JP2016224114A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can achieve both a tinting power and light resistance at a high level.SOLUTION: There is provided a toner comprising toner particles including a binder resin, crystalline resin, and colorant, wherein the crystalline resin has a half value (ΔTc) of an exothermic peak in a spectrum of 5.0°C or less in differential scanning calorimetry (DSC), the half value obtained when the crystalline resin is heated to 150°C and subsequently cooled at a temperature drop rate of 10°C/min.; the colorant includes a compound represented by formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and a toner jet method.

Currently, power saving is demanded in copying machines and printers.
As a method for saving power, there is a reduction in power by lowering the temperature at the time of thermal fixing of toner in an electrophotographic process. For this purpose, it is effective to reduce the amount of toner on paper, and to reduce the amount of toner, it is necessary to increase the coloring power of the toner.

An example of a colorant for improving the coloring power of the toner is to use a colorant (dye) having high solubility in a resin.
When a dye is used as a toner colorant, the entire resin constituting the toner is colored. Therefore, the dye has been used as an effective means for improving the coloring power.

For example, in Patent Document 1, the coloring power can be improved by using a dye.
However, generally, when a dye is used, the light resistance is a problem. This is because the dye is easily affected by ultraviolet rays in the image after printing because the dye is dispersed in the toner resin at a molecular level.

  In Patent Document 2, the light resistance is improved by improving the dye. As a result, both coloring power and light resistance can be achieved.

JP 2013-137443 A JP 2014-63156 A

  However, in recent years, a higher level of coloring power and light resistance have been demanded, and the toner described in Patent Document 2 has room for improvement in both coloring power and light resistance. SUMMARY An advantage of some aspects of the invention is that it provides a toner that can achieve both high coloring strength and light fastness.

（式（１）中、Ｒ^１、Ｒ^２、およびＲ^３は、各々独立して、水素原子または炭素数１以上５以下であるアルキル基を表わし、Ａｒはアリール基を表わす） The present invention is a toner having toner particles containing a binder resin, a crystalline resin and a colorant, wherein the half-value width (ΔTc) of the exothermic peak of the crystalline resin is 5.0 ° C. or less (ΔTc is In the differential scanning calorimetry (DSC), the full width at half maximum of the exothermic peak of the spectrum obtained when the crystalline resin is heated to 150 ° C. and then cooled at a cooling rate of 10 ° C./min.), The colorant. Relates to a toner comprising a compound represented by the following formula (1).

(In Formula (1), R ¹ , R ² , and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar represents an aryl group)

  As described above, according to the present invention, it is possible to provide a toner having both a high level of coloring power and light resistance.

Embodiments of the present invention will be specifically described below.
As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have found that a toner having toner particles containing a crystalline resin having high crystallinity and a compound represented by the above formula (1) has high coloring. It has been found that the effect of strength and light resistance is manifested. That is, in differential scanning calorimetry (DSC), the half-value width (ΔTc) of the exothermic peak of the spectrum obtained when heated to 150 ° C. and then cooled at a temperature decrease rate of 10 ° C./min is 5.0 ° C. or less. It has been found that in a toner (yellow toner) having toner particles containing a crystalline resin and a colorant containing a compound represented by the above formula (1), both a high level of coloring power and light resistance can be achieved.

  As described in the background, the compound of the above formula (1) has high solubility in an organic solvent and is uniformly dispersed in the toner resin. Therefore, the compound is effective for improving the coloring power.

（式（１）中、Ｒ^１、Ｒ^２、およびＲ^３は、各々独立して、水素原子または炭素数１以上５以下であるアルキル基を表わし、Ａｒはアリール基を表わす） The colorant used in the present invention is characterized by having a compound represented by the formula (1). When the compound represented by the formula (1) is used, the entire resin constituting the toner is colored, so that a high level of coloring power can be obtained. As the compound represented by the formula (1), a compound synthesized by a method described later can be used, and a known colorant can be used.
As a known colorant, solvent yellow 162, disperse yellow 114, 231 and the like can be used.

(In Formula (1), R ¹ , R ² , and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar represents an aryl group)

  On the other hand, a crystalline resin having high crystallinity generally tends to have a high refractive index. A material having a high refractive index has strong scattering and absorption in the ultraviolet region. As a result, when the toner in the image after heat fixing is irradiated with light including ultraviolet light such as sunlight, the crystallized crystalline resin is considered to scatter and absorb ultraviolet light. In this way, it is estimated that the light resistance is improved by protecting the colorant in the image from ultraviolet rays.

