Toner

Abstract

To provide a toner that has excellent developability, low temperature fixability, and scratch resistance.SOLUTION: A toner has a toner particle containing a binder resin and hydrocarbon wax. The binder resin contains a crystalline resin. The crystalline resin has a weight average molecular weight of 200000 or more and 1000000 or less and has a first monomer unit and a second monomer unit different from the first monomer unit. The ratio of the first monomer unit in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less based on the total mass of all the monomer units of the crystalline resin. The ratio of the second monomer unit in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less based on the total mass of all the monomer units of the crystalline resin. The hydrocarbon wax has an acid value of 5 mgKOH / g or more and 50 mgKOH / g or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to toner used in electrophotographic systems, electrostatic recording systems, electrostatic printing systems, toner jet systems, and the like.

Background Art

[0002] As copiers and printers have become widespread, the performance required of toner has become more sophisticated. In recent years, digital printing technology that directly prints without going through a plate-making process called print-on-demand (POD) has attracted attention. In the POD market, higher speed and higher image quality than ever are expected. As one means of achieving higher image quality, large-particle-size toner with high electric field followability has been proposed from the viewpoint of suppressing scattering of toner to non-image areas. However, compared with small-particle-size toner, large-particle-size toner has a smaller amount of deformation during fixing. Therefore, there are problems such as poor low-temperature fixability to media and difficulty in high-speed printing. In order to achieve higher speed, there is a demand for toner with excellent low-temperature fixability that can be efficiently fixed at a lower temperature. Materials having sharp meltability have been proposed to improve low-temperature fixability. For example, Patent Document 1 discloses toner using a crystalline resin excellent in low-temperature fixability as a main binder.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The crystalline resin described in Patent Document 1 has a hydrocarbon-based unit side chain in the molecule. Therefore, the hydrocarbon units between molecules are oriented with each other and have crystal sites, thereby exhibiting sharp meltability. However, since there is little entanglement between molecular chains at the crystalline sites, it is considered that the toner containing the above resin has low hardness and stickiness. When the toner containing the above resin is printed and the surface of the printed matter is rubbed, there is a possibility that the toner may shift to the back. As a means for relaxing the stress against rubbing and suppressing the back transfer of the toner, there is a method of exposing a lubricating material on the image surface. For example, Patent Document 2 discloses a toner that suppresses back transfer by exposing a lubricating material on the image surface and relaxing the stress applied to the image surface. However, when a lubricating material is exposed on the image surface, the fixing member may be contaminated during fixing. The present invention has been made in view of the above-described problems. The present invention provides a toner having excellent developability, low-temperature fixability, and abrasion resistance without contaminating the member.

Means for Solving the Problems

[0005] The present invention is a toner having toner particles containing a binder resin and a hydrocarbon-based wax, the binder resin contains a crystalline resin, the crystalline resin, The tetrahydrofuran-soluble content measured by gel permeation chromatography has a weight average molecular weight of 200,000 or more and 1,000,000 or less, The crystalline resin satisfies the following provisions (I) or (II), (I): (I-i) a first monomer unit represented by the following formula (1), and (I-ii) a second monomer unit selected from the group consisting of acrylonitrile units, methacrylonitrile units, vinyl acetate units, and acrylic acid units and has (I-iii) the total of the first monomer unit and the second monomer unit is 100% by mass based on the total mass of all the monomer units of the crystalline resin, (II): (II-i) a first monomer unit represented by the following formula (1), (II-ii) a second monomer unit selected from the group consisting of acrylonitrile units, methacrylonitrile units, vinyl acetate units, and acrylic acid units, and (II-iii) a third monomer unit which is a styrene unit and has (II-iv) the total of the first monomer unit, the second monomer unit, and the third monomer unit is 100% by mass based on the total mass of all the monomer units of the crystalline resin, a ratio of the first monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less; a ratio of the second monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less; The hydrocarbon wax is has a carboxylic acid group, The acid value is 5 mgKOH / g or more and 50 mgKOH / g or less. The present invention relates to a toner characterized by the above-mentioned.

[0006] [ka] (In formula (1), R Z1 represents a hydrogen atom or a methyl group, R 1 is a compound with 18 to 36 carbon atoms. linear represents an alkyl group. Effect of the Invention

[0009] According to the present invention, it is possible to provide a toner that does not contaminate components and has excellent developability, low-temperature fixability, and abrasion resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the present invention, the expressions "xx or more and xx or less" and "xx to xx" expressing a numerical range mean a numerical range including the lower and upper limit endpoints, unless otherwise specified.

[0011] In the present invention, the (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.

[0012] In the present invention, the term "monomer unit" refers to one section of carbon-carbon bonds in the main chain of a polymer formed by polymerization of a vinyl monomer. The vinyl monomer can be represented by the following formula (Z).

[0013] [Chemical formula] [In formula (Z), R Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R Z2 represents an arbitrary substituent.]

[0014] A crystalline resin refers to a resin that exhibits a distinct endothermic peak in differential scanning calorimetry (DSC) measurement.

[0015] Hereinafter, embodiments for carrying out the present invention will be described in detail.

[0016] The present invention is a toner having toner particles containing a binder resin and a hydrocarbon wax, the binder resin contains a crystalline resin, the crystalline resin has a weight average molecular weight of 200,000 or more and 1,000,000 or less, (i) a first monomer unit represented by the following formula (1), and (ii) a second monomer unit represented by the following formula (2) or (3) different from the first monomer unit and the proportion of the first monomer unit in the crystalline resin is 20.0% by mass or more and 70.0% by mass or less with respect to the total mass of all monomer units of the crystalline resin, the proportion of the second monomer unit in the crystalline resin is 20.0% by mass or more and 70.0% by mass or less with respect to the total mass of all monomer units of the crystalline resin, the hydrocarbon wax has an acid value of 5 mgKOH / g or more and 50 mgKOH / g or less, and is characterized by the above.

[0017] [Chemical formula] (In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1represents an alkyl group having 18 to 36 carbon atoms.)

[0018]

Chemical formula

[0019]

Chemical formula

[0020] As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by controlling the composition and ratio of the monomer units of the crystalline resin and the acid value of the wax within specific ranges, leading to the present invention. The present inventors speculate the reasons for achieving the above problems as follows.

[0021] Resins having hydrocarbon-based units in the side chains within the molecule have crystallinity. This is considered to be because the hydrocarbon units between molecules are oriented and have crystal sites. Therefore, resins having hydrocarbon-based units in the side chains have sharp melt properties and exhibit good low-temperature fixing properties.

[0022] However, it is considered that the hardness and stickiness of the resin are low at the crystal sites because there is little entanglement between the molecular chains. When printing a toner containing the above crystalline resin, if rubbing occurs on the image surface of the printed matter, there may be a problem that the toner migrates to the back.

[0023] On the other hand, in order to increase the hardness and stickiness of the resin, when the entanglement between the molecular chains is improved, it is presumed that the crystallinity of the resin is lost and the low-temperature fixing property deteriorates.

[0024] Therefore, in order to improve the abrasion resistance without deteriorating the low-temperature fixing property, it is considered necessary to increase the entanglement between molecules and increase the resin strength while maintaining the crystallinity.

[0025] The present inventors have discovered that by using a toner in which a hydrocarbon-based wax having an acid value is added to a crystalline resin having a polar group, it is possible to increase the strength of the toner particles while maintaining the sharp melt property derived from the crystalline resin, and to achieve both low-temperature fixing property and abrasion resistance. As a result of detailed studies, it has been found that the crystalline resin in the toner particles has a polar group and the hydrocarbon-based wax has an acid value, which affects the expression of the effect, leading to the present invention.

