JP6704795B2 - toner - Google Patents

Description

The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system and a toner jet system.

With the recent widespread use of electrophotographic full-color copying machines, demands for high-speed printing and energy saving have been further increased. In order to support high-speed printing, a technique for melting the toner more quickly in the fixing process is being studied. Further, as an energy-saving measure, a technique of fixing toner at a lower fixing temperature is being studied in order to reduce power consumption in the fixing process.
In recent years, in order to improve low-temperature fixability of toner, a toner has been developed in which a binder resin contains a crystalline polyester resin. By including the crystalline polyester in the toner, the hardness can be maintained up to the fixing temperature even though it is quickly melted at the fixing temperature, and thus it is possible to improve the storage stability and the durability.
By adding crystalline polyester to the toner, various characteristics including a sharp melt property are added to the toner, and therefore various technical proposals have been made to make the best use of these characteristics or to suppress the shortcomings.

Patent Document 1 describes a method in which a toner having a high circularity can be obtained by containing a crystalline polyester in a toner and heat-treating the toner, and a toner having excellent transferability is obtained. There is disclosed a toner manufacturing technique that makes good use of the property.
In Patent Document 2, in addition to the main binder resin and crystalline polyester, a crystalline polyester dispersant is used to define the solubility parameter of each. As a result, the exposure of the crystalline polyester to the toner surface layer is suppressed, and the crystalline polyester is finely dispersed inside the toner particles to suppress toner filming to other members and improve the hot offset resistance. ing.
Patent Document 3 proposes a toner in which a surface layer of toner particles is covered with an amorphous resin in a toner in which crystalline polyester is finely dispersed. As a result, the toner containing the crystalline polyester and excellent in low-temperature fixability satisfies the heat-resistant storage stability and the durability stability.

Patent Document 4 proposes that the relationship between the cross-sectional area of the crystalline domain of the crystalline polyester in the toner and the cross-sectional area of the release agent domain be regulated to improve the fixing separability. According to this, it is said that the balance between the speed at which the wax oozes out onto the toner surface and the melting speed of the toner binder resin is optimized, and in addition to the low-temperature fixability, the fix separability is improved.
In Patent Document 5, the hot offset resistance is improved by setting the major axis diameter of the crystal of the crystalline polyester in the toner to 0.5 μm or more and 1/2 or less of the toner diameter.
In Patent Document 6, crystalline polyester is laminated in a lamella shape on the toner surface and unevenly distributed, thereby improving low-temperature fixability.
As can be seen from these disclosed techniques, the characteristics of the toner greatly change depending on the presence state of the crystalline polyester in the toner. Therefore, controlling the presence state is one of important techniques for maximizing the performance of the crystalline polyester. It has become one. In particular, the presence of the crystalline polyester in the toner surface layer is effective for the fixing performance and the like, but has a trade-off performance such as when the durability performance is difficult, as can be seen from the above-described disclosed technology. For this reason, there is a demand for a toner technology that improves the performance other than the fixing performance while taking advantage of the excellent fixing performance of the crystalline polyester.

JP, 2003-270856, A JP 2012-63559 A JP2012-18391A JP, 2011-145587, A JP 2004-279476 A JP, 2011-197274, A

An object of the present invention is to provide a toner that solves the above problems. Specifically, it is intended to provide a toner having a high developability by utilizing the physical properties of crystalline polyester while satisfying the fixability at low temperature and high temperature.

The present invention is a toner having toner particles containing a crystalline polyester resin and an amorphous polyester resin,
In cross-sectional observation of the toner with a transmission electron microscope (TEM),
The crystalline polyester resin dispersed to the depth of 0.30 μm from the toner surface has a number average diameter (D1) of the major axis length of 40 nm or more and 110 nm or less,
The crystalline polyester in which the number average diameter (D1) of the major axis lengths of the crystalline polyester resin dispersed inward from the toner surface by 0.30 μm is dispersed to the depth of 0.30 μm from the toner surface. The toner is characterized in that the major axis length of the resin is 1.25 times or more and 4.00 times or less of the number average diameter (D1).

According to the present invention, it is possible to provide a toner having high developing performance while having high fixing performance at low temperature and high temperature.

Cross-sectional view of the toner of the present invention by a transmission electron microscope (TEM) The figure which shows the major-axis length and the minor-axis length of crystalline polyester in a toner cross section. Crystal length distribution diagram of crystalline polyester in toner cross section Cross-sectional view of a device for manufacturing toner

In the toner of the present invention, the number average diameter (D1) of the major axis lengths of the crystalline polyester resin (of the toner surface layer) dispersed to a depth of 0.30 μm from the toner surface is 40 nm or more and 110 nm. From 0.30 μm to the inside (toner interior) of the crystalline polyester resin, the number average diameter (D1) of the major axis lengths of the crystalline polyester resin dispersed to the depth of 0.30 μm from the toner surface. It is important that the major axis length of the polyester resin is 1.25 times or more and 4.00 times or less of the number average diameter (D1).
Since the major axis length of the crystalline polyester crystals in the toner surface layer is small and the major axis length of the crystalline polyester crystals in the toner is large, excellent developability and fixability that take advantage of the characteristics of the crystalline polyester can be obtained. Can be applied to the toner.
The present inventors examined the mechanism.

Crystals of crystalline polyester having a certain length in the toner can improve low-temperature fixability due to its sharp melting property.
In addition, crystalline polyester has lower electric resistance and smaller charging performance than amorphous polyester. Therefore, the presence of large crystalline domains of the crystalline polyester in the toner surface layer causes variation in the surface charge of the toner.
As a countermeasure, when the toner surface layer is formed of a material not containing crystalline polyester, the low temperature and high temperature fixing performance is likely to be impaired. Further, when a resin in which a crystalline polyester is completely compatible with an amorphous polyester is formed on the surface layer of the toner, the thermal and mechanical strength of the toner surface is likely to decrease when the resin is formed on the surface layer.
On the basis of the above experimental results, a trial production of a toner in a crystalline state, which is optimal for the crystalline polyester to exert the releasing effect, was conducted, and the present invention was accomplished.

Specifically, the crystalline polyester is present as crystals in the toner, and the number average diameter (D1) of the major axis lengths of the crystalline polyester crystals in the region (toner surface layer) from the toner surface to the inside of 0.30 μm. When (hereinafter, also referred to as Ls) is 40 nm or more and 110 nm or less, the low electrical resistance of the crystalline polyester effectively acts, and the charging uniformity on the toner surface is improved. As a result, even in a low-humidity environment where the electrostatic adhesive force tends to increase, the electrostatic adhesive force of the toner on the carrier or the developing roller decreases, so that the developing efficiency improves. This is considered to be because if there are uniformly low electric resistance portions uniformly on the toner surface, electric charges easily move on the toner surface, spread easily evenly on the toner surface, and the portions having a high charge density protruding are reduced.
The number average diameter (D1) of the major axis length of the crystalline polyester crystals of the toner surface layer is preferably 50 nm or more and 100 nm or less.