  In differential scanning calorimetry (DSC), the half-value width (ΔTc) of the exothermic peak of the spectrum obtained when heating to 150 ° C. and then cooling at a rate of temperature decrease of 10 ° C./min is the crystallization rate of the crystalline resin. And is considered to be an index of crystallinity. That is, it is suggested that the smaller the ΔTc, the faster the crystallization speed and the higher the crystallinity. When the crystallization speed is high, the crystallized quickly immediately after heat fixing, so that the crystalline resin can exist in a crystallized state in the fixed image. When the degree of crystallinity is high, the number of crystallized portions of the added crystalline resin tends to increase, so that the amount of crystallized crystalline resin in the fixed image increases. Therefore, as ΔTc is smaller, the above-described mechanism protects the colorant from ultraviolet rays and improves light resistance. Therefore, the smaller ΔTc of the crystalline resin is preferable. However, since a crystalline resin having extremely high crystallinity tends to be very expensive, it is practically preferable to use a resin having ΔTc of 1.0 ° C. or higher.

On the other hand, when ΔTc is large, it suggests that the crystallization speed is slow and the degree of crystallization is low, and the crystalline resin in the fixed image hardly exists in a crystallized state, and the amount crystallized is small. Conceivable. Therefore, when a crystalline resin having a ΔTc of greater than 5.0 ° C. is used, it is difficult to obtain an excellent light resistance effect. From the above, in order to obtain the effect of the present invention, ΔTc needs to be 5.0 ° C. or less.
Therefore, ΔTc is preferably 1.0 ° C. or higher and 5.0 ° C. or lower. ΔTc can be controlled by changing the monomer composition of the crystalline resin, the molecular weight of the crystallinity, or the like.

  The crystalline resin is preferably 0.5% by mass or more and 30.0% by mass or less based on the total amount of the binder resin and the crystalline resin. When the crystalline resin is 0.5% by mass or more with respect to the total amount of the binder resin and the crystalline resin, a sufficient amount for expressing the light resistance effect is secured, and the light resistance is easily improved. When the content is 30.0% by mass or less, the dispersibility after fixing is easily maintained, and the light resistance is easily improved. More preferably, it is 3.0 mass% or more and 20.0 mass% or less.

（式（２）中、ｍは４乃至１０の整数であり、ｎは６乃至１２の整数である。） The crystalline resin preferably has a structural unit represented by the following formula (2).

(In Formula (2), m is an integer of 4 to 10, and n is an integer of 6 to 12.)

  When m in the formula (2) is 4 or more and n is 6 or more, the crystallinity of the crystalline resin is increased, and the light resistance is easily improved. When m in the formula (2) is 10 or less and n is 12 or less, the compatibility with the binder resin is improved, and the light resistance is easily improved by improving the dispersibility in the image after fixing. Become.

The crystalline resin having a structural unit represented by the above formula (2) further has a terminal structure derived from an aliphatic carboxylic acid represented by the following formula (3) or an aliphatic alcohol represented by the following formula (4). More preferably.
Equation _{(3) H 3 C- (CH} 2) o -COOH
(In formula (3), o is an integer of 5 to 17.)
Equation _{(4) H 3 C- (CH} 2) p -OH
(In formula (4), p is an integer of 6 to 18.)

  When o in Formula (3) and Formula (4) is 5 or more and p is 6 or more, the crystallinity of the crystalline resin is increased, and light resistance is easily improved. When o in the formulas (3) and (4) is 17 or less and p is 18 or less, the compatibility with the binder resin is improved, and the dispersibility in the image after fixing is improved. It becomes easy to improve property. More preferably, o is an integer from 5 to 11, and p is an integer from 6 to 12.

  When the crystalline resin having the structural unit represented by the above formula (2) is produced with an acid and an alcohol such as the formula (3) and the formula (4), the above formula (3) or A long-chain alkyl moiety derived from the above formula (4) can be introduced. Thus, when there is a long-chain alkyl moiety at the terminal of the crystalline resin, the long-chain alkyl moiety serves as a nucleation site when crystallization occurs, and the crystallization speed can be improved and ΔTc can be reduced. As a result, the light resistance is further improved.