[0026] Hydrocarbon waxes having an acid value have carboxylic acid groups or the like in the molecule. The carboxylic acid of the hydrocarbon wax having an acid value in the toner particles and the polar groups in the main chain of the crystalline resin exhibit dipole-dipole interaction. It is considered that the hydrocarbon wax having an acid value bridges between the molecules of the crystalline resin and plays a role of attracting the molecules of the crystalline resin to each other. Therefore, it is presumed that the stickiness and elastic modulus of the toner particles are improved.

[0027] In addition, since the hydrocarbon wax having an acid value interacts with the polar groups of the crystalline resin, it does not inhibit the crystal formation of the side chains of the crystalline resin. Since the side chains of the crystalline resin are oriented so as to avoid the hydrocarbon wax having an acid value, it is presumed that the crystalline resin efficiently forms crystals.

[0028] As a result, the toner particles have sharp meltability derived from the crystalline resin and the resin strength derived from the cohesion between molecules is improved.

[0029] Therefore, it is considered that the toner of the present invention can achieve both low-temperature fixability and abrasion resistance.

[0030] In addition, since the hydrocarbon wax having an acid value interacts with the crystalline resin, excessive migration to the image surface during fixing is reduced. As a result, it is considered that the toner of the present invention is less likely to cause member contamination such as the hydrocarbon wax having an acid value in the toner migrating to the fixing member during fixing.

[0031] In addition, since the hydrocarbon wax having an acid value strongly interacts with the polar groups of the crystalline resin, it is uniformly dispersed in the toner particles. Therefore, since the hydrocarbon wax having an acid value is not locally unevenly distributed on the toner surface, it is considered that the adhesion force of the toner particles is reduced and the fluidity is improved.

[0032] Therefore, it is considered that the toner of the present invention does not aggregate during development and has good dot reproducibility.

[0033] The toner of the present invention contains a binder resin having a crystalline resin and a wax.

[0034] <Crystalline resin> The crystalline resin of the present invention has a weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component measured by gel permeation chromatography (GPC) of 200,000 or more and 1,000,000 or less, preferably 220,000 or more and 300,000 or less. When the weight average molecular weight of the crystalline resin is within the above range, since the polar groups of the crystalline resin that interact with the wax having an acid value are appropriately present, the resin strength is improved. Further, due to the interaction between the polar groups of the crystalline resin and the wax having an acid group, the wax having an acid group does not inhibit the crystallinity of the resin, so excellent low-temperature fixability can be obtained. Further, it is difficult for the wax to be exposed on the toner surface, the adhesion of the toner matrix is reduced, and the fluidity of the toner is improved. Further, when the toner is fixed, excessive exposure of the wax to the image surface is reduced, and contamination of the member is reduced.

[0035] Therefore, the toner of the present invention has good low-temperature fixability, member contamination suppression, abrasion resistance, and dot reproducibility.

[0036] The crystalline resin of the present invention has a first monomer unit represented by the above formula (1). The first monomer unit represented by the above formula (1) is derived from at least one first polymerizable monomer selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 or more and 36 or less carbon atoms.

[0037] When the first monomer unit is a (meth)acrylic acid ester having an alkyl group having 18 or more and 36 or less carbon atoms, crystallinity can be imparted to the resin. Therefore, the toner exhibits sharp meltability and excellent low-temperature fixability can be obtained.

[0038] Examples of the (meth)acrylic acid ester having an alkyl group with 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms [(stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, cerinyl (meth)acrylate, octacosanyl (meth)acrylate, myricyl (meth)acrylate, dotriacontanyl (meth)acrylate, etc.)] and (meth)acrylic acid esters having a branched alkyl group with 18 to 36 carbon atoms [(2-decyltetradecyl (meth)acrylate, etc.)].

[0039] Among these, from the viewpoint of low-temperature fixability, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms is preferable, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms is more preferable, and linear behenyl (meth)acrylate is even more preferable.

[0040] The polymerizable monomer derived from the first monomer unit represented by the above formula (1) may be used alone or in combination of two or more.

[0041] The crystalline resin of the present invention has a second monomer unit represented by the above formula (2) or (3) different from the first monomer unit. By including the second monomer unit, the crystallization of the first monomer unit is promoted, and it has excellent low-temperature fixability.

[0042] The reason is considered as follows. Specifically, the first monomer unit is incorporated into the crystalline resin, and crystallinity is exhibited by the aggregation of the first monomer units. Generally, the crystallization of the first monomer unit is inhibited when other monomer units are incorporated. Therefore, it becomes difficult for the crystalline resin to exhibit crystallinity. This tendency becomes remarkable when a plurality of types of monomer units are randomly bonded in the molecule of the crystalline resin.

[0043] However, when a first monomer unit and a second monomer unit having a higher polarity than the first monomer unit are used in combination as the constituent monomers of the crystalline resin, it is considered that the first monomer units can be appropriately continuously bonded during the polymerization of the crystalline resin. Since the crystalline resin tends to have a structure similar to that of a block copolymer, even if other monomer units are incorporated, the crystallinity can be enhanced.

[0044] Therefore, the toner of the present invention has good low-temperature fixability derived from the crystal sites of the crystalline resin. Furthermore, the high-polarity sites of the crystalline resin improve the resin strength due to the interaction with the wax having an acid value and have good abrasion resistance.

[0045] Specifically, as the second monomer unit, for example, among the polymerizable monomers listed below, a polymerizable monomer satisfying the above formula (2) or (3) can be used.

[0046] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.

[0047] Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, acrylic acid, etc.

[0048] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method.

[0049] Monomers having a urea group; for example, amines having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as dinormal ethylamine, dinormal propylamine, dinormal butylamine, etc.), aniline, and cyclohexylamine, etc.], and monomers obtained by reacting an isocyanate having 2 to 30 carbon atoms with an ethylenically unsaturated bond by a known method, etc.

[0050] Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.

[0051] Among them, it is preferable to use monomers having a nitrile group, an amide group, a hydroxy group, or a urea group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, and a urea group and an ethylenically unsaturated bond. Acrylonitrile, methacrylonitrile, and acrylic acid are particularly preferable.

[0052] Also, as the second monomer unit, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate are also preferably used. Among them, vinyl esters are non-conjugated monomers, and the reactivity with the first polymerizable monomer is moderately maintained, and it is easy to increase the crystallinity of the polymer. Therefore, they are preferable from the viewpoint of low-temperature fixability.

[0053] The proportion of the first monomer unit in the crystalline resin of the present invention is 20.0% by mass or more and 70.0% by mass or less, preferably 30.0% by mass or more and 60.0% by mass or less, based on the total mass of all monomer units in the crystalline resin.

[0054] When the proportion of the first monomer unit is within the above range, the resin has crystallinity and the toner exhibits sharp meltability, so excellent low-temperature fixability can be obtained. Further, since polar groups derived from the second monomer unit are present, the resin strength is moderately improved by the interaction with the wax having an acid group. Further, the exposure of the wax on the toner surface is reduced, and the adhesion of the toner matrix is reduced. Therefore, the fluidity of the toner is improved. Further, when the toner is fixed, the excessive exposure of the wax on the image surface is reduced, and the contamination of the member is reduced.

[0055] Therefore, the toner of the present invention has good low-temperature fixability, member contamination suppression, abrasion resistance, and dot reproducibility.