The number average diameter (D1) (hereinafter, also referred to as Li) of the major axis length of the crystal of the crystalline polyester in the region (inside the toner) further inside 0.30 μm from the surface of the toner is 0. It is 1.25 times or more and 4.00 times or less (preferably 1.5 times or more and 3.7 times or less) of the number average diameter (D1) of the major axis length of the crystalline polyester crystals in the region up to 30 μm inside. Thus, the low temperature fixing performance is improved. The smaller the major axis of the crystal of the crystalline polyester, the faster the compatibility with the amorphous polyester and the faster the endothermic heat of fusion. It is considered that the low temperature fixing performance is further improved because the toner particles are easily bonded to each other through the surface layer even if they are not melted.
The major axis length D1 of the crystalline polyester of the toner surface layer can be controlled by the cooling temperature (cooling rate) of the toner surface after the heat treatment. Further, the major axis length D1 of the crystalline polyester crystals inside the toner can be controlled by the cooling temperature (cooling rate) after the toner material is melt-kneaded.
In the present invention, the number average diameter (D1) of the major axis lengths of the crystalline polyester resin dispersed 0.30 μm inward (inside the toner) from the toner surface is 60 nm or more and 300 nm or less (more preferably 100 nm). It is preferably 250 nm or less). When Li is in the above range, hot offset of the toner is less likely to occur during fixing.

If the crystal aspect ratio of the crystalline polyester in a region more than 0.30 μm from the surface of the toner is 6.0 or more and 30.0 or less, the rise of charging at high humidity is quick and the developing device is high. This is preferable because it improves scattering and fog. The aspect ratio is more preferably 8.0 or more and 20.0 or less. The aspect ratio can be controlled by the cooling temperature (cooling rate) of the toner surface after the heat treatment, and the polarity difference between the crystalline polyester material and the amorphous polyester material.
The aspect ratio of the crystalline polyester crystals of the toner surface layer is preferably 4.0 or more and 10.0 or less.
In the number distribution of the major axis length of the crystalline polyester resin dispersed 0.30 μm inward (inside the toner) from the toner surface, the maximum value is 80 nm or more and 200 nm or less (more preferably 100 nm or more and 160 nm or less). This is preferable because the hot offset resistance is improved. The maximum value can be controlled by the temperature at the time of kneading the toner, in addition to the above-described aspect ratio control means.
Further, in the number distribution of the major axis lengths of the crystalline polyester resin dispersed up to a depth of 0.30 μm (toner surface layer) from the toner surface, the maximum is 50 nm or more and 100 nm or less (more preferably 70 nm or more and 90 nm or less). A value of this is preferable because variations in charging are reduced in a low-humidity environment and fog is improved. The maximum value can be controlled by the heat treatment temperature of the toner surface in addition to the aspect ratio control means described above.

The toner particles according to the present invention are characterized by containing a crystalline polyester resin and an amorphous polyester resin.
<Amorphous polyester resin A/B constitution>
The toner of the present invention contains, as a binder resin, a polyester resin A containing an aromatic diol as a main component and a small weight average molecular weight and a polyester resin B containing an aromatic diol as a main component and a large weight average molecular weight. Is preferred. The weight average molecular weight (Mw) of the polyester resin A is preferably 3,000 or more and 10,000 or less. The weight average molecular weight (Mw) of the polyester resin B is preferably 30,000 or more and 300,000 or less.
The "main component" means that the content is 50% by mass or more.
By using two polyesters having different weight average molecular weights as a binder resin, a polyester having a small weight average molecular weight improves low-temperature fixability of the toner, and a polyester having a high weight average molecular weight improves hot offset resistance of the toner. You can
The sum of the contents of polyester resin A and polyester resin B in the toner is preferably 60% by mass or more and 99% by mass or less.
In the present invention, the content ratio (A/B) of the polyester resin B to the polyester resin A is preferably 60/40 or more and 80/20 or less on a mass basis. When (A/B) is in this range, the low temperature fixability and the hot offset resistance are well balanced.

Both the polyester resin A and the polyester resin B preferably have a polyhydric alcohol unit and a polyhydric carboxylic acid unit. In the present invention, the polyhydric alcohol unit is a component derived from the polyhydric alcohol used in the condensation polymerization of polyester. Further, in the present invention, the polyvalent carboxylic acid unit is a component derived from the polyvalent carboxylic acid used in the condensation polymerization of polyester or its anhydride, or a lower (for example, having 1 to 8 carbon atoms) alkyl ester. That is.
Both the polyester resin A and the polyester resin B of the present invention have a polyhydric alcohol unit and a polycarboxylic acid unit, and the polyhydric alcohol unit derived from an aromatic diol is 90 mol with respect to the total number of moles of the polyhydric alcohol unit. % Or more and 100 mol% or less is preferable. Fog can be suppressed when the polyhydric alcohol unit derived from the aromatic diol is 90 mol% or more based on the total number of moles of the polyhydric alcohol unit.
Since the polyhydric alcohol unit of the polyester resin A has a structure derived from an aromatic diol common to the polyester resin B, they are easily compatible with each other, and the dispersibility of the polyester A and the polyester B is improved.
Examples of the aromatic diol include bisphenol represented by the formula (1) and its derivatives.

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 to 10.)
Above all, it is preferable that the R in the formula (1) of the polyester resin A and the polyester resin B are the same because they are easily compatible with each other during melt-kneading. Further, a propylene oxide adduct of bisphenol A in which both R are propylene groups and the average value of x+y is 2 to 4 is preferable from the viewpoint of charge stability.

<Amorphous polyester resin A>
The polyester resin A of the present invention preferably contains 90 mol% or more and 100 mol% or less of a polyhydric alcohol unit derived from an aromatic diol with respect to the total number of moles of the polyhydric alcohol unit. In order to ensure the compatibility with the polyester B in the present invention, it is preferably 95 mol% or more, more preferably 100 mol%.
As the components other than the aromatic diol forming the polyhydric alcohol unit of the polyester resin A, the following polyhydric alcohol components can be used. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol , Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylol Ethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.

The polyester resin A of the present invention may contain 90.0 mol% or more and 99.9 mol% or less of a polyvalent carboxylic acid unit derived from an aromatic dicarboxylic acid or a derivative thereof, based on the total number of polyvalent carboxylic acid units. preferable.
When the polyvalent carboxylic acid unit derived from the aromatic dicarboxylic acid or its derivative is in the above range, the compatibility with the polyester A is improved and it is possible to suppress the density fluctuation and fog after printing for a long time.
Examples of the aromatic dicarboxylic acid or its derivative include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides.
Further, when the polyvalent carboxylic acid unit derived from the aliphatic dicarboxylic acid or its derivative is contained in an amount of 0.1 mol% or more and 10.0 mol% or less with respect to the total number of moles of the polyvalent carboxylic acid unit, the low temperature fixability of the toner is further improved. It is preferable because it improves the quality.

Examples of the aliphatic dicarboxylic acid or its derivative include alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms or Anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof. Of these, succinic acid, adipic acid, fumaric acid, acid anhydrides thereof, and lower alkyl esters are preferably used.
Examples of polyvalent carboxylic acid units other than these include trivalent or tetravalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

<Amorphous polyester resin B>
As the component constituting the polyhydric alcohol unit of the polyester resin B, other than the aromatic diol and the oxyalkylene ether of the novolac type phenol resin, the polyhydric alcohol unit described in the amorphous resin A may be used, if necessary. Alcohol components can be used.