  In the differential scanning calorimetry (DSC) of the crystalline resin, when the endothermic peak of the spectrum obtained when heated from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min is taken as the melting point (Tm), the melting point (Tm) is preferably 50 ° C. or higher and 90 ° C. or lower. When the melting point is 50 ° C. or higher, the crystallinity of the crystalline resin tends to increase, and the light resistance is easily improved. When the melting point is 90 ° C. or lower, it is easy to dissolve during heat fixing, so that the compatibility becomes high, and the light resistance is easily improved by dispersing the crystalline resin in the image. A more preferable range of the melting point is 55 ° C or higher and 85 ° C or lower. The melting point of the crystalline resin can be controlled by changing the monomer composition.

  The crystalline resin preferably has a weight average molecular weight (Mw) measured using size exclusion chromatography (GPC) of 5000 or more and 30000 or less. When it is 5000 or more, the crystallinity is easily improved, so that the light resistance is easily improved. When it is 30000 or less, it is easily compatible with the binder resin, so that dispersibility in the image is improved and light resistance is easily improved. The Mw of the crystalline resin can be controlled by changing the reaction time, reaction temperature, or monomer charge ratio during production. The weight average molecular weight (Mw) of the crystalline resin is more preferably 7500 or more and 25000 or less.

  The toner preferably further contains a hydrocarbon-based release agent. Light resistance is further improved by using a hydrocarbon-based release agent for the toner. As a result of various studies by the present inventors, it has been found that the crystallization speed is improved when the toner particles containing the crystalline resin contain a hydrocarbon release agent. This is presumed to be because the crystallization speed of the hydrocarbon-based release agent is higher than the nucleation speed of the crystal part compared to other toner materials. As a result, it is considered that the crystallizing resin is crystallized by using the hydrocarbon-based release agent as a nucleation site, thereby increasing the crystallization speed and further improving the light resistance.

  Examples of hydrocarbon release agents that can be used in the present invention include low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.

Moreover, you may use together 1 type, or 2 or more types of the following mold release agents as needed. Examples include the following:
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate wax; and deoxidation The fatty acid esters such as carnauba wax may be partially or wholly deoxidized. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as pracidic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscaprin Saturated fatty acid bisamides such as acid amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl Unsaturated fatty acid amides such as dipinamide, N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylenebisstearic acid amide, N, N-distearylisophthalic acid amide; calcium stearate, laur Grafted with fatty acid metal salts such as calcium phosphate, zinc stearate, magnesium stearate (generally called metal soap), and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples of waxes include partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.
The addition amount of the release agent is preferably 0.5 parts by mass or more and 30 parts by mass or less, and more preferably 1.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the resin.

  The toner preferably further contains a fatty acid metal salt. When the toner further contains a fatty acid metal salt, the light resistance is further improved. This is considered to be the same mechanism as the light resistance by the hydrocarbon release agent. That is, it is considered that the light resistance is further improved by adding a fatty acid metal salt in advance as a nucleation site serving as a crystal nucleus.

  Examples of fatty acid metal salts that can be used in the present invention include calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, lithium stearate, sodium stearate, calcium montanate, zinc montanate, magnesium montanate. , Aluminum montanate, lithium montanate, sodium montanate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, sodium behenate, calcium laurate, zinc laurate, barium laurate and lithium laurate It is done.

  The addition amount of the fatty acid metal salt is preferably 0.05% by mass or more and 3.0% by mass or less with respect to the total amount of the binder resin and the crystalline resin.

  The content of the compound represented by the formula (1) is preferably 0.5% by mass or more and 10.0% by mass or less with respect to the total amount of the binder resin and the crystalline resin. When it is 0.5% by mass or more, the effect of the compound represented by the formula (1) is easily exhibited, and the coloring power is easily improved. When the content is 10.0% by mass or less, the effect of deterioration of light resistance by the compound represented by the formula (1) is reduced, and the light resistance is easily improved.

（式（５）中、Ｒ^１、Ｒ^２およびＲ^３は、各々独立して、水素原子または炭素数１以上５以下であるアルキル基を表わし、Ｒ^４およびＲ^５は、各々独立して、水素原子または炭素数１以上１２以下のアルキル基を表わす。） The compound represented by the formula (1) is preferably a compound represented by the following formula (5).

(In Formula (5), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ are each independently Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

  If it is a compound (structure) represented by this Formula (5), since the light resistance of a coloring agent itself will improve, light resistance will improve further.

The compound represented by the formula (1) used in the present invention can be combined with a general yellow pigment. Particularly effectively, C.I. I. This is a case where it is used in combination with CI Pigment Yellow 74, 93, 120, 151, 155, 180, 185, 213 or the like. These pigments may be used alone or in combination of two or more.
The amount of yellow pigment added is preferably in the range of 0.5 to 15.0 parts per 100 parts of resin. Particularly preferred is 1.0 part or more and 10.0 parts or less.