[0056] The proportion of the second monomer unit is 20.0% by mass or more and 70.0% by mass or less.

[0057] When the proportion of the second monomer unit is within the above range, the interaction between the polar group of the crystalline resin and the wax having an acid group is exhibited, and the resin strength is moderately improved. Further, due to the interaction between the polar group of the crystalline resin and the wax having an acid group, the wax having an acid group does not inhibit the crystallinity of the resin, so excellent low-temperature fixability can be obtained. Further, it is difficult for the wax to be exposed on the toner surface, the adhesion of the toner matrix is reduced, and the fluidity of the toner is improved. Further, when the toner is fixed, the excessive exposure of the wax on the image surface is reduced, and the contamination of the member is reduced.

[0058] Therefore, the toner of the present invention has good low-temperature fixability, member contamination suppression, abrasion resistance, and dot reproducibility.

[0059] In addition, when the crystalline resin has a monomer unit derived from a (meth)acrylic acid ester having two or more alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit represents the total mass ratio thereof.

[0060] The crystalline resin of the present invention may contain a third monomer unit derived from a third polymerizable monomer as long as the mass ratio of the above-described first monomer unit and second monomer unit is not impaired. For example, the following monomers can also be used.

[0061] Styrene and its derivatives such as styrene and o-methylstyrene, (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among them, the third polymerizable monomer is preferably styrene. When it is styrene, the aromatic ring of styrene exhibits π-π interaction between molecules, and the strength is improved as toner particles. Therefore, it is preferable because the toner particle adhesion force is reduced and the dot reproducibility is improved.

[0062] The proportion of the third monomer unit is preferably 5.0% by mass or more and 40.0% by mass or less, more preferably 10.0% by mass or more and 20.0% by mass or less, based on the total mass of all monomer units in the crystalline resin.

[0063] The melting point of the crystalline resin is preferably 50°C or higher and 80°C or lower, more preferably 53°C or higher and 70°C or lower. When the melting point of the crystalline resin is within the above range, better low-temperature fixability is exhibited. The melting point of the crystalline resin can be adjusted by the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like.

[0064] <Softening point of the crystalline resin> The softening point of the crystalline resin is preferably 70°C or higher and 115°C or lower. More preferably, it is 100°C or higher and 120°C or lower. When the softening point is within the above range, it is possible to suppress the excessive amount of the wax of the present invention on the image surface during image formation, and it is possible to achieve both low-temperature fixability and abrasion resistance of the printed matter.

[0065] The crystalline resin is preferably a vinyl polymer. Examples of the vinyl polymer include polymers of monomers containing ethylenically unsaturated bonds. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

[0066] <Hydrocarbon wax> The wax having an acid value of the present invention has a hydrocarbon chain as a main skeleton, and is generally a modified hydrocarbon wax in which an acid group is introduced through a modification step. Examples of the modified hydrocarbon wax including the production method will be described.

[0067] For example, there is a production method in which paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, etc. are polymerized using a Ziegler catalyst, and after the polymerization is completed, oxidized to form an alkoxide of a catalyst metal and polyethylene, and then hydrolyzed.

[0068] In addition, there is a production method in which a hydrocarbon wax is subjected to liquid-phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. As the catalyst, a mixture of boric acid and boric anhydride, metaboric acid, and pyrophosphoric acid can also be used.

[0069] In addition, oxygen acids of boron, oxygen acids of phosphorus, and oxygen acids of sulfur are included. Specifically, boric acid, nitric acid, phosphoric acid, or sulfuric acid is included. As the molecular oxygen-containing gas blown into the reaction system, a wide range of oxygen, air, or those diluted with an inert gas can be used. The liquid-phase oxidation reaction is usually carried out without using a solvent, and is carried out in a molten state of the raw material hydrocarbon wax. The reaction temperature is 120 to 280 ° C, preferably 150 to 250 ° C. The reaction time is preferably 1 to 15 hours.

[0070] The acid value of the wax of the present invention is 5 mgKOH / g or more and 50 mgKOH / g or less. Preferably, it is 20 mgKOH / g or more and 40 mgKOH / g or less.

[0071] When the acid value of the wax is within the above range, the wax having a polar group and an acid group derived from the second monomer unit effectively interacts with each other and does not inhibit the crystallinity of the resin, so excellent low-temperature fixability can be obtained. Further, due to the interaction between the wax having a polar group and an acid group derived from the second monomer unit, the resin strength is moderately improved. Further, the exposure of the wax on the toner surface is reduced, and the adhesion of the toner matrix is reduced. Therefore, the fluidity of the toner is improved. Further, when the toner is fixed, excessive exposure of the wax on the image surface is reduced, and the contamination of the member is reduced.

[0072] Therefore, when the acid value of the wax is within the above-described range, the low-temperature fixability, the suppression of member contamination, the abrasion resistance, and the dot reproducibility are good.

[0073] The wax having an acid value used in the present invention preferably has a maximum endothermic peak temperature of 80 ° C or higher and 150 ° C or lower when the crystal structure composed of hydrocarbon chains measured by a differential scanning calorimeter (DSC) melts. More preferably, it is 90 ° C or higher and 140 ° C or lower. When the maximum endothermic peak temperature and the acid value are within the above-described ranges, it is possible to achieve both suppression of member contamination and wear resistance of the printed matter.

[0074] The content of the wax having an acid value in the present invention is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably, it is 1.0 part by mass or more and 16.0 parts by mass or less, and still more preferably 5.0 parts by mass or more and 12.0 parts by mass or less. When the content of the wax having an acid value is within the above range, it is possible to achieve both suppression of member contamination and wear resistance of the printed matter.

[0075] <Other resins> The binder resin of the toner of the present invention may contain a resin other than the crystalline resin as necessary.

[0076] Examples of the resin other than the crystalline resin used in the binder resin of the toner of the present invention include the following resins. Homopolymers of styrene and its substituents such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; Styrene copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, 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 copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; Polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, 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, etc. can be mentioned.

[0077] Among these, styrene copolymers and polyester resins are preferred. Also, it is preferably amorphous.

[0078] The binder resin contains amorphous polyester. The amorphous polyester preferably has a softening point of 85°C or higher and 105°C or lower, more preferably 90°C or higher and 100°C or lower.

[0079] It is preferable that at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols is condensed at the end of the amorphous resin.

[0080] Further, the amorphous resin preferably includes an amorphous polyester resin containing a bisphenol derivative and ethylene glycol as the alcohol component of the polyester resin. The content ratio of the bisphenol derivative to ethylene glycol is preferably such that the mol% of the bisphenol derivative / mol% of ethylene glycol is 2.0 or more and 6.0 or less, and more preferably 3.0 or more and 5.0 or less. When the content ratio of the bisphenol derivative to ethylene glycol is within the above range, the steric hindrance of the polyester resin molecules is reduced.

[0081] Here, the wax having an acid value plays a role of bridging between crystalline resin molecules by the interaction between its polar group and the polar group of the crystalline resin under the condition of active molecular motion. The polyester resin molecules can enter between the crystalline resin molecules because of the small steric hindrance of the ethylene glycol part. At this time, the ester bond or the acid group at the molecular end of the polyester resin molecule interacts with the polar part of the crystalline resin molecule. In the process of crystallization of the wax having an acid value, the main chain of the crystalline resin and the ester bond or the acid part at the molecular end of the polyester resin molecule are incorporated into the crystal part of the wax.

[0082] As a result, the strength of the toner particles is increased and the abrasion resistance is improved. It is considered that the above effect appears remarkably because the presence of ethylene glycol in the molecule of the amorphous polyester resin increases the ester group concentration per molecule.