The polyester resin B of the present invention is derived from an aliphatic dicarboxylic acid having a main chain of a linear hydrocarbon having 4 to 16 carbon atoms and carboxyl groups at both ends, based on the total number of moles of polyvalent carboxylic acid units. It is preferable that the polyvalent carboxylic acid unit is contained in an amount of 15 mol% or more and 50 mol% or less, because the dispersibility of the resins improves.
An aliphatic dicarboxylic acid having a linear hydrocarbon having 4 to 16 carbon atoms as a main chain and having carboxyl groups at both ends has a linear hydrocarbon structure in the main chain of polyester when reacted with an alcohol component. Therefore, the main chain has a partially flexible structure. Therefore, in the melt-kneading step of the toner, the polyester resin A having a low softening point is mixed with the polyester resin B having a high softening point starting from this flexible structure, and the main chain of the polyester resin A is entangled to improve the dispersibility. The dispersibility of the crystalline polyester is also improved.

Examples of the aliphatic dicarboxylic acid having a straight chain hydrocarbon having 4 to 16 carbon atoms and a carboxyl group at both ends as a main chain include, for example, adipic acid, azelaic acid, sebacic acid, tetradecanedioic acid and octadecanedioic acid. Examples thereof include dicarboxylic acid, its anhydride, and lower alkyl ester. Further, a compound having a structure in which a part of the main chain is branched with an alkyl group such as a methyl group, an ethyl group, an octyl group, or an alkylene group can be given. The carbon number of the linear hydrocarbon is preferably 4 or more and 12 or less, and more preferably 4 or more and 10 or less.
Other polycarboxylic acid units contained in the polyester resin B include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl groups or alkenyl groups having 6 to 18 carbon atoms. Substituted succinic acid or its anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or its anhydride. Among these, carboxylic acids having an aromatic ring or derivatives thereof such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides are likely to have improved hot offset resistance. Therefore, it is preferably used.

<Other binder resin>
Examples of the binder resin used in the toner of the present invention include the following polyester resin A and polyester resin B in addition to the above-mentioned polyester resin A and polyester resin B for the purpose of improving the pigment dispersibility and the charging stability and blocking resistance of the toner. It is also possible to add the polymer D in an amount that does not impair the effects of the present invention.
The polymer D has a structure in which a vinyl resin component and a hydrocarbon compound are bonded. As the polymer D, a polymer in which a polyolefin is bound to a vinyl resin component or a polymer having a vinyl resin component in which a vinyl monomer is bound to the polyolefin is preferable. It is considered that the polymer D enhances the affinity between the polyester resin and the wax. Therefore, even when the temperature of the surface of the fixing device is high, the exudation of wax onto the outermost surface of the toner in the inorganic fine particle portion is favorably suppressed, thereby contributing to the improvement of gloss uniformity.

The content of the polymer D relative to 100 parts by mass of the amorphous polyester resin is preferably 2 parts by mass or more and 10 parts by mass or less, more preferably 3 parts by mass or more and 8 parts by mass or less. When the content of the polymer D is in the above range, it is possible to further improve the gloss uniformity while maintaining the low temperature fixing property of the toner.
The polyolefin in the polymer D is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon monomer having one double bond, and various polyolefins can be used. In particular, polyethylene type and polypropylene type polyolefins are preferably used.

Examples of the vinyl monomer used as the vinyl resin component in the polymer D include the following.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl. Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrenic monomers such as styrene and its derivatives.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based compounds containing N atom such as acrylic acid or methacrylic acid derivative such as acrylonitrile, methacrylonitrile and acrylamide monomer.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid esters such as dimethyl maleic acid, dimethyl fumaric acid; acrylic acid, Α,β-unsaturated acids such as methacrylic acid, crotonic acid, cinnamic acid; α,β-unsaturated acid anhydrides such as crotonic anhydride, cinnamic acid anhydride, and the aforementioned α,β-unsaturated acids Anhydrides with lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof, and vinyl monomers containing a carboxyl group such as monoesters thereof.

Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4-(1-hydroxy-1-methylbutyl)styrene, 4-(1-hydroxy-1-methyl) Hexyl) Vinyl-based monomers containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate -2- Acrylic esters such as chloroethyl and phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acidate and diethylaminoethyl methacrylate.

The polymer D having a structure in which the vinyl-based resin component and the hydrocarbon compound used in the present invention react with each other, and the reaction between these vinyl-based monomers described above, the monomer as the raw material of one polymer and the other polymer It can be obtained by a known method such as a reaction with
The constitutional unit of the vinyl resin component preferably contains a styrene unit, an ester unit, and further an acrylonitrile unit or a methacrylonitrile unit.

In the present invention, if the dispersibility of the release agent or the pigment is improved, the dispersibility of the fine crystals of the crystalline polyester on the surface is improved. Therefore, it is preferable to add another resin as a dispersant to the toner.
Examples of other resins used as the binder resin of the toner of the present invention include the following resins. Polystyrene, poly-p-chlorostyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic acid resins, acrylic resins , Methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin and the like.

<Release agent (wax)>
Examples of the wax used in the toner of the present invention include the following. Hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof. Waxes containing a fatty acid ester such as carnauba wax as a main component; Deoxidized fatty acid ester such as carnauba wax, which is partially or entirely deoxidized. Further, the following may be mentioned. Saturated straight chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol Saturated alcohols such as melicyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol , Esters with alcohols such as ceryl alcohol, melysyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislaurin Acid amides, saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'dioleyl adipamide, N,N'dioleyl sebacic acid amide Such unsaturated fatty acid amides; aromatic bisamides such as m-xylene bisstearic acid amide, N,N' distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts (generally called metallic soap); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride Partial esterified product of polyhydric alcohol; methyl ester compound having hydroxyl group obtained by hydrogenation of vegetable oil.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable because the hot offset resistance is further improved.
In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the amorphous polyester resin.
Further, in the endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) device, the peak temperature of the maximum endothermic peak of the wax is preferably 45°C or higher and 140°C or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax is within the above range because both the storage stability and the hot offset resistance of the toner can be achieved.

<Colorant>
Examples of the colorant that can be contained in the toner include the following.
Examples of the black colorant include carbon black; those obtained by toning black with a yellow colorant, a magenta colorant and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.

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, 282; C.I. I. Pigment Violet 19; C.I. I. Butt Red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse Red 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 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. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. There is 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, 185; I. Bat Yellow 1, 3, 20. Examples of dyes for yellow toner include C.I. I. There is Solvent Yellow 162.
The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin.

<Charge control agent>
The toner may contain a charge control agent, if necessary. As the charge control agent contained in the toner, known charge control agents can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is preferable.
As the negative charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a polymer type compound having a sulfonic acid or a carboxylic acid in the side chain, a sulfonate or a sulfonate ester compound in the side chain Examples thereof include a polymer type compound, a polymer type compound having a carboxylic acid salt or a carboxylic ester as a side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin.

<Crystalline polyester resin>
The toner of the present invention contains a crystalline polyester resin.
The crystalline polyester resin 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 a polycondensation reaction. .
The crystalline resin refers to a resin in which a clear endothermic peak (melting point) is observed in the reversible specific heat change curve of the specific heat change measurement by the differential scanning calorimeter.
The aliphatic diol having 2 to 22 carbon atoms (more preferably 4 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol. , Pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol. Among these, particularly preferred are straight chain aliphatic such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and α,ω-diol.

Of the above alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.
In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol may be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropyleneated bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, trivalent or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol. Fats such as 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane Group alcohols and the like can be mentioned.
Further, in the present invention, monovalent alcohol may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monohydric alcohol include monofunctional compounds such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol and dodecyl alcohol. Examples include alcoholic alcohol.