“Crystallinity” in the present invention refers to having a clear endothermic peak in differential scanning calorimetry (DSC), not a stepwise endothermic change.
Even if the crystalline resin is in the form of a graft body or a block body having a crystalline part and an amorphous part, it may have a clear endothermic peak in differential scanning calorimetry (DSC). Is also contained in the crystalline resin.

  The “binder resin” in the present invention refers to a resin having a molecular weight distribution of 2,000 or more in a molecular weight distribution measured using size exclusion chromatography (GPC).

  As the binder resin used in the toner of the present invention, known resins such as a styrene vinyl resin, a maleic acid copolymer, a polyester resin, and an epoxy resin can be used.

  As the polymerizable monomer constituting the styrene vinyl resin, a vinyl polymerizable monomer capable of radical polymerization can be used. Examples of the vinyl polymerizable monomer include monofunctional polymerizable monomers and polyfunctional polymerizable monomers.

Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 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, p-methoxy styrene, and , Styrene derivatives such as p-phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Acrylic polymerizable monomers such as N, nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Methacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, Examples include 2,2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  Monofunctional polymerizable monomers alone or in combination of two or more, or a combination of monofunctional polymerizable monomers and polyfunctional polymerizable monomers, or polyfunctional polymerizable Monomers can be used alone or in combination of two or more.

  As the polycondensation monomer constituting the polyester resin, polyvalent carboxylic acid and polyol can be used.

As polyvalent carboxylic acid,
Oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, di Glycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p -Carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4 -Dicarboxylic acid, naphthalene-1,5- Carboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexane dicarboxylic acid and the like. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.

As a polyol,
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 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, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-buta Triol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide addition And hydrogenated bisphenol A propylene oxide adduct and the like.

  The crystalline resin that can be used in the present invention is preferably a polyester having a structural unit represented by the formula (2) by condensation polymerization of a divalent acid and a divalent alcohol. When the crystalline resin is a polyester, examples of preferable divalent acids include alkanedicarboxylic acids (for example, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid). , Octadecane dicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.), alkene dicarboxylic acid (eg maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl) Succinic acid, dimer acid, etc.), aromatic dicarboxylic acids (eg, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). These may be used in the form of acid anhydrides and alkyl esters.

  Preferred divalent alcohols include alkylene glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3- Propanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and spiroglycol, etc.), alkylene ether glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol, etc.), bisphenols (bisphenol A, Phenol F, bisphenol S, bisphenol A · ethylene oxide 2 mole adduct, bisphenol A · propylene oxide 2.5 mol adduct), and the like.

A divalent acid and a divalent alcohol can be used singly or in combination of two or more.
Of these divalent acids and divalent alcohols, alkanedicarboxylic acids and alkylene glycols that produce polyesters having high crystallinity are preferred.

  In addition, a terminal sealing agent may be used as the crystalline resin. By using a terminal blocking agent, it is possible to adjust the molecular weight, acid value, hydroxyl value, crystallinity, etc. of the crystalline polyester. For example, examples of the end capping agent include monovalent acids and derivatives thereof, and monovalent alcohols.

  Specifically, monovalent acids and derivatives thereof include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, stearic acid, benzoic acid and These acid anhydrides are mentioned. Among them, preferred are hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, stearic acid and acid anhydrides thereof represented by the formula (3). The acid anhydride may be an acid anhydride in which monovalent acids are condensed with each other, or a mixed acid anhydride in which two kinds of acids form an acid anhydride.

  Examples of the monovalent alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, stearyl alcohol and the like. Among these, heptanol, octanol, nonanol, decanol, lauryl alcohol, and stearyl alcohol represented by the formula (4) are preferable.

  In the condensation reaction, a known esterification catalyst such as a tin compound or a titanium compound may be used as necessary.

  In the present invention, the manufacturing method for manufacturing the toner particles may be any manufacturing method. For example, a suspension polymerization method in which a polymerizable monomer for obtaining a binder resin and a solution of a colorant, a release agent and the like are suspended in an aqueous solvent for polymerization; various toner constituent materials are kneaded, pulverized, Kneading and pulverizing method for classifying; emulsifying and aggregating method in which a dispersion obtained by emulsifying and dispersing a binder resin and a dispersion such as a colorant and a release agent are mixed and agglomerated and heat-fused to obtain toner particles; Emulsion polymerization of the polymerizable monomer of the binder resin, and the formed dispersion and, if necessary, a dispersion of a colorant, a release agent, etc., are mixed, agglomerated, and heat-fused to form toner particles. An emulsion polymerization aggregation method to be obtained; a solution suspension method in which a binder resin and a solution of a colorant, a release agent, etc. are suspended in an aqueous solvent and granulated; can be used.

