at 0.5s ^-1 The rotation time was 5 minutes to mix so that the toner concentration was 95.0 mass%, resulting in the supplemental developers 1 to 24 shown in table 6.

Example 1

< evaluation >

The following low-temperature fixability evaluation, image heat resistance evaluation, and curl resistance evaluation were performed using the two-component developer 1 and the supplemental developer 1.

The full-color copier imagePress C800 manufactured by Canon inc. Is modified so that the fixing temperature and the process speed can be freely set. A two-component developer of a cyan toner was placed in each color developer, and a supplemental developer container containing a supplemental developer of a cyan toner was placed in each color unit to form an image, and various evaluations were performed while performing a durability test.

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

[ evaluation 1. Evaluation of Low temperature fixing Property ]

At normal temperatureThe image was output in a monochrome mode under a normal humidity environment (temperature 23 ℃ C., relative humidity 50% to 60%) so that the amount of toner on the paper was adjusted to 1.2mg/cm ² The print ratio was 25% and the image was not fixed. The evaluation paper used was a copy paper GF-C081 (A4, basis weight 81.4g/m ² Sold by Canon Marketing Japan inc.).

Then, in a low-temperature and low-humidity environment (temperature 15 ℃ C., relative humidity 10% or less), the process speed was set to 450mm/sec, the fixing temperature was gradually increased from 120 ℃ to 2.5 ℃ each time, and the lowest temperature without offset was defined as the fixable temperature.

(evaluation criteria for fixable temperature)

A: below 150 ℃ (very good)

B:150 ℃ above and below 155 ℃ (good)

C:155 ℃ or higher and lower than 160 ℃ (the level at which the effect of the present invention can be obtained)

D:160 ℃ or higher (not acceptable in the present invention)

[2. Evaluation of image Heat resistance ]

Coating paper: image Coat Gloss 128 (128.0 g/m) ² ) (sold by Canon Marketing Japan Inc.)

Amount of toner applied: 1.20mg/cm ²

Evaluation image: 100cm of the A4 paper was placed at the center ² (10 cm. Times.10 cm) image

Fixing test environment: low temperature and humidity environment (temperature 15 ℃, humidity 10% RH)

Treatment speed: 450mm/s

Fixing temperature: low temperature fixing evaluation temperature +10℃

A fixed image was output under the above conditions using the above image forming apparatus, and a bundle of papers (CS-680 (sold by Canon Marketing Japan Inc.; 500 sheets) was stacked thereon, and the output and bundle of papers were placed in a constant temperature bath set at 30℃and 80% RH, and allowed to stand for 1 hour. After that, the temperature of the constant temperature bath was reset to the following evaluation conditions, and then left to stand for 10 hours. Next, the output and one sheet of paper thereon were taken out of the constant temperature bath and allowed to cool for 1 hour, after which the two sheets were separated. At this time, whether the image is adhered or not is evaluated.

(evaluation criteria)

A1: the output was easily peeled off under the temperature condition of constant temperature bath 65 ℃. (very good)

A2: the load was felt when the output was peeled off under the temperature condition of the constant temperature bath of 65 ℃, but no uneven gloss was observed in the image. (very good)

B1: the output was easily peeled off at a temperature of 60℃in a constant temperature bath. (good)

B2: the load was felt when the output was peeled off under the temperature condition of the constant temperature bath of 60 ℃, but no uneven gloss was observed in the image. (good)

C: the outputs do not adhere to each other under the temperature conditions of the constant temperature bath of 55 ℃. (in the present invention, the level is not problematic)

D: under the temperature conditions of the constant temperature bath of 55 ℃, the outputs adhere to each other, and if strongly peeled, the outputs break. (this is not acceptable in the present invention)

[ evaluation 3: evaluation of curl resistance ]

PB paper (66.0 g/m under high temperature and high humidity (temperature 35 ℃ C., humidity 85% RH) ² Letter paper, sold by Canon Marketing Japan inc.) as evaluation paper, evaluation was performed using the above-described image forming apparatus.