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 14 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. . Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, Examples thereof include maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also include those obtained by hydrolyzing these acid anhydrides or lower alkyl esters.
In the present invention, preferably 50% by mass or more, and more preferably 70% by mass or more of the carboxylic acid component is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.

In the present invention, a polyvalent carboxylic acid other than the above aliphatic dicarboxylic acid having 2 to 22 carbon atoms can also be used. Among other polyvalent carboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; cyclohexanedicarboxylic acid. Examples thereof include alicyclic carboxylic acids such as acids, and also include acid anhydrides or lower alkyl esters thereof. Among the other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1, Aromatic carboxylic acids such as 2,4-naphthalene tricarboxylic acid and pyromellitic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 And aliphatic carboxylic acids such as methylene carboxypropane, etc., and derivatives thereof such as acid anhydrides or lower alkyl esters thereof are also included.
Further, in the present invention, a monovalent carboxylic acid may be contained to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

The crystalline polyester in the present invention can be produced according to a usual polyester synthesis method. For example, after the esterification reaction or the transesterification reaction of the carboxylic acid monomer and the alcohol monomer described above, a desired polycondensation reaction is carried out under a reduced pressure or by introducing nitrogen gas in accordance with a conventional method. A crystalline polyester can be obtained.
The above-mentioned esterification or transesterification reaction can be carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate or magnesium acetate, if necessary.
Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. . 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, all the monomers are batch-charged in order to increase the strength of the crystalline polyester obtained, or a divalent monomer is first reacted in order to reduce low molecular weight components. After this, a method of adding a monomer having a valence of 3 or more and reacting it may be used.
In the present invention, the content of the crystalline polyester in the toner is preferably 2% by mass or more and 15% by mass or less in order to exhibit high fixing performance and developability.

<Inorganic fine particles>
The toner of the present invention may contain inorganic fine particles, if necessary. 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 particles such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
When used as an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² /g or more and 400 m ² /g or less are preferable, and a specific surface area of 10 m ² /g for stabilizing durability. It is preferable that the inorganic fine particles have a particle size of 50 m ² /g or less. In order to achieve both improvement of fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used together.
The external additive is preferably used in an amount of 0.1 part by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

<Developer>
The toner of the present invention can be used also as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier to be used as a two-component developer, and a stable image can be obtained for a long period of time. Is preferred in that
As the magnetic carrier, for example, iron powder whose surface is oxidized, or unoxidized iron powder, iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, metal particles such as rare earth, Magnetic materials such as alloy particles, oxide particles, and ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are generally known. Can be used.
When the toner of the present invention is mixed with a magnetic carrier to be used as a two-component developer, the carrier mixing ratio at that time is 2% by mass or more and 15% by mass or less, as the toner concentration in the two-component developer. When 4% by mass or more and 13% by mass or less, good results are usually obtained.

<Manufacturing method>
As a method for producing the toner particles, a pulverization method in which a binder resin, a colorant, a wax, etc., if necessary, are melt-kneaded, and the kneaded product is cooled, pulverized and classified is preferable.
Hereinafter, a toner manufacturing procedure by the pulverization method will be described.
In the raw material mixing step, as a material forming the toner particles, for example, a binder resin and, if necessary, other components such as a colorant, a wax, and a charge control agent are weighed in predetermined amounts, mixed, and mixed. . Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.).

Next, the mixed materials are melt-kneaded to disperse wax, crystalline polyester and the like in the binder resin. The kneading and discharging temperature is preferably 100 to 170°C. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder becomes the mainstream because of the advantage of continuous production. ing. For example, KTK twin-screw extruder (Kobe Steel Co., Ltd.), TEM twin-screw extruder (Toshiba Machinery Co., Ltd.), PCM kneader (Ikegai Tekko), twin-screw extruder (KCK) ), Co-Kneader (manufactured by Buss), Needex (manufactured by Nippon Coke Industry Co., Ltd.) and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with a two-roll mill or the like and cooled with water or the like in the cooling step. The cooling rate is 1 to 50° C./min. Is preferred.
Next, the cooled product of the resin composition is crushed to a desired particle size in a crushing step. In the crushing process, for example, after roughly crushing with a crusher such as a crusher, a hammer mill, and a feather mill, further, for example, Kryptron system (Kawasaki Heavy Industries Co., Ltd.), super rotor (Nisshin Engineering Co., Ltd.), turbo Finely pulverize with a mill (manufactured by Turbo Kogyo) or an air jet type fine pulverizer.

After that, if necessary, such as an inertia classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal force classification type turboplex (manufactured by Hosokawa Micron), a TSP separator (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron) Classification is performed using a classifier or a sieve classifier to obtain toner particles.
Thereafter, external additives such as inorganic fine powder and resin particles selected as necessary may be added and mixed (externally added). For example, in order to impart fluidity, an external additive can be added, and toner particles before heat treatment can be obtained.
As the mixing device, a mixing device having a rotating body having a stirring member and a main body casing provided with a gap from the stirring member is used. As an example of such a mixing device, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Co., Ltd.); a ribocon (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron) Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) and the like. In particular, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is preferably used to uniformly mix and loosen the silica aggregates.
The mixing apparatus conditions include the amount of processing, the number of rotations of the stirring shaft, the stirring time, the shape of the stirring blade, the temperature inside the tank, etc., but in order to achieve the desired toner performance, various physical properties of the toner particles and additives It is appropriately selected in consideration of the type and the like, and is not particularly limited.

In the present invention, it is important to form a layer in which a crystalline polyester having a fine crystal size is dispersed in the surface layer of the toner particles obtained by the above production method or the like.
The method is not particularly limited, but after forming toner particles in which the crystals of crystalline polyester are present in a certain size, the surface modification of the particles forms a resin layer in which the crystalline polyester is present as fine crystals. The formation method is preferable because the adhesion between the surface layer of the toner and the binder resin inside is high and the storage stability of the toner is good.
As a method for surface modification, there is a method in which crystals of the crystalline polyester are once made compatible with the amorphous polyester resin only in the toner surface layer by light or heat and then re-precipitated.
Among them, surface modification by heat is preferable from the viewpoint of freedom of material selection and productivity.

A method for modifying the toner surface by heat will be described.
As the surface modification step, in the present invention, the surface treatment is performed with hot air using the surface treatment device shown in FIG. 4, for example.
The mixture quantitatively supplied by the raw material quantitative supply means 1 is guided by the compressed gas adjusted by the compressed gas adjusting means 2 to the introduction pipe 3 installed on the vertical line of the raw material supply means. The mixture that has passed through the introduction pipe is uniformly dispersed by the conical projection-shaped member 4 provided in the central portion of the raw material supply means, and is introduced into the radially extending supply pipes 5 in eight directions, where the heat treatment is performed. Be led to.
At this time, the flow of the mixture supplied to the processing chamber is regulated by the regulation means 9 for regulating the flow of the mixture provided in the processing chamber. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling in the processing chamber and then cooled.