[0083] The amorphous resin of the present invention preferably includes an amorphous polyester resin condensed from at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols having a specific number of carbon atoms.

[0084] The aliphatic compound introduced into the polyester resin is preferably at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols. The number of carbon atoms (average value of the number of carbon atoms of the aliphatic compound) is preferably 30 or more and 80 or less, and more preferably 30 or more and 60 or less.

[0085] Further, the aliphatic compound is preferably monovalent. By being monovalent, the aliphatic compound will condense at the molecular terminals of the amorphous polyester resin. The carbon chain derived from the aliphatic compound condensed at the molecular terminals has an affinity for the wax having an acid value and effectively exhibits an interaction.

[0086] Specifically, the wax having an acid value plays a role of a bridge connecting between the molecules of the crystalline resin. Under the situation where the polar part of the crystalline resin molecule and the polar part of the wax having an acid value interact with each other, the aliphatic hydrocarbon part bonded to the molecular terminal of the amorphous polyester resin can enter between the molecules of the crystalline resin by having an affinity for the wax having an acid value. At that time, the ester bond of the amorphous polyester resin molecule approaches the polar part of the crystalline resin molecule and exhibits an interaction.

[0087] As a result, it is considered that the strength as toner particles is increased and the abrasion resistance is improved.

[0088] The addition amount of the aliphatic compound is preferably 0.10 parts by mass or more and 10.0 parts by mass or less, more preferably 0.10 parts by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the total mass of the monomers constituting the polyester resin condensed with the aliphatic compound. By the addition amount of the aliphatic compound being within the above range, the interaction with the wax having an acid value can be effectively exhibited without inhibiting the crystallization of the wax having an acid value.

[0089] The aliphatic compound used in the present invention is not particularly limited as long as it is an aliphatic monocarboxylic acid or aliphatic monoalcohol having a specific chain length. For example, any of primary, secondary, and tertiary ones can be used. Specifically, examples of the aliphatic monocarboxylic acid include melissic acid, lacceric acid, tetracosanoic acid, pentacanoic acid, and the like. Further, examples of the aliphatic monoalcohol include melissyl alcohol, tetracosanol, and the like.

[0090] The method of condensing an aliphatic compound at the terminal of the polyester resin is not particularly limited. As a preferred embodiment, when producing the polyester resin, it is preferable to simultaneously add the aliphatic compound to the monomers constituting the polyester resin and perform polycondensation. By this, the aliphatic compound can be condensed more uniformly at the terminal of the polyester resin.

[0091] In the present invention, the method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned divalent carboxylic acid compound and divalent alcohol compound are charged simultaneously with an aliphatic monocarboxylic acid or aliphatic monoalcohol, and polymerized through an esterification reaction or transesterification reaction, and a condensation reaction to produce a polyester resin. Also, the polymerization temperature when producing the polyester resin is not particularly limited, but a range of 180 °C or higher and 290 °C or lower is preferable. When polymerizing the polyester unit, for example, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used. In particular, it is more preferable that the binder resin in the present invention contains a polyester unit polymerized using a titanium-based catalyst. By using a titanium-based catalyst, the charge uniformity in the toner is improved.

[0092] Specific examples of the titanium compound include titanium diisopropylate bis(triethanolamineate) [Ti(C 6 H 14 O 3 N) 2 (C 3 H 7 O) 2 , titanium diisopropylate bis(diethanolamineate) [Ti(C 4 H 10 O 2 N) 2 (C 3 H 7 O) 2 , titanium dipentylate bis(triethanolamineate) [Ti(C 6 H 14 O 3 N) 2 (C 5H 11 O) 2 〕, titanium diethoxide bistriethanolamine [Ti(C 6 H 14 O 3 N) 2 (C 2 H 5 O) 2 〕, titanium dihydroxyoctylate bistriethanolamine [Ti(C 6 H 14 O 3 N) 2 (OHC 8 H 16 O) 2 〕, titanium distearate bistriethanolamine [Ti(C 6 H 14 O 3 N) 2 (C 18 H 37 O) 2 〕, titanium triisopropylate triethanolamine [Ti(C 6 H 14 O 3 N) 1 (C 3 H 7 O) 3 〕, titanium monopropylate tris(triethanolamine) [Ti(C 6 H 14 O 3 N) 3 (C 3 H 7 O) 1 〕, etc. Among these, titanium diisopropylate bistriethanolamine, titanium diisopropylate bisdiethanolamine, and titanium dipentylate bistriethanolamine are preferred.

[0093] Specific examples of other titanium catalysts include tetra-n-butyl titanate [Ti(C 4 H 9 O) 4 〕, tetrapropyl titanate [Ti(C 3 H 7 O) 4 〕, tetrastearyl titanate [Ti(C18 H 37 O) 4 〕, tetramyristyl titanate [Ti(C 14 H 29 O) 4 〕, tetraoctyl titanate [Ti(C 8 H 17 O) 4 〕, dioctyldihydroxyoctyl titanate [Ti(C 8 H 17 O) 2 (OHC 8 H 16 O) 2 〕, dimyristyldioctyl titanate [Ti(C 14 H 29 O) 2 (C 8 H 17 O) 2Examples include [compounds]. Among these, tetra-stearyl titanate, tetra-myristyl titanate, tetra-octyl titanate, and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting titanium halide with the corresponding alcohol. Further, it is more preferable that the titanium compound contains an aromatic carboxylic acid titanium compound. The aromatic carboxylic acid titanium compound is preferably obtained by reacting an aromatic carboxylic acid with a titanium alkoxide. Also, as the aromatic carboxylic acid, it is preferable that it is a divalent or higher aromatic carboxylic acid (i.e., an aromatic carboxylic acid having two or more carboxyl groups) and / or an aromatic oxycarboxylic acid. Examples of the above divalent or higher aromatic carboxylic acids include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid or their anhydrides, polycarboxylic acids such as trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, naphthalene tetracarboxylic acid or their anhydrides, esterified products, etc. Examples of the above aromatic oxycarboxylic acids include salicylic acid, m-hydroxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, tropic acid, etc. Among these, it is more preferable to use a divalent or higher carboxylic acid as the aromatic carboxylic acid, and in particular, it is preferable to use isophthalic acid, terephthalic acid, trimellitic acid or naphthalene dicarboxylic acid.

[0094] <Inorganic fine particles> The toner of the present invention may be a conductive toner or an insulating toner. The toner of the present invention may contain inorganic fine particles as required. The inorganic fine particles may be incorporated into the toner particles or mixed with the toner as an external additive.

[0095] In the case of a conductive toner, examples of the inorganic fine particles include fine particles such as carbon black, silica fine particles, titanium oxide fine particles, alumina fine particles, or their complex oxide fine particles. Among the inorganic particles, carbon black and silica fine particles are preferred for improving fluidity and uniformizing conductivity. The volume resistivity (Ω·cm) of the conductive toner is 1.0×106 It is preferably 3.0×10 or less as follows. 6 It is preferably as follows.

[0096] In the case of the insulating toner, examples of the inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or complex oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and charge uniformity.

[0097] The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0098] From the viewpoint of improving fluidity, the inorganic fine particles as an external additive preferably have a specific surface area of 50 m 2 / g or more and 400 m 2 / g or less. From the viewpoint of improving durable stability, the inorganic fine particles as an external additive preferably have a specific surface area of 10 m 2 / g or more and 50 m 2 / g or less. In order to achieve both improved fluidity and durable stability, inorganic fine particles having a specific surface area within the above range may be used in combination.