  Hereinafter, the measurement method of various physical properties according to the present invention will be described.

<Measurement method of molecular weight>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin and polymer are measured using gel permeation chromatography (GPC) as follows.
First, a resin or polymer is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (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 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Equipment: High-speed GPC equipment “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: Duplex of LF-604 [manufactured by Showa Denko KK]
Eluent: THF
Flow rate: 0.6 ml / min Oven temperature: 40 ° C
Sample injection amount: 0.020 ml
In calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement Method of Half-width (ΔTc) and Melting Point (Tm) of Exothermic Peak>
The half width (ΔTc) and melting point (Tm) of an exothermic peak of a crystalline resin or the like are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. The measurement is performed by heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, and then cooling to 0 ° C. at a temperature lowering rate of 10 ° C./min. At that time, the half-value width (ΔTc) of the exothermic peak of the obtained DSC curve is obtained. Thereafter, heating is performed again at a temperature rising rate of 10 ° C./min. The peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 0 ° C. to 150 ° C. in the second heating process is defined as the melting point (Tm).

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner was measured using a Coulter Multisizer (manufactured by Coulter), and connected to an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC). Measure according to the operation manual. Specifically, a 1% NaCl aqueous solution is prepared using primary sodium chloride as the electrolyte. As the electrolytic solution, commercially available ISOTON R-II (manufactured by Coulter Scientific Japan Co., Ltd.) can also be used. To 100 ml of the electrolytic aqueous solution, 5 mg of a measurement sample (toner) and 0.1 ml of a contamination aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) are added. The electrolyte in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the volume and number of toner particles of 2.0 μm or more are measured with the Coulter Multisizer using a 100 μm aperture, and the number average particle diameter is measured. (D4) is obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

上記スキームに従いアミン化合物（Ａ１）０．７２１ｇのメタノール（ＭｅＯＨ）２０ｍＬ溶液を５℃に冷却し、濃硫酸２ｍＬ、ニトロシル硫酸（４０質量％）１．４ｍＬを滴下した（ジアゾ化Ａ液）。また別途、ピリドン化合物（Ｐ１）０．４９６ｇのメタノール（ＭｅＯＨ）２０ｍＬ溶液を５℃に冷却し、これにジアゾ化Ａ液を５℃以下の温度に保持されるようにゆっくりと滴下し、氷浴中で２０分撹拌した。反応終了後、炭酸ナトリウム水溶液を滴下し、ｐＨを６に中和した後、クロロホルムで抽出した。その後、溶媒を留去して得られた固体をカラムクロマトグラフィーにより精製（展開溶媒：ヘプタン／酢酸エチル）し、さらにヘプタン溶液で再結晶して０．８ｇの上記式（Ｓ１）の構造の着色剤１を得た。
尚、得られた着色剤１の同定は、ＭＡＬＤＩ ＭＳ（ａｕｔｏｆｌｅｘ装置、ブルカー・ダルトニクス社製）を用いた分析方法によって行った。ＭＡＬＤＩ ＭＳにおいて検出イオンはネガティブモードを採用した。
ＭＡＬＤＩ ＭＳによる質量分析：ｍ／ｚ＝６１８．６１２（Ｍ−Ｈ）− <Synthesis Example of Colorant 1>
A colorant 1 having a structure represented by the following formula (S1) was obtained.

According to the above scheme, a solution of amine compound (A1) 0.721 g in methanol (MeOH) in 20 mL was cooled to 5 ° C., and 2 mL of concentrated sulfuric acid and 1.4 mL of nitrosylsulfuric acid (40 mass%) were added dropwise (diazotized A solution). Separately, a solution of 0.496 g of pyridone compound (P1) in 20 mL of methanol (MeOH) is cooled to 5 ° C., and the diazotized solution A is slowly added dropwise to the solution so that the temperature is kept at 5 ° C. or lower. Stir in for 20 minutes. After completion of the reaction, an aqueous sodium carbonate solution was added dropwise to neutralize the pH to 6, followed by extraction with chloroform. Thereafter, the solid obtained by distilling off the solvent was purified by column chromatography (developing solvent: heptane / ethyl acetate), and further recrystallized with a heptane solution to give 0.8 g of the structure of the above formula (S1). Agent 1 was obtained.
The obtained colorant 1 was identified by an analysis method using MALDI MS (autoflex apparatus, manufactured by Bruker Daltonics). In MALDI MS, a negative mode was adopted as a detection ion.
Mass spectrometry by MALDI MS: m / z = 618.612 (M−H) −

<Synthesis Example of Colorant 2>
Except having changed the pyridone compound (P1) into the pyridone compound (P2) shown below, the colorant 2 having the structure of the following formula (S2) was obtained in the same manner as the synthesis example of the colorant 1.