The heat for heat-treating the supplied mixture is supplied from the heat supply means 7 and distributed by the distribution member 12, and the swirling member 13 for swirling the hot air swirls the hot air into the processing chamber for introduction. To be done. As its configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied to the processing chamber at the outlet of the hot air supply means 7 is preferably equal to or higher than the melting point of the crystals of the crystalline polyester and 20° C. to 70° C. higher than the softening point Tm of the toner particles. . For example, it is preferably 120 to 170°C. If the temperature at the outlet of the hot air supply means is within the above range, the toner particles are surface-modified uniformly and uniformly while preventing fusion or coalescence of the toner particles due to overheating of the mixture. It becomes possible to do. Hot air is supplied from the hot air supply means outlet 11. Moreover, the hot air flow rate is 2 to 20 m ³ /min. Is preferred.

Further, the heat-treated toner particles that have been further heat-treated are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably −40° C. to 20° C. When the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the crystalline polyester once compatible with the surface layer of the toner particles is deposited in a fine size, and It is possible to prevent fusion and coalescence. The absolute water content of the cold air is preferably 0.5 g/m ³ or more and 15.0 g/m ³ or less. The flow rate of cold air is 1 to ³⁰ m ³ /min. Is preferred.
Next, the cooled heat-treated toner particles are collected by the collecting means 10 at the lower end of the processing chamber. A blower (not shown) is provided at the tip of the collecting means, and suction and conveyance are performed by the blower.

Further, the powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same direction, and the collecting means 10 of the surface treatment device is arranged to collect the swirled powder particles. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be horizontally and tangentially supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirl direction of the toner particles before heat treatment supplied from the powder supply port, the swirl direction of the cold air supplied from the cold air supply unit, and the swirl direction of the hot air supplied from the hot air supply unit are all in the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before heat treatment, and the dispersibility of the toner particles before heat treatment is further improved. Heat-treated toner particles can be obtained.
In order to impart fluidity to the toner before it is introduced into the heat treatment apparatus, if fine particles are externally added to and mixed with the toner particles in advance, the dispersibility of the toner in the apparatus is improved and the coalescence particles are reduced. In addition, it is possible to suppress variations between particles in the surface modification treatment.

After that, external additives such as inorganic fine powder and resin particles selected as necessary are added and mixed (externally added), for example, to impart fluidity and improve charging stability, to obtain a toner. As the mixing device, a mixing device having a rotating body having a stirring member and a main body casing provided with a gap from the stirring member is used.
As an example of such a mixing device, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Co., Ltd.); a ribocon (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron) Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) and the like. In particular, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is preferably used to uniformly mix and loosen the silica aggregates.
The mixing apparatus conditions include throughput, agitation shaft rotation speed, agitation time, agitation blade shape, tank temperature, and the like. The number is appropriately selected in consideration of the type, and is not particularly limited.
Furthermore, for example, when coarse aggregates of additives are present in the obtained toner in a free state, a sieving machine or the like may be used if necessary.

The methods for measuring various physical properties of the toner and the raw materials will be described below.
<Evaluation of crystalline state of crystalline polyester by TEM observation>
The cross-sectional observation of the toner with a transmission electron microscope (TEM) and the evaluation of the crystalline polyester domain can be carried out as follows.
By ruthenium dyeing the cross section of the toner, the crystalline polyester resin can be obtained as a clear contrast. The crystalline polyester resin is dyed weaker than the organic component that constitutes the inside of the toner. It is considered that this is because the dyeing material soaked into the crystalline polyester resin is weaker than the organic components inside the toner due to the difference in density. Since the amount of ruthenium atoms varies depending on the strength of dyeing, there are many of these atoms in the strongly dyed part, the electron beam does not penetrate, and the part that is weakly dyed becomes black on the observed image. The electron beam is easily transmitted and becomes white on the observed image.
The ruthenium dye that has not permeated the inside of the crystalline polyester is likely to remain at the interface between the crystalline polyester and the amorphous polyester, and when the crystals are needle-shaped, the crystalline polyester is observed as black as a result.
After applying Os film (5 nm) and naphthalene film (20 nm) to the toner as a protective film using osmium plasma coater (filgen company, OPC80T), and embedding with photocurable resin D800 (JEOL Ltd.) A toner cross section having a film thickness of 60 nm (or 70 nm) was prepared at a cutting speed of 1 mm/s using a sonic ultramicrotome (Leica, UC7).
The obtained cross section was subjected to RuO ₄ gas 5 using a vacuum electron dyeing device (VSC4R1H, manufactured by filgen).
It was dyed for 15 minutes in an atmosphere of 00 Pa, and STEM observation was performed using TEM (JEM2800, JEOL).
The STEM probe size was 1 nm, and the image size was 1024×1024 pixels.
For the obtained images, the image processing software "Image-Pro Plus (made by Media Cybernetics)"
, And binarize (120/255 threshold levels).
The obtained cross-sectional image before binarization is shown in FIG. As shown in FIG. 1, the crystalline domain of the crystalline polyester can be confirmed as a black needle shape, and the obtained image is binarized to extract the crystalline domain and measure its size. In the present invention, when the cross-section of 20 randomly selected toners is observed, the total lengths of the major axis and the minor axis of the crystalline domains of the crystalline polyester of which the length can be measured are measured. At that time, the number average (number average diameter (D1)) of the crystal lengths of the crystalline polyester in the region from the surface of the toner to a depth of 0.30 μm (range of arrow a sandwiched by the dotted line in FIG. 1) The number average (number average diameter (D1)) of the crystal lengths of the crystalline polyester in the region further inside the region of the arrow a is determined. It should be noted that crystals that cross the boundary of 0.30 μm from the surface of the toner (exist on the boundary) are not measured.
Here, the major axis length of the crystalline domain of the crystalline polyester is the longest distance (a in FIG. 2) in the crystalline domain of the cross-sectional image, and the minor axis length is the middle of the major axis of the crystal, as shown in FIG. It is the shortest distance (b in FIG. 2) at the point position.
Further, the aspect ratio of the crystalline polyester resin dispersed more than 0.30 μm from the toner surface is calculated from the lengths of the major axis and the minor axis of the crystalline domains of the crystalline polyester measured as described above. The arithmetic mean value of is used.
The acicular shape in the present invention is an elongated shape having a high straightness, a minor axis length of 25 nm or less, an aspect ratio (major axis length/minor axis length) of 3 or more, and a crystalline shape. When the center points in the short axis direction at both ends in the long axis direction are connected by a straight line, the deviation of the crystal contour from the straight line is defined as a shape within 100% of the crystal short axis length. ..

(Number distribution of the major axis length of the crystalline polyester resin and its maximum value)
The number distribution graph of the major axis length of the crystalline polyester resin is prepared and the maximum value is calculated as follows. First, the major axis lengths of crystalline polyesters of 20 randomly selected toner cross-sections were measured in a region from the toner surface to a depth of 0.30 μm and in a region inside the toner surface from 0.30 μm. Using the data of 1., the number distribution of the major axis length is created by classifying into the intervals of 5 nm intervals such as 0 nm to 5 nm or less and 5 nm to 10 nm or less. Next, the major axis length having the largest number frequency in the number distribution is obtained, and the value is set as the maximum major axis length. An example of the number distribution graph is shown in FIG.

<Measurement method of weight average molecular weight of resin>
The molecular weight distribution of the THF-soluble component of the resin is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maeshoridisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Device: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 806, 80
7 series of 7 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml/min
Oven temperature: 40.0°C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corp.) is used.