[0099] The content of the external additive is preferably 0.1 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. Mixing of the toner particles and the external additive can be performed using a known mixer such as a Henschel mixer.

[0100] <Colorant> The toner of the present invention may be a magnetic toner or a non-magnetic toner.

[0101] When the toner of the present invention is used as a non-magnetic toner, if necessary, carbon black or one or more of any conventionally known pigments and dyes can be used as the colorant. The addition amount of the colorant is preferably 0.1 part by mass or more and 100.0 parts by mass or less, more preferably 0.5 part by mass or more and 95.0 parts by mass or less, with respect to 100.0 parts by mass of the binder resin.

[0102] When the toner of the present invention is used as a magnetic toner, magnetic iron oxide particles can be used. Specifically, magnetic iron oxide particles such as magnetite, maghemite, ferrite, and magnetic iron oxide particles containing other metal oxides can be mentioned. Conventionally, iron tetroxide (Fe 3 O 4 ), iron sesquioxide (γ-Fe 2 O 3 ), zinc ferrite (ZnFe 2 O 4 ), yttrium ferrite (Y 3 Fe 5 O 12 ), cadmium ferrite (Cd 3 Fe 2 O 4 ), gadolinium ferrite (Gd 3 Fe 5 O 12 ), copper ferrite (CuFe 2 O 4 ), lead ferrite (PbFe 12 O 19 ), nickel ferrite (NiFe 2 O 4 ), neodymium ferrite (NdFe 2 O 3 ), barium ferrite (BaFe 12 O 19 ), magnesium ferrite (MgFe 2 O 4 ), manganese ferrite (MnFe 2 O 4 ), lanthanum ferrite (LaFeO 3 ), iron powder (Fe), etc. are known. Particularly preferred magnetic iron oxide particles are fine powders of iron tetroxide or γ-iron sesquioxide. Also, the above-mentioned magnetic iron oxide particles can be selected and used alone or in combination of two or more kinds.

[0103] The shape of the magnetic iron oxide particles used in the toner of the present invention is more preferably an octahedron in which the dispersibility in the toner is better and the filler effect is more likely to be exhibited.

[0104] <Toner particle size> The toner of the present invention is not particularly limited in terms of its particle size, but better effects can be exerted in high-speed printing with large particles. The weight average particle size (D4) of the toner is preferably 10.0 μm or more and 20.0 μm or less, and more preferably 12.0 μm or more and 18.0 μm or less. When the toner particle size is within the above-described range, the electric field followability is improved and the dot reproducibility is enhanced.

[0105] <Softening point of the toner> The softening point of the toner of the present invention is preferably 70°C or more and 130°C or less. More preferably, it is 100°C or more and 120°C or less. When the softening point is within the above-described range, it is possible to suppress the excessive amount of the wax of the present invention on the image surface during image formation, and it is possible to achieve both low-temperature fixability and abrasion resistance of the printed matter.

[0106] <Method for manufacturing the toner> Regarding the toner of the present invention, its manufacturing method is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used.

[0107] Hereinafter, the toner manufacturing procedure by the pulverization method will be described.

[0108] In the raw material mixing step, as materials constituting the toner particles, for example, a binder resin, a wax, a colorant, and other components such as a charge control agent as required are weighed in predetermined amounts, blended, 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 & Engineering Co., Ltd.).

[0109] Next, the mixed materials are melt-kneaded to disperse waxes and the like in the binder resin. In this melt-kneading process, batch kneaders such as pressure kneaders and Banbury mixers, or continuous kneaders can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin-screw extruder (manufactured by K.C.K. Co., Ltd.), co-kneader (manufactured by Buss Co., Ltd.), Nidex (manufactured by Nippon Coke & Engineering Co., Ltd.), etc. can be mentioned. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling process.

[0110] Next, the cooled resin composition is pulverized to a desired particle size in the pulverization process. In the pulverization process, for example, after coarsely pulverizing with a pulverizer such as a crusher, hammer mill, or feather mill, it is further finely pulverized with a fine pulverizer such as a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industry), or an air jet type fine pulverizer.

[0111] After that, if necessary, it is classified using a classifier or sieve such as an elbow jet of the inertial classification method (manufactured by Nippon Steel Mining Co., Ltd.), a turbo plex of the centrifugal classification method (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), or a faculty (manufactured by Hosokawa Micron Corporation).

[0112] Furthermore, if necessary, an external additive is externally added to the surface of the toner particles. As a method of externally adding an external additive, a classified toner and various known external additives are blended in a predetermined amount, and a double con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, mechano hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Corporation), etc. are used as an external addition machine and stirred and mixed.

[0113] The measurement methods of various physical properties of toner particles and raw materials will be described below.

[0114] <Method for Separating Each Material from Toner> Each material contained in the toner can be separated from the toner by utilizing the difference in solubility of each material in a solvent. First Separation: Dissolve the toner (crystalline resin, wax, colorant, inorganic fine particles, etc.) in methyl ethyl ketone (MEK) at 100 °C, and separate the soluble components (crystalline resin, wax) from the insoluble components (colorant, inorganic fine particles, etc.). Second Separation: Dissolve the soluble components (crystalline resin, wax) obtained in the first separation in chloroform at 23 °C, and separate the soluble components (crystalline resin) from the insoluble components (wax).

[0115] <Method for Measuring the Ratio of Monomer Units Derived from Various Polymerizable Monomers in a Crystalline Resin> The measurement of the content ratio of monomer units derived from various polymerizable monomers in the crystalline resin is 1 performed by 1H-NMR under the following conditions. Measuring Device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring Frequency: 400 MHz Pulse Condition: 5.0 μs Frequency Range: 10500 Hz Number of Integrations: 64 times Measuring Temperature: 30 °C Sample: Put 50 mg of the measurement sample into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl 3 ) as a solvent, and dissolve it in a constant temperature bath at 40 °C for preparation.

[0116] Obtained 1 From the obtained 1H-NMR chart, for example, in the polymer, select a peak independent of the peaks attributed to the components of monomer units derived from other monomer units from among the peaks attributed to the components of the monomer units derived from the first polymerizable monomer, and calculate the integral value S 1 of this peak.

[0117] Similarly, from among the peaks attributed to the components of the monomer units derived from the second polymerizable monomer, a peak independent of the peaks attributed to the components of the monomer units derived from others is selected, and the integrated value S 2 of this peak is calculated.

[0118] Furthermore, when a third polymerizable monomer is used, from the peaks attributed to the components of the monomer units derived from the third polymerizable monomer, a peak independent of the peaks attributed to the components of the monomer units derived from others is selected, and the integrated value S 3 of this peak is calculated.

[0119] The content ratio of the monomer units derived from the first polymerizable monomer is determined as follows using the above integrated values S 1 , S 2 and S 3 . Here, n 1 , n 2、 n 3 is the number of hydrogens in the component to which the peak focused on for each site is attributed.

[0120] Content ratio (mol%) of the monomer units derived from the first polymerizable monomer = {(S 1 / n 1 ) / ((S 1 / n 1 ) + (S 2 / n 2 ) + (S 3 / n 3 ))} × 100 Similarly, the content ratios of the monomer units derived from the second polymerizable monomer and the third polymerizable monomer are determined as follows.