In the single-sided continuous printing mode, 100 sheets of paper having a front margin of 3mm, a rear margin of 3mm, and left and right margins of 3mm each were continuously printed, and 1.20mg/cm was output ² Is a solid image of (a).

Under the same circumstances, 100 sheets of paper were stacked with the solid image after image output facing upward, and then a weight of 210mm×30mm heavy 100g was placed on the trailing edge side of the paper with the 210mm side surface aligned with the trailing edge line of the paper. Then, the height of the trailing edge of the paper and the height of the leading edge of the paper were measured, the height of the trailing edge side was subtracted from the height of the leading edge side, and then divided by the height of the trailing edge side and multiplied by 100 to obtain a height ratio (%). The larger the height ratio, the more curled, and evaluated according to 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: the height ratio is more than 16%.

Examples 2 to 18 and comparative examples 1 to 6

The 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 shown in table 6. Table 6 shows the results.

TABLE 6

The present invention can provide a toner excellent in low-temperature fixability, heat-resistant storage stability and curl resistance.

While the invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A toner, comprising:

toner particles comprising a binder resin comprising a crystalline polyester, characterized in that,

when the differential scanning calorimeter DSC of the toner successively goes through: (i) a first temperature-raising process of raising the temperature of the toner from normal temperature to 180 ℃ at a rate of 10 ℃/min, (ii) a first cooling process of cooling the toner from 180 ℃ to 25 ℃ at a rate of 10 ℃/min, (iii) a second cooling process of subsequently cooling the toner from 25 ℃ to 15 ℃ at a rate of 3 ℃/min, and (iv) a second temperature-raising process of raising the temperature of the toner to 180 ℃ again at a rate of 10 ℃/min,

the exothermic amount P1 of exothermic peaks derived from the crystalline polyester, which are observed in the first cooling process at 40 ℃ or higher and 80 ℃ or lower, is 1.00J/g or lower,

an exotherm amount P2 of 0.10J/g or more, which is observed in the second cooling process, derived from an exothermic peak of the crystalline polyester, and

when the sum of the heat absorption amounts of the endothermic peaks at 40 ℃ or higher observed in the second temperature raising process is expressed as P3 in J/g and the sum of the heat release amounts of the exothermic peaks at 40 ℃ or higher observed in the first cooling process is expressed as P4 in J/g, P3-P4 satisfies the following formula (1):

The formula (1) is 2.0-P3-P4-10.0.

2. The toner according to claim 1, wherein an exothermic amount P1 of an exothermic peak derived from the crystalline polyester, which is present at 40 ℃ or higher and 80 ℃ or lower, observed in the first cooling process is 0.50J/g or lower.

3. The toner according to claim 1 or 2, wherein a content ratio of the crystalline polyester to the binder resin in the toner is 8.0 mass% or more and 15.0 mass% or less.

4. The toner according to claim 1 or 2, wherein the toner contains a hydrocarbon-based wax, and a difference T1-T2 between a melting point T1 ℃ of the hydrocarbon-based wax in the toner and a melting point T2 ℃ of the crystalline polyester satisfies the following formula (2):

the formula (2) is 2-T1-T2-10.

5. The toner according to constitution 1 or 2, wherein the binder resin comprises an amorphous resin a, an amorphous resin B, and an amorphous resin C, and when the SP value of the amorphous resin a is denoted as SP1, the SP value of the amorphous resin B is denoted as SP2, the SP value of the amorphous resin C is denoted as SAt P3, and when the SP value of the crystalline polyester is represented as SP4, the SP value is expressed in units of (J/cm ³ ) ^0.5 SP1, SP2, SP3, and SP4 satisfy the following formulas (3) to (5):

6. A two-component developer, comprising:

a toner; and

a magnetic carrier, characterized in that,

the toner is the toner according to any one of claims 1 to 5.