<Measurement method of weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) by a pore electrical resistance method equipped with an aperture tube of 100 μm. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis, the measurement data is measured with 25,000 effective measurement channels. Is analyzed and calculated.
The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before the measurement and analysis, the dedicated software is set as follows.
On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). (Manufactured by the company) is used to set the value obtained. The threshold and noise level are automatically set by pressing the threshold/noise level measurement button. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the flash of the aperture tube after the measurement is checked.
On the "pulse-to-particle size conversion setting screen" of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measuring method is as follows.
(1) About 200 ml of the electrolytic aqueous solution was placed in a glass 250 ml round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles inside the aperture tube are removed by the "aperture flush" function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat-bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precision measurement as a dispersant was added to this). Approximately 0.3 ml of a diluted solution prepared by diluting a 10 mass% aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water to 3 mass times is added.
(3) Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electric output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker becomes maximum.
(5) About 10 mg of the toner is added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10°C or higher and 40°C or lower.
(6) To the round-bottom beaker of (1) installed in the sample stand, the electrolytic solution of (5) in which the toner is dispersed is dropped using a pipette, and the concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “average diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measuring method of softening point of resin>
The softening point of the resin is measured by the constant-load extrusion type capillary rheometer "Flow characteristic evaluation device".
Flow tester CFT-500D" (manufactured by Shimadzu Corporation) is used according to the manual attached to the apparatus. With this device, while applying a constant load from the top of the measurement sample by the piston, the temperature rises and melts the measurement sample filled in the cylinder, and the molten measurement sample is extruded from the die at the bottom of the cylinder. It is possible to obtain a flow curve showing the relationship between temperature and temperature.
In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation apparatus Flow Tester CFT-500D" is defined as the softening point. The melting temperature in the ½ method is calculated as follows. First, 1/2 of the difference between the piston drop amount Smax at the time when the outflow ends and the piston drop amount Smin at the time when the outflow starts is obtained (this is X. X=(Smax-Smin)/ 2). The temperature of the flow curve when the piston drop amount is X in the flow curve is the melting temperature in the 1/2 method.
As a measurement sample, about 1.0 g of resin was compression-molded at about 10 MPa for about 60 seconds using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25° C. A cylinder having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method start temperature: 50°C
Ultimate temperature: 200℃
Measurement interval: 1.0°C
Temperature rising rate: 4.0°C/min
Cross-sectional area of piston: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Diameter of die hole: 1.0mm
Die length: 1.0mm

<Production Example of Amorphous Polyester Resin A1>
-Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane:
71.9 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols) terephthalic acid:
26.8 parts by mass (0.16 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
1.3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180° C. (second reaction step), and polyester resin A1 having a weight average molecular weight (Mw) of 5000 Got

<Production Example of Amorphous Polyester Resin A2>
-Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 71.9 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols)-Terephthale acid:
26.8 parts by mass (0.16 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
1.3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180° C. (second reaction step), and polyester resin A2 having a weight average molecular weight (Mw) of 4800 Got

<Production Example of Amorphous Polyester Resin A3>
-Polyoxybutylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 71.9 parts by mass (0.20 mol; 100.0 mol% relative to the total number of polyhydric alcohols)-Terephthale acid:
26.8 parts by mass (0.16 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
1.3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180° C. (second reaction step), and the polyester resin A3 having a weight average molecular weight (Mw) of 5300. Got

<Production Example of Amorphous Polyester Resin A4>
2,2-bis(4-hydroxyphenyl)propane:
71.9 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols) terephthalic acid:
26.8 parts by mass (0.16 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
1.3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180° C. (second reaction step), and the polyester resin A4 having a weight average molecular weight (Mw) of 4900 Got

<Production Example of Amorphous Polyester Resin A5>
Production of Polyester A 100 g of propylene oxide adduct of bisphenol A and 100 g of terephthalic acid were prepared as an acid component, and these were stored in a flask equipped with a nitrogen introduction tube and a dehydration tube at 200° C. for 6 hours. The reaction was carried out under the conditions. Then, the atmosphere pressure was set to 8 kPa, and the reaction was further performed for 1 hour, and the obtained reaction product was designated as polyester resin A5. The measured value of the glass transition point Tg [°C] of the polyester resin A5 was 58°C.

<Production Example of Amorphous Polyester Resin B1>
-Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane:
71.8 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols) terephthalic acid:
15.0 parts by mass (0.09 mol; 55.0 mol% based on the total number of polyvalent carboxylic acids)
・Adipic acid:
6.0 parts by mass (0.04 mol; 25.0 mol% based on the total number of polycarboxylic acid mols)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160° C. (second reaction step). Polyester resin B1 having a weight average molecular weight (Mw) of 100,000. Got

<Production Example of Amorphous Polyester Resin B2>
-Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 71.8 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)-Terephthale acid:
15.0 parts by mass (0.09 mol; 55.0 mol% based on the total number of polyvalent carboxylic acids)
・Adipic acid:
6.0 parts by mass (0.04 mol; 25.0 mol% based on the total number of polycarboxylic acid mols)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160° C. (second reaction step). Polyester resin B2 having a weight average molecular weight (Mw) of 110,000. Got

<Production Example of Amorphous Polyester Resin B3>
-Polyoxybutylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 71.8 parts by mass (0.20 mol; 100.0 mol% relative to the total number of polyhydric alcohols)-Terephthale acid:
15.0 parts by mass (0.09 mol; 55.0 mol% based on the total number of polyvalent carboxylic acids)
・Adipic acid:
6.0 parts by mass (0.04 mol; 25.0 mol% based on the total number of polycarboxylic acid mols)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was reduced to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160° C. (second reaction step). Polyester resin B3 having a weight average molecular weight (Mw) of 120,000. Got

<Production Example of Amorphous Polyester Resin B4>
-2,2-bis(4-hydroxyphenyl)propane: 71.8 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols)
·Terephthalic acid:
15.0 parts by mass (0.09 mol; 55.0 mol% based on the total number of polyvalent carboxylic acids)
・Adipic acid:
6.0 parts by mass (0.04 mol; 25.0 mol% based on the total number of polycarboxylic acid mols)
-Titanium tetrabutoxide: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polyvalent carboxylic acids)
Then, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160° C. (second reaction step). Polyester resin B4 having a weight average molecular weight (Mw) of 110,000. Got

<Production Example of Crystalline Polyester Resin C1>
*1,6-hexanediol:
34.5 parts by mass (0.29 mol; 100.0 mol% relative to the total number of polyhydric alcohols) dodecanedioic acid:
65.5 parts by mass (0.28 mol; 100.0 mol% with respect to the total number of polyvalent carboxylic acids)
The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140°C.
-Tin 2-ethylhexanoate: 0.5 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining the temperature at 200°C to give a crystalline polyester resin C1. Got The obtained crystalline polyester resin C1 had a clear endothermic peak.

<Production Example of Crystalline Polyester Resin C2>
・1,4-Butanediol:
27.4 parts by mass (0.29 mol; 100.0 mol% relative to the total number of polyhydric alcohols) tetradecanedioic acid:
72.6 parts by mass (0.28 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids)
The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140°C.
-Tin 2-ethylhexanoate: 0.5 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining the temperature at 200°C to give a crystalline polyester resin C2. Got The obtained crystalline polyester resin C2 had a clear endothermic peak.

<Production Example of Crystalline Polyester Resin C3>
・1,8-Octanediol:
42.0 parts by mass (0.29 mol; 100.0 mol% based on the total number of polyhydric alcohols) sebacic acid:
58.0 parts by mass (0.29 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids)
The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140°C.
-Tin 2-ethylhexanoate: 0.5 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining the temperature at 200°C to give crystalline polyester resin C3. Got The obtained crystalline polyester resin C3 had a clear endothermic peak.