[0121] Content ratio (mol%) of the monomer units derived from the second polymerizable monomer = {(S 2 / n 2 ) / ((S 1 / n 1 ) + (S 2 / n 2 ) + (S 3 / n3 ))}×100 Content ratio (mol%) of monomer unit derived from the third polymerizable monomer = {(S 3 / n 3 ) / ((S 1 / n 1 )+(S 2 / n 2 )+(S 3 / n 3 ))}×100

[0122] In the case where a polymerizable monomer containing no hydrogen atom in a component other than a vinyl group is used in the above polymer, 13 Using C-NMR, the measured nuclear is 13 C, and measurement is performed in single pulse mode, 1 It is calculated in the same manner by H-NMR.

[0123] <Measurement of acid value of wax> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value is measured as follows in accordance with JIS K 0070-1992.

[0124] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution.

[0125] Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide gas, etc., leave it for 3 days, and then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the above potassium hydroxide solution is obtained from the amount of the above potassium hydroxide solution required for neutralization by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the above phenolphthalein solution, and titrating with the above potassium hydroxide solution. The above 0.1 mol / L hydrochloric acid is prepared in accordance with JIS K 8001-1998.

[0126] (2) Operation (A) This test Precisely weigh 2.0 g of the pulverized sample into a 200 mL Erlenmeyer flask, add 100 mL of a mixed solution of toluene / ethanol (2:1), and dissolve it over 5 hours. Then, add a few drops of the above phenolphthalein solution as an indicator and titrate with the above potassium hydroxide solution. Note that the end point of the titration is when the faint red color of the indicator persists for about 30 seconds.

[0127] (B) Blank test Perform the same titration as the above operation except without using a sample (i.e., using only the mixed solution of toluene / ethanol (2:1)).

[0128] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(C - B) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (mL), C: amount of potassium hydroxide solution added in this test (mL), f: factor of the potassium hydroxide solution, S: mass of the sample (g).

[0129] <Method for measuring the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of crystalline resin> <Method for measuring the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of wax> The peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of crystalline resin and the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of wax are measured in accordance with ASTM D3418 - 82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

[0130] For temperature correction of the device detection part, use the melting points of indium and zinc, and for heat quantity correction, use the heat of fusion of indium.

[0131] Specifically, accurately weigh approximately 3 mg of the sample, place it in an aluminum pan, and perform measurements under the following conditions using an empty aluminum pan as a reference. Heating rate: 10 °C / min Measurement start temperature: 30 °C Measurement end temperature: 180 °C

[0132] Perform measurements at a heating rate of 10 °C / min within the measurement range of 30 to 180 °C. First, heat up to 180 °C and hold for 10 minutes, then cool down to 30 °C, and then heat up again. In this second heating process, calculate the peak top temperature of the crystalline resin and wax from the temperature-endotherm curve in the temperature range of 30 °C to 150 °C.

[0133] <Softening point of crystalline resin, binder resin, and toner> The softening points of the crystalline resin, binder resin, and toner are measured using a capillary rheometer of the constant load extrusion type "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) in accordance with the manual attached to the device.

[0134] In this device, while applying a constant load from the top of the measurement sample with a piston, the measurement sample filled in the cylinder is heated to melt, and the melted measurement sample is extruded from the die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and temperature at this time is obtained.

[0135] In the present invention, the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Characteristic Evaluation Device Flow Tester CFT-500D" is used as the softening point. The melting temperature in the 1 / 2 method is calculated as follows. First, obtain 1 / 2 of the difference between the piston descent amount Smax at the end of the outflow and the piston descent amount Smin at the start of the outflow (let this be X. X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston descent amount in the flow curve becomes the sum of X and Smin is the melting temperature in the 1 / 2 method.

[0136] The measurement sample used is a cylindrical sample with a diameter of approximately 8 mm, which is obtained by compression molding 1.0 g of a binder resin at about 10 MPa for about 60 seconds using a tablet molding compression machine (NT-100H, manufactured by NPE Systems) at 25°C.

[0137] The measurement conditions of the CFT-500D are as follows. Test mode: Heating rate method Initial temperature: 30°C Final temperature: 200°C Measurement interval: 1.0°C Heating rate: 4.0°C / min Piston cross-sectional area: 1.000 cm 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Diameter of die hole: 1.0 mm Length of die: 1.0 mm

[0138] <Measurement of the weight average particle size (D4) of toner> The weight average particle size (D4) of the toner is measured with a precision particle size distribution measuring device "Coulter Counter Multisizer3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube and the dedicated software "Beckman Coulter Multisizer 3 Version3.51" (manufactured by Beckman Coulter) attached for setting measurement conditions and analyzing measurement data, at an effective measurement channel number of 25,000 channels, and the measurement data is analyzed and calculated.

[0139] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1 mass%, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0140] In addition, before measurement and analysis, the settings of the dedicated software are made as follows.

[0141] On the "Standard Measurement Method (SOM) Change Screen" of the dedicated software, set the total count of the control mode to 50,000 particles, the number of measurements to 1 time, and set the Kd value to the value obtained using "Standard Particle 10.0μm" (manufactured by Beckman Coulter). By pressing the measurement button for the threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.

[0142] On the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0143] The specific measurement method is as follows. (1) Pour about 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Flash" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Pour about 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottom glass beaker, and add about 0.3 mL of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant 3 times by mass with ion-exchanged water. (3) Put a predetermined amount of ion-exchanged water into the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a 180-degree phase shift, and add about 2 mL of the Contaminon N to this water tank. (4) Set the beaker in (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized. (5) With the electrolytic aqueous solution in the beaker of (4) irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so that it is 10°C or higher and 40°C or lower. (6) Using a pipette, the electrolytic aqueous solution in which the toner is dispersed in the round-bottom beaker of (1) installed in the sample stand is dropped, and adjusted so that the measured concentration is about 5%. Then, the measurement is carried out until the number of measured particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle diameter (D4). Note that when set to graph / volume% in the dedicated software, the "average diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle diameter (D4).

Example

[0144] The basic configuration and features of the present invention have been described above. Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited thereto.

[0145] <Production Example of Crystalline Resin 1> · Solvent: 100.0 parts by mass of toluene · Monomer composition: 100.0 parts by mass (The monomer composition is a mixture of behenyl acrylate·acrylonitrile·styrene shown below in the following ratios.) · Behenyl acrylate (first polymerizable monomer): 50.00 parts by mass · Acrylonitrile (second polymerizable monomer): 35.00 parts by mass · Styrene (third polymerizable monomer): 15.00 parts by mass · Polymerization initiator t-butylperoxypivalate (manufactured by NOF Corporation: Perbutyl PV): 0.5 part by mass Into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, the above materials were charged under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, it was heated to 70 °C and subjected to a polymerization reaction for 20 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after cooling the above solution to 24 °C, the above solution was charged into 1000.0 parts by mass of methanol while stirring to precipitate a methanol-insoluble component. The obtained methanol-insoluble component was filtered off, further washed with methanol, and then vacuum dried at 40 °C for 24 hours to obtain crystalline resin 1. The weight average molecular weight of crystalline resin 1 was 263700, and the peak top temperature of the temperature-endotherm curve was 61 °C.

[0146] <Production Examples of Crystalline Resins 2 to 17> In the production example of crystalline resin 1, the reaction was carried out in the same manner except that each polymerizable monomer and the number of parts were changed as shown in Table 1 to obtain crystalline resins 2 to 17.