<Synthesis Example of Colorant 3>
Except that the amine compound (A1) is changed to the amine compound (A3) shown below, and the pyridone compound (P1) is changed to the pyridone compound (P3) shown below, the following formula is used. A colorant 3 having a structure of (S3) was obtained.

<Synthesis Example of Colorant 4>
Except that the amine compound (A1) is changed to the amine compound (A4) shown below, and the pyridone compound (P1) is changed to the pyridone compound (P4) shown below, the following formula is used. A colorant 4 having a structure of (S4) was obtained.

<Synthesis Example of Colorant 5>
Except that the amine compound (A1) is changed to the amine compound (A5) shown below, and the pyridone compound (P1) is changed to the pyridone compound (P5) shown below, the following formula is used. A colorant 5 having a structure of (S5) was obtained.

<Example of production of crystalline resin 1>
Add 100.0 parts by mass of sebacic acid and 87.2 parts by mass of 1,9-nonanediol to a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device, and stir. While heating to 130 ° C. After adding 0.7 parts by mass of titanium (IV) isopropoxide as an esterification catalyst, the mixture was heated to a temperature of 160 ° C. and subjected to condensation polymerization for 5 hours. Then, it was made to react until it became desired molecular weight, heating at the temperature of 180 degreeC and reducing pressure. Thereafter, 6.6 parts by mass of lauryl alcohol was added and reacted at 160 ° C. for 3 hours to obtain a crystalline resin 1.
The weight average molecular weight (Mw) of the crystalline resin 1 measured according to the method described above was 23000, the melting point (Tm) was 68 ° C., and the half-value width (ΔTc) of the exothermic peak was 2.6 ° C. The properties of the crystalline resin 1 are shown in Table 1.

<Production example of crystalline resins 2 to 11>
According to the production example of the crystalline resin 1, the properties were adjusted as shown in Table 1 to obtain crystalline resins 2 to 11.

<Production Example of Toner 1>
[Preparation Step of Colorant Dispersion 1]
-Styrene (St) monomer 270 parts by mass-N-butyl acrylate (BA) monomer 90 parts by mass-Polar resin 20 parts by mass (a copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14800, Tg = 89 ° C, acid value AV = 22 mgKOH / g, hydroxyl value OHv = 8 mgKOH / g)
Colorant 1 16 parts by mass Pigment Yellow 155 (PY155) 20 parts by mass (Toner Yellow 4G: Clariant)
The above material was introduced into an attritor (Mitsui Miike Chemical Co., Ltd.) and stirred for 180 minutes at 200 rpm and 25 ° C. using zirconia beads (200 parts) with a radius of 2.5 mm to prepare a colorant dispersion 1 did.

[Toner Composition Solution Preparation Process]
-Colorant dispersion 1 312 parts by mass-Crystalline resin 1 15 parts by mass-Hydrocarbon wax 21 parts by mass (Fischer-Tropsch wax; HNP-9)
・ 3 parts by mass of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)]
The above materials are mixed, heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to dissolve the toner composition. A liquid was obtained.

[Toner particle dispersion adjustment process]
In a 2 liter four-necked flask equipped with a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 900 parts by mass of ion-exchanged water and 150 parts by mass of 0.5M-Na ₃ PO ₄ aqueous solution. After adding 6.5 parts by mass of a 10% -hydrochloric acid aqueous solution, the TK homomixer was adjusted to 12,000 rpm and heated to 60 ° C. Thereafter, 6.5 parts by mass of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound.

Next, 25 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate is dissolved in the toner composition solution, and after sufficiently mixing, It poured into the aqueous medium. This was measured at a temperature of 62 ° C. under N ₂ atmosphere. K. The polymerizable monomer composition was granulated by stirring for 10 minutes at 12,000 rpm with a homomixer. Then, it heated at the temperature of 75 degreeC, stirring with a paddle stirring blade, and reaction was completed by performing superposition | polymerization for 7.5 hours. Next, the remaining solvent was distilled off under reduced pressure, and the aqueous medium was cooled to obtain a toner particle dispersion. The obtained toner particles had a weight average particle size (D4) of 6.3 μm.

Hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. This was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Next, ion-exchanged water was added to the pressure filter until it was full, and washing was performed by performing solid-liquid separation at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles. 1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added to 100 parts by mass of the obtained toner particles, and a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.) is added. Toner 1 was obtained through a mixing process for 300 seconds.
The toner particle composition of toner 1 is shown in Tables 2 and 3. Note that the polar resin used in the production example of the toner 1 is included as a binder resin.

<Production Examples of Toners 2 to 22 and Comparative Toners 1 to 3>
Toners 1 to 22 and comparative toners 1 to 3 were obtained in the same manner except that the composition of toner 1 was changed as shown in Tables 2 and 3 in the toner 1 production example. The toner particle compositions of toners 2 to 22 and comparative toners 1 to 3 are shown in Tables 2 and 3.
The trade name “C105”, which is a release agent used for the production of the toner particles 5 in Table 3, is a coal-based Fischer-Tropsch wax having an endothermic peak temperature of 105 ° C. manufactured by Sazol.

<Production example of toner 23>
[Synthesis of Amorphous Resin A]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 76.9 parts (0.167 mol%), terephthalic acid 24.1 parts (0.145 mol%), and titanium tetra 0.5 part of butoxide was put into a glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the mixture was gradually heated with stirring, and reacted at a temperature of 180 ° C. for 4 hours (first reaction step). Thereafter, 1.0 part (0.010 mol%) of trimellitic anhydride was added and reacted at 160 ° C. for 1 hour (second reaction step) to obtain an amorphous resin A.
The molecular weight of this amorphous resin A by GPC was weight average molecular weight (Mw) 6,500, number average molecular weight (Mn) 2,500, peak molecular weight (Mp) 3,700, and softening point was 90 ° C.

[Synthesis of Amorphous Resin B]
71.3 parts (0.155 mol%) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 24.1 parts (0.145 mol%) of terephthalic acid, and titanium tetra 0.6 parts of butoxide was put into a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the mixture was gradually heated with stirring and reacted at a temperature of 200 ° C. for 4 hours (first reaction step). Thereafter, 5.8 parts (0.030 mol%) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step) to obtain an amorphous resin B.
The molecular weight of this amorphous resin B by GPC was a weight average molecular weight (Mw) of 200,000, a number average molecular weight (Mn) of 5,000, a peak molecular weight (Mp) of 10,000, and a softening point of 130 ° C.

Amorphous resin A 60.0 parts by mass Amorphous resin B 35.0 parts by mass Crystalline resin 3 5.0 parts by mass Colorant 2 5.0 parts by mass Pigment Yellow 155 4.0 parts by mass (Toner Yellow 4G: Clariant)
・ 1.0 mass part of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Industries)]
Hydrocarbon wax 5.0 parts by mass (Fischer-Tropsch wax; HNP-9)
The materials of the above prescription were mixed well with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) and then kneaded with a biaxial kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a coarsely pulverized product.

The obtained coarsely pulverized product was crushed to a weight average particle size of 100 μm using ACM10 manufactured by Hosokawa Micron Corporation, and the obtained pulverized product was mechanically pulverized (Turbo Kogyo Co., Ltd .; turbo mill type T250-RS). Used and pulverized. Thereafter, the resulting finely pulverized product was subjected to coarse particle classification using a turboplex 100ATP manufactured by Hosokawa Micron Corporation to obtain toner particles. The obtained toner particles had a weight average particle diameter (D4) of 7.2 μm. 1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added to 100 parts by mass of the obtained toner particles, and a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.) is added. The toner 23 was obtained through a mixing process for 300 seconds.
The toner particle composition of the toner 23 is shown in Tables 2 and 3.

<Production Example of Toners 24 and 25>
Toners 24 and 25 were obtained in the same manner as in the production example of toner 23 except that the composition of toner 23 was changed as shown in Tables 2 and 3.

[Example 1]
The toner 1 was evaluated for tinting strength and light resistance according to the following evaluation procedure. The evaluation results are shown in Table 4. Good results were obtained for all items.