<Production Example of Crystalline Polyester Resin C4>
100 g of propylene glycol was prepared as an alcohol component, and 100 g of terephthalic acid was prepared as an acid component, and these were reacted in a flask equipped with a nitrogen introduction tube and a dehydration tube at 200° C. for 6 hours. Then, the atmosphere pressure was set to 8 kPa, and the reaction was further performed for 1 hour, and the obtained reaction product was used as a crystalline polyester resin C4. The obtained crystalline polyester resin C4 had a clear endothermic peak.

<Production Example of Vinyl Resin Polymer D>
-Polyethylene having one or more unsaturated bonds (Mw: 1400, Mn: 850, endothermic peak by DSC: 100°C) 20 parts by mass-Styrene 59 parts by mass-Acrylonitrile-n-butyl 18.5 parts by mass-Acrylonitrile 2.5 parts by mass The above raw materials were charged into an autoclave, the system was purged with nitrogen, and the temperature was maintained at 180° C. with stirring. Into the system, 50 parts by mass of a 2% by mass solution of di-tert-butylperoxide in xylene was continuously added dropwise for 5 hours, and after cooling, the solvent was separated and removed, and the vinyl-based resin polymer grafted with polyethylene was used. Obtained a coalescence E. The obtained vinyl resin polymer E has a softening point of 110° C. and a glass transition temperature of 64° C. The molecular weight of the THF-soluble component of the polymer E measured by GPC is weight average molecular weight (Mw) 7400, number average molecular weight. It was (Mn) 2800. No peak corresponding to polyethylene having one or more unsaturated bonds in the raw material was observed.

<Toner Production Example 1>
Amorphous polyester resin A1 70 parts by mass Amorphous polyester resin B1 30 parts by mass Crystalline polyester resin C1 7.5 parts by mass Vinyl resin polymer D 5 parts by mass Hydrocarbon wax (maximum endothermic peak Peak temperature 78°C) 5 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass, 3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts by mass The raw materials shown in the above formulation were used in a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). Then, the mixture was mixed at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 135° C. The obtained kneaded product was cooled (cooling rate 15° C./min) and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. The operating conditions of the rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) were that the classification rotor rotation speed was 50.0 s ⁻¹ for classification. The toner particles obtained had a weight average particle diameter (D4) of 5.7 μm.
0.5 parts by mass of silica fine particles having a primary average particle diameter of 110 nm was added to 100 parts by mass of the obtained toner particles, and the rotation speed was 30 s ⁻¹ with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). Mixing was carried out for a rotation time of 10 min. The obtained mixture was heat-treated by the surface treatment apparatus shown in FIG. 4 to obtain heat-treated toner particles. The operating conditions were a feed rate of 5 kg/hr, a hot air temperature of 145° C., and a hot air flow rate of 6 m ³ /min. , Cold air temperature=0° C., cold air flow rate=4 m ³ /min. , Cold air absolute water content=3 g/m ³ , blower air flow=20 m ³ /min. , Injection air flow rate=1 m ³ /min. And The weight average particle diameter (D4) of the obtained heat-treated toner particles was 6.2 μm.
To 100 parts by mass of the obtained heat-treated toner particles, 1.0 part by mass of silica fine particles having a primary average particle size of 13.0 nm was added, and a peripheral speed of 45 m/with a Henschel mixer (FM75 type, manufactured by Mitsui Miike Kakoki Co., Ltd.). After mixing for 5 sec, toner 1 was obtained by passing through an ultrasonic vibrating screen having an opening of 54 μm.

<Toner Production Examples 2 to 19>
Toners 2 to 19 were produced in the same manner as in Toner Production Example 1 except that the amounts and types of resin A, resin B, and resin C, kneading temperature, cooling rate after kneading, heat treatment temperature, and cooling temperature after heat treatment were varied. Table 1 shows the material formulation and manufacturing conditions.

<Toner Production Example 20>
Amorphous polyester resin A5 100 parts by weight Crystalline polyester resin C4 10 parts by weight Copper phthalocyanine pigment 5 parts by weight Chromic salicylate complex 1 part by weight These raw materials were mixed using a Henschel mixer.
Next, this raw material (mixture) was kneaded using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 150°C.
The kneaded product extruded from the extrusion port of the kneader was cooled. The cooled kneaded material was coarsely pulverized (average particle diameter: 1 to 2 mm) and then finely pulverized. A hammer mill was used for coarse pulverization of the kneaded product, and a jet mill was used for fine pulverization. The pulverized material thus obtained was classified by an airflow distributor. Thereafter, the classified pulverized product (powder for producing toner) was subjected to a thermal spheronization treatment. The thermal spheronization treatment was performed using a thermal spheronizer (manufactured by Nippon Pneumatic Co., Ltd., SFS3 type). The temperature of the atmosphere during the thermal sphering treatment was 300°C. The hot air flow rate was 1.0 m ³ /min (hot air cross-sectional area 1.26×10 ⁻³ m ² , heat treatment zone length about 0.4 m). The amount of raw material charged was 1.0 kg/hr, and the contact time with hot air was 0.03 seconds.
Then, 1.2 parts by weight of silica was mixed with 100 parts by weight of the heat-treated toner particles in a Henschel mixer to obtain a toner 20. The average particle diameter of the finally obtained toner was 8.0 μm.

得られたトナーの各種分析結果を表２に示す。

Table 2 shows various analysis results of the obtained toner.

Ｌｓ：トナー表層の結晶性ポリエステル樹脂の長軸長さの個数平均径
Ｌｉ：トナー内部の結晶性ポリエステル樹脂の長軸長さの個数平均径

Ls: number average diameter of major axis length of crystalline polyester resin in toner surface layer Li: number average diameter of major axis length of crystalline polyester resin inside toner

<Production Example of Magnetic Core Particles>
Process 1 (weighing/mixing process):
Fe ₂ O ₃ 60.2% by mass
MnCO ₃ 33.9 mass%
Mg(OH) ₂ 4.8 mass%
SrCO ₃ 1.1% by mass
The ferrite raw material was weighed so that Then, it was pulverized and mixed for 2 hours with a dry ball mill using zirconia (φ10 mm) balls.
Process 2 (preliminary baking process):
After crushing and mixing, it was fired at 1000° C. for 3 hours in the atmosphere using a burner type firing furnace to prepare a calcined ferrite. The composition of ferrite is as follows.
(MnO) a (MgO) b (SrO) c (Fe 2 O 3) d
In the above formula, a=0.39, b=0.11, c=0.01, d=0.50
Process 3 (crushing process):
After crushing to about 0.5 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using balls of zirconia (φ10 mm), and crushed for 2 hours with a wet ball mill.
The slurry was pulverized with a wet bead mill using zirconia beads (φ1.0 mm) for 4 hours to obtain a ferrite slurry.
Process 4 (granulation process):
2.0 parts by mass of polyvinyl alcohol was added to 100 parts by mass of calcined ferrite as a binder in the ferrite slurry, and granulated into spherical particles of about 36 μm with a spray dryer (manufacturer: Okawara Kakohki).
Step 5 (main firing step):
In order to control the firing atmosphere, firing was performed in an electric furnace in a nitrogen atmosphere (oxygen concentration of 1.00 vol% or less) at 1150° C. for 4 hours.
Process 6 (selection process):
After crushing the agglomerated particles, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles 1.