[0147]

Table 1

[0148] <Production Example of Wax 1> ·Aliphatic hydrocarbon wax: 100 mol parts ·Mixture of boric acid and boric anhydride (boric acid mol parts / boric anhydride mol parts = 1.5): 2 mol parts The above aliphatic hydrocarbon wax (maximum endothermic peak temperature: 125.1 °C) was melted at a container temperature of 200 °C, the boric acid and boric anhydride mixture was added, and the wax was oxidized in an O 2 / N 2 gas with an oxygen concentration of 5% by volume. The oxidation treatment time was adjusted so as to obtain a desired acid value. After completion of the oxidation treatment, water was added and then purification was carried out to obtain Wax 1 having an acid value. The acid value of Wax 1 was 30 mgKOH / g, and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC) was 130 °C.

[0149] <Production Examples of Wax 2 to 6> In the production example of Wax 1, the reaction was carried out in the same manner except that the respective acid values and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC) were changed to those shown in Table 2 to obtain Wax 2 to 6.

[0150]

Table 2

[0151] <Production Example of Amorphous Resin 1> The monomers constituting the polyester unit used in producing Amorphous Resin 1 are listed below. · Bisphenol A ethylene oxide (2.2 mol adduct): 40.0 mol parts · Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts · Ethylene glycol: 20.0 mol parts · Terephthalic acid: 100.0 mol parts First, the above monomers were charged into a 5-liter autoclave together with 0.2 part by mass of titanium tetrabutoxide so that the amount was 95 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the polyester unit, and an aliphatic monoalcohol having 50 carbon atoms (a secondary monoalcohol having a hydroxyl group in paraffin wax, average value of carbon atoms: 50) was 5 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the polyester unit. Therein, a reflux condenser, a moisture separator, N 2A gas introduction tube, a thermometer, and a stirring device were attached, and N was placed in an autoclave. 2 While introducing N gas, a polycondensation reaction was carried out at 230 °C. When conducting the reaction, the reaction time was adjusted so as to obtain a desired softening point. After the reaction was completed, the resin was taken out from the container, cooled, and pulverized to obtain amorphous resin 1.

[0152] <Production Examples of Amorphous Resins 2 to 7> In the production example of amorphous resin 1, the reaction was carried out in the same manner except that each polymerizable monomer and the number of parts were changed as shown in Table 3 to obtain amorphous resins 2 to 7.

[0153]

Table 3

[0154] <Production Example of Magnetic Iron Oxide Particles 1> (First Reaction Step) Fe 2+ 16 L of an aqueous solution of ferrous sulfate containing 1.5 mol / L (Fe 2+ 24 mol) and 15.2 L of a 3.0 N sodium hydroxide solution (equivalent to 0.95 equivalents relative to Fe 2+ , i.e., 2OH / Fe = 0.95) were mixed and adjusted to pH 8.3 to prepare a ferrous salt suspension. At this time, as the silicon component, 26.6 g of No. 3 water glass (SiO 2 28.8 mass%) (equivalent to 0.50 atomic% in terms of Si relative to Fe, i.e., Si / Fe (atomic%) = 0.50) diluted in 0.5 L of ion-exchanged water was added to sodium hydroxide. The above ferrous salt suspension was aerated with 70 L of air per minute at a temperature of 90 °C, and the oxidation reaction was carried out until the oxidation reaction rate of the ferrous salt reached 12% to obtain a ferrous salt suspension containing magnetite nuclei particles.

[0155] (Second Reaction Step) An appropriate amount of a 3.0 N sodium hydroxide solution was added to the ferrous salt suspension containing the magnetite nuclei particles to adjust the pH to 10.5, and the mixture was aerated with 70 L of air per minute at a temperature of 90 °C to obtain magnetic iron oxide core particle precursor 1.

[0156] (Third reaction step + coating process) To the suspension containing the magnetic iron oxide core particle precursor 1, sodium silicate No. 3 as a silicon component and a 1.9 mol / L aluminum sulfate solution as an aluminum component were added in appropriate amounts so that Si / Fe and Al / Fe became the values shown in Table 4. Further, dilute sulfuric acid was added to adjust the pH to 5.8, and the temperature of the suspension was adjusted to 90 °C to form a coating layer, obtaining magnetic iron oxide 1.

[0157] The obtained magnetic iron oxide 1 was washed with water using a filter press. The electrical conductivity after washing with water was 40 mS. Further, it was filtered, dried, and pulverized by a conventional method. The obtained magnetic iron oxide 1 contained 8% of spherical magnetic iron oxide particles and 92% of octahedral magnetic iron oxide particles, and the number average particle diameter was 0.14 μm.

[0158] The adjustment conditions and composition values of magnetic iron oxide 1 are described in Tables 4 and 5.

[0159] <Production example of magnetic iron oxide particles 2>[ In the production example of magnetic iron oxide 1, magnetic iron oxide particles 2 were obtained by adjusting the production conditions as shown in Table 4. The composition values of the obtained magnetic iron oxide particles 2 are shown in Table 5.

[0160]

Table 4

[0161]

Table 5

[0162] 〔Example 1 (Production of toner 1)〕 · 60.0 parts by mass of crystalline resin 1 · 32.0 parts by mass of amorphous resin 1 · 8.0 parts by mass of wax 1 · 100.0 parts by mass of magnetic iron oxide particles 1 The raw materials shown in this formulation were used with a Henschel mixer (Model FM75J, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 20 s -1, after mixing for 5 minutes of rotation time, it was kneaded with a twin-screw kneader (Model TEM-26SS, Toshiba Machine Co., Ltd.) set at a temperature of 140°C and a barrel rotation speed of 250 rpm. The obtained kneaded product was cooled 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 with a mechanical pulverizer (Model T-250, manufactured by Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (Model 200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.

[0163] To 100.0 parts by mass of the obtained toner particles 1, 2.0 parts by mass of hydrophobic silica (BET: 200 m 2 / g) was mixed with a Henschel mixer (Model FM75J, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 30 s -1 , and mixed for 5 minutes of rotation time, and passed through an ultrasonic vibration sieve with an aperture of 54 μm to obtain toner 1.

[0164] 〔Examples 2 to 25 (Production of Toners 2 to 25), Comparative Examples 1 to 7 (Production of Toners 26 to 32)〕 In Example 1, except that the types and amounts of the crystalline resin, amorphous resin, wax, and magnetic iron oxide were changed to those described in Table 6, the toner was produced in the same manner to obtain toners 2 to 32.

[0165]

Table 6

[0166] Using each of the obtained toners 1 to 32, the following various evaluations were performed, and the results are shown in Table 7. Here, for all evaluations, the process speed of a commercially available copying machine was increased by modification, and the applicability to high-speed printing was confirmed.

[0167] [Evaluation of Low-Temperature Fixing Property] For this evaluation, a fixing device of a commercially available digital copying machine (image press 1135, manufactured by Canon Inc.) was taken out externally, and an evaluation machine was used in which the fixing roller temperature could be arbitrarily set and the process speed was modified to 1000 mm / s. It was carried out under normal temperature and normal humidity (23°C, 50%RH) environment. The evaluation paper was 157 g / m 2Paper (GF-C157, A4) was used. The developing bias of the image press 1135 was set so that the image density became 1.2, and nine solid black unfixed images were output. Then, the temperature control of the fuser was changed from 80 °C to 120 °C at 5 °C intervals, and the paper was passed one by one at each temperature. The fixed image was cut out to a size of 45 mm × 210 mm width, and it was folded in half so that the image part was inside from the center of the long side, and a load of 150 g / cm 2 (14.7 kPa) was applied. After rubbing the folding part with a brush, the density was measured and compared with the density before folding. The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500 Series). The value obtained by dividing the density after folding by the density before folding was plotted for each fixing temperature to create an approximate curve, and the temperature at which the value obtained by dividing the density after folding by the density before folding was 0.95 or more was defined as the fixable temperature.