<Output of evaluation image>
The toner contained inside was removed from a cartridge for a commercially available color laser printer, Satel LBP7700C (manufactured by Canon Inc.), the interior was cleaned by air blow, and then toner 1 (150 g) was filled. Also, a part of the Satera LBP7700C (manufactured by Canon Inc.) was remodeled and changed so that an unfixed image could be output by removing the fixing device, and the image density could be adjusted by the controller. Furthermore, it has been modified to work even when only one color process cartridge is installed. The above cartridge is mounted on a printer, a controller is set so that the applied toner amount is 0.30 mg / cm ^2, and a rectangular solid image of 6.5 cm × 14.0 cm is output at the center of the transfer material, and an evaluation image It was. As the transfer material, letter size HP LASERJET PAPER (manufactured by Hewlett-Packard Company, 90.0 g / m ² ) was used.

<Evaluation method of coloring power>
The image density in the evaluation image was measured to evaluate the coloring power. The image density was measured using an X-Rite color reflection densitometer (color reflection densitometer X-Rite 404A). Measure the relative density of the white background portion and the solid image portion where the original density is 0.00, measure the density at the upper right, upper left, center, lower right and lower left of the solid image portion, and use the average value as the image density evaluated. The evaluation criteria are as follows.
A: The image density is 1.60 or more and the coloring power is very excellent.
B: The image density is 1.50 or more and less than 1.60, and the coloring power is excellent.
C: The image density is 1.40 or more and less than 1.50, and the coloring power is good.
D: The image density is less than 1.40 and the coloring power is inferior.

<Light resistance evaluation method>
In a super fluorescent lamp fade meter FL (manufactured by Suga Test Instruments Co., Ltd.), light having an intensity of 80000 (lux) was irradiated for 300 hours, and the residual ratio of image density before and after irradiation was determined. From the value of the residual rate, light resistance was evaluated based on the following evaluation criteria. The image density was measured in the same manner as the evaluation of the coloring power.
A: The image density residual ratio is 90% or more, and the light resistance is very excellent.
B: The image density remaining rate is 85% or more and less than 90%, and the light resistance is excellent.
C: Image density remaining rate is 75% or more and less than 85%, and light resistance is good.
D: Image density remaining rate is less than 75%, and light resistance is poor.
Table 4 shows the evaluation results obtained for the toner 1. As is clear from Table 4, good results were obtained for all items.

[Examples 2 to 25 and Comparative Examples 1 to 3]
For toners 2 to 25 and comparative toners 1 to 3, the tinting strength and light resistance were evaluated in the same manner as in Example 1. The obtained evaluation results are shown in Table 4.

Claims (10)

A toner having toner particles containing a binder resin, a crystalline resin and a colorant,
The half width (ΔTc) of the exothermic peak of the crystalline resin is 5.0 ° C. or less,
(ΔTc indicates the half-value width of the exothermic peak of the spectrum obtained when the crystalline resin is heated to 150 ° C. and then cooled at a temperature decrease rate of 10 ° C./min in differential scanning calorimetry (DSC).)
The toner, wherein the colorant contains a compound represented by the following formula (1).

(In formula (1), R ¹ , R ² , and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar represents an aryl group.)   The toner according to claim 1, wherein the crystalline resin is 0.5% by mass or more and 30.0% by mass or less based on a total amount of the binder resin and the crystalline resin. The toner according to claim 1, wherein the crystalline resin has a structural unit represented by the following formula (2).

(In the formula (2),
m is an integer of 4 to 10, and n is an integer of 6 to 12. ) The toner according to claim 3, wherein the crystalline resin further has a terminal structure derived from an aliphatic alcohol represented by the following formula (3) or an aliphatic carboxylic acid represented by the following formula (4).
Equation _{(3) H 3 C- (CH} 2) o -COOH
(In formula (3), o is an integer of 5 to 17.)
Equation _{(4) H 3 C- (CH} 2) p -OH
(In formula (4), p is an integer of 6 to 18.)   In the differential scanning calorimetry (DSC) of the crystalline resin, when the endothermic peak of the spectrum obtained when heated from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min is defined as the melting point (Tm) The toner according to claim 1, wherein Tm) is 50 ° C. or higher and 90 ° C. or lower.   6. The toner according to claim 1, wherein the crystalline resin has a weight average molecular weight (Mw) measured using size exclusion chromatography (GPC) of 5,000 or more and 30,000 or less.   The toner according to claim 1, further comprising a hydrocarbon-based release agent.   The toner according to claim 1, further comprising a fatty acid metal salt.   The colorant represented by the general formula (1) is 0.5% by mass or more and 10.0% by mass or less with respect to the total amount of the binder resin and the crystalline resin. The toner according to claim 1. The toner according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (5).

(In Formula (5), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ are each independently Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)