<Production example of coat resin>
Cyclohexyl methacrylate monomer 26.8 parts by weight Methyl methacrylate monomer 0.2 parts by weight Methyl methacrylate macromonomer 8.4 parts by weight (macromonomer having 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 Add the above materials to a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer, and introduce nitrogen gas sufficiently. The atmosphere was nitrogen. Then, the mixture was heated to 80° C., 2.0 parts by mass of azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried in vacuum to obtain a coat resin.

<Example of magnetic carrier production>
Coat resin 20.0% by mass
Toluene 80.0% by mass
The above materials were dispersed and mixed by a bead mill to obtain a resin liquid.
100 parts by mass of the magnetic core particles were put into a Nauta mixer, and further, the resin liquid was put into the Nauta mixer as a resin component so as to be 2.0 parts by mass. The mixture was heated to a temperature of 70° C. under reduced pressure, mixed at 100 rpm, and solvent removal and coating operations were performed for 4 hours. Then, the obtained sample was transferred to a Julia mixer, heat-treated at a temperature of 100° C. for 2 hours in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier. The volume distribution-based 50% particle diameter (D50) of the obtained magnetic carrier was 38.2 μm.
The toners 1 to 20 and the magnetic carrier described above were mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at 0.5 s ^{−1 at} a rotation time of 5 min so that the toner concentration was 8.0% by mass. By mixing, two-component developers 1 to 20 were obtained. The following evaluations were performed using two-component developers 1-20.

<Fixability (hot offset resistance, low temperature fixability) evaluation>
A full color copying machine image RUNNER ADVANCE C5051 manufactured by Canon was modified so that the fixing temperature could be freely set, and a test in the fixing temperature range was conducted. The image was adjusted in a single-color mode in a normal temperature and normal humidity environment (23° C./50% Rh) so that the amount of toner on the paper was 0.8 mg/cm ² , and an unfixed image was formed. Copy paper GF-C081 (A4, basis weight 81.4 g/m ² , sold by Canon Marketing Japan Co., Ltd.) was used as the evaluation paper, and images were formed at an image printing ratio of 25%. After that, the fixing temperature is increased by 1° C. from 110° C. in order, and the temperature range where offset does not occur (fixable temperature or more and less than offset occurrence temperature) is set as the fixable region, the lower limit temperature is the low temperature fixing temperature, and the upper limit temperature is the hot offset resistance. The temperature was used.
(Evaluation criteria: Hot offset resistance)
A: 225°C or higher (quite excellent)
B: 210°C or higher and lower than 225°C (excellent)
C: more than 195°C and less than 210°C (somewhat excellent)
D: 170°C or higher and lower than 195°C (prior art level)
E: less than 170°C (inferior to conventional technology)
(Evaluation criteria: low temperature fixability)
A: less than 120°C (quite excellent)
B: 120°C or higher and lower than 135°C (excellent)
C: 135°C or higher but lower than 150°C (slightly superior)
D: 150°C or higher and lower than 170°C (prior art level)
E: 170°C or higher (inferior to conventional technology)

<Low humidity environment development evaluation>
Using a Canon full-color copying machine image RUNNER ADVANCE C5051 as an image forming apparatus, the developing property was evaluated in a low humidity environment at room temperature and low humidity (23° C., 5% RH). The development evaluation was carried out by idly rotating a developing device charged with developers 1 to 2 for 2 minutes. The dark potential (background potential) of the photoconductor is -700V, the exposure potential (image potential) is -230V, the developing bias is DC component of -580V, and the AC component is frequency of 8kHz·1.2kVpp rectangular wave. After developing the latent image in the exposed area, the surface potential of the photoconductor was measured and the development charging efficiency was measured. The development charging efficiency is expressed by the photoconductor potential after toner development/photoconductor exposure potential before toner development×100 (%), and is an index showing how much the latent image potential can be filled with toner.
Also, the toner (fog) adhering to the background portion (white background portion) of the photoconductor after development is collected by taping, and the adhered amount is measured by a Photovoltaic reflection densitometer (trade name: TC-6DS/A; Tokyo Denshoku Co., Ltd.). (Made by the company).
(Evaluation criteria: low humidity development charging efficiency)
A: 98% or more (excellent)
B: 95% or more and less than 98% (somewhat excellent)
C: 85% or more and less than 95% (prior art level)
D: less than 85% (inferior to conventional technology)
(Evaluation criteria: Low humidity fog)
A: less than 0.05 (quite excellent)
B: 0.05 or more and less than 0.10 (excellent)
C: 0.10 or more and less than 0.30 (prior art level)
D: 0.30 or more (inferior to the conventional technology)

<Humidity environment toner scattering evaluation>
In a high temperature and high humidity environment (30° C., 80% RH), evaluation of toner scattering in the developing device was performed using a Canon full color copying machine image RUNNER ADVANCE C5051 as an image forming apparatus. After outputting 1000 images using a horizontal ruled line chart with an image ratio of 5%, the sample was left in a high humidity environment for 1 week. After leaving it for a while, the main body is activated again, and only the developing device is idle-rotated for 30 seconds in the main body of the image forming apparatus, and the toner adhering to the surface of the facing photoconductor is sampled by taping. Name: TC-6DS/A; manufactured by Tokyo Denshoku Co., Ltd.).
(Evaluation criteria: Toner scattering fog)
A: less than 0.25 (quite excellent)
B: 0.25 or more and less than 0.50 (excellent)
C: 0.50 or more (prior art level)
Table 3 shows the results of evaluating the toner according to the above evaluation methods and criteria.

As shown by the above results, the toner of the present invention has excellent fixability and developability.

1. Raw material quantitative supply means 2. Compressed gas flow rate adjusting means, 3. Introductory pipe, 4. Protruding member, 5. Supply pipe, 6. Processing chamber, 7. Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Collection means, 11. Hot air supply means outlet, 12. Distribution member, 13. Turning member, 14. Powder particle supply port

Claims (4)

A toner having toner particles containing a crystalline polyester resin and an amorphous polyester resin,
In cross-sectional observation of the toner with a transmission electron microscope (TEM),
The crystalline polyester resin dispersed to the depth of 0.30 μm from the toner surface has a number average diameter (D1) of the major axis length of 40 nm or more and 110 nm or less,
The crystalline polyester in which the number average diameter (D1) of the major axis lengths of the crystalline polyester resin dispersed inward from the toner surface by 0.30 μm is dispersed to the depth of 0.30 μm from the toner surface. A toner characterized by having a major axis length of resin of 1.25 times or more and 4.00 times or less of a number average diameter (D1). The toner according to claim 1, wherein a number average diameter (D1) of major axis lengths of the crystalline polyester resin dispersed inward from the surface of the toner by 0.30 μm is 60 nm or more and 300 nm or less. The toner according to claim 1 or 2, wherein an aspect ratio of the crystalline polyester resin dispersed inward of 0.30 μm from the toner surface is 6.0 or more and 30.0 or less. In the number distribution of the major axis length of the crystalline polyester resin dispersed inward from the toner surface by 0.30 μm, the maximum value is 80 nm or more and 200 nm or less,
The number distribution of the major axis length of the crystalline polyester resin dispersed to a depth of 0.30 μm from the toner surface has a maximum value of 50 nm or more and 100 nm or less. Toner.

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