[0168] (Evaluation Criteria) A: The fixable temperature is less than 95 °C. B: The fixing start temperature is 95 °C or more and less than 100 °C. C: The fixing start temperature is 100 °C or more and less than 105 °C. D: The fixing start temperature is 105 °C or more and less than 110 °C. E: The fixing start temperature is 110 °C or more.

[0169] [Evaluation of Abrasion Resistance (Scratch Resistance) of Printed Images] For this evaluation, an evaluation machine in which the process speed of a commercially available digital copying machine (image press 1135 manufactured by Canon Inc.) was modified to 1000 mm / s and the fixing temperature control was modified to 120 °C was used. The evaluation paper was 157 g / m 2 Paper (GF-C157, A4) was used. The developing bias was set so that the image density became 1.0, and a solid black image was output. Using a tribogear TYPE40 friction and wear tester manufactured by Shinto Kagaku Co., Ltd., the output image was rubbed while applying a load with an unused evaluation paper, and the amount of toner adhering to the rubbing paper was evaluated. The rubbing conditions were as follows. Weight: 500 g Contact area with rubbing paper: 2 mm × 20 mm Rubbing speed: 1000 mm / min Rubbing distance: 40 mm

[0170] The evaluation of the toner adhesion amount on the rubbing paper was carried out as follows. Using an optical microscope image, multiple 100x magnification photos were taken so that the entire rubbing area was included. The captured images were binarized by image processing to calculate the area ratio of the adhered part. The average value of the adhered part area ratios of all the captured photos was taken as the toner adhesion amount.

[0171] (Evaluation criteria) A: The adhesion area ratio is less than 1.5%. B: The adhesion area ratio is 1.5% or more and less than 2.5%. C: The adhesion area ratio is 2.5% or more and less than 3.5%. D: The adhesion area ratio is 3.5% or more and less than 4.0%. E: The adhesion area ratio is 4.0% or more.

[0172] [Evaluation of member contamination suppression] For this evaluation, an evaluation machine was used in which the process speed of a commercially available digital copying machine (Image Press 1135, manufactured by Canon Inc.) was set to 1000 mm / s, the fixing temperature control was set to 120 °C, and the cleaning mechanism of the fixing roller was removed and modified. The evaluation paper used was 157 g / m 2 paper (GF-C157, A4). The developing bias was set so that the image density became 1.0, and a pattern with a width of 45 mm was output in the short-axis direction of the A4 paper, and 5000 images were output in a high-temperature and high-humidity (30 °C, 80% RH) environment. After that, the fixing roller was removed, and the wax adhesion amount on the fixing roller corresponding to the image pattern was evaluated using a Fourier transform infrared spectroscopic analyzer. The details of the evaluation method are described below. Fourier transform infrared spectroscopic analyzer: Spectrum One (manufactured by PerkinElmer) Measurement mode: ATR method Incident angle of infrared light (λ = 5 μm): 45° ATR crystal: Ge (refractive index: 4.0) Measurement range: 4000 cm -1 to 600 cm-1 Obtained wavelength width: 4.00 cm -1 Number of integrations: 16

[0173] The infrared absorption spectrum obtained under the above conditions is subjected to baseline correction by Automatic Correction. The maximum value of the peak intensity in the range of 2800 cm -1 ~2900 cm -1 derived from the methylene of hydrocarbon wax is calculated (Wp). The average value of the absorption intensities at 1100 cm -1 and 1250 cm -1 derived from the surface layer member of the fixing roller is calculated (Bp). The value of Wp / Bp is taken as the wax adhesion amount.

[0174] (Evaluation criteria) A: Wp / Bp is less than 0.01%. B: Wp / Bp is 0.01% or more and less than 0.02%. C: Wp / Bp is 0.02% or more and less than 0.04%. D: Wp / Bp is 0.04% or more and less than 0.08%. E: Wp / Bp is 0.08% or more

[0175] [Evaluation of developability (dot reproducibility)] For this evaluation, an evaluation machine in which the process speed of a commercially available digital copier (image RUNNER ADVANCE 8105 PRO, manufactured by Canon Inc.) was modified to 600 mm / s was used. Using each magnetic toner, after 100,000 sheets of durability in a high temperature and high humidity (30°C, 80% RH) environment, a halftone (30H) image was formed, and the coarseness of this image was evaluated based on the following criteria. The paper used was CS-068 A4 paper (basis weight 68.0 g / m 2, it was used for sales by Canon Marketing Japan Inc. The 30H image is a value obtained by displaying 256 gradations in hexadecimal. When 00H is solid white (non-image) and FFH is solid black (full-image), it is a halftone image. The image was measured for an area of 1000 dots using a digital microscope VHX-500 (lens wide-range zoom lens VH-Z100 manufactured by Keyence Corporation). The average number (S) of dot areas and the standard deviation (σ) of dot areas were calculated, and the dot reproducibility index was calculated by the following formula. Dot reproducibility index (I) = σ / S × 100

[0176] (Evaluation criteria) A: I is less than 2.0 B: I is 2.0 or more and less than 4.0 C: I is 4.0 or more and less than 6.0 D: I is 6.0 or more and less than 8.0 E: I is 8.0 or more

[0177]

Table 7

Claims

1. A toner having toner particles containing a binder resin and a hydrocarbon wax, wherein the binder resin contains a crystalline resin, the crystalline resin has a weight-average molecular weight of the tetrahydrofuran-soluble content measured by gel permeation chromatography of 200,000 or more and 1,000,000 or less, the crystalline resin satisfies the following requirement (I) or (II), (I): (I-i) a first monomer unit represented by the following formula (1), and (I-ii) a second monomer unit selected from the group consisting of acrylonitrile units, methacrylonitrile units, vinyl acetate units, and acrylic acid units and has, (I-iii) the total of the first monomer unit and the second monomer unit is 100% by mass based on the total mass of all monomer units of the crystalline resin, (II): (II-i) a first monomer unit represented by the following formula (1), (II-ii) a second monomer unit selected from the group consisting of acrylonitrile units, methacrylonitrile units, vinyl acetate units, and acrylic acid units, and (II-iii) a third monomer unit which is a styrene unit and has, (II-iv) the total of the first monomer unit, the second monomer unit, and the third monomer unit is 100% by mass based on the total mass of all monomer units of the crystalline resin, the proportion of the first monomer unit in the crystalline resin is 20.0% by mass or more and 70.0% by mass or less based on the total mass of all monomer units of the crystalline resin, the proportion of the second monomer unit in the crystalline resin is 20.0% by mass or more and 70.0% by mass or less based on the total mass of all monomer units of the crystalline resin, the hydrocarbon wax has a carboxylic acid group and an acid value of 5 mgKOH / g or more and 50 mgKOH / g or less, and the toner is characterized by this. 【Chemical Formula 1】 (In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1 represents a linear alkyl group having 18 to 36 carbon atoms.)

2. The toner according to claim 1, wherein the content of the hydrocarbon wax contained in the toner particles is 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

3. The toner according to claim 1 or 2, wherein the first monomer unit is behenyl acrylate.

4. The binder resin contains an amorphous polyester, the amorphous polyester, (i) has a softening point of 85°C or more and 105°C or less, The toner according to any one of claims 1 to 3, wherein at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid and an aliphatic monoalcohol is condensed at the end.

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