JP6504920B2 - toner - Google Patents

Description

  The present invention relates to toners used in imaging methods such as electrophotography, electrostatic recording and toner jet methods.

At present, power saving is required for copying machines and printers.
As a method of power saving, there is a reduction in power by lowering the temperature of the toner during heat fixing in the electrophotographic process. For that 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.

As a coloring agent for improving the coloring power of a toner, using a coloring agent (dye) with high solubility to resin is mentioned.
When a dye is used as a colorant for toner, the entire resin constituting the toner is colored, and thus 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, when a dye is generally used, it is a subject that light resistance falls. This is because the dye is susceptible to ultraviolet light in the image after printing because the dye is dispersed at the molecular level into the toner resin.

  In Patent Document 2, light resistance is improved by improving the dye. As a result, it is possible to achieve both coloring power and light resistance.

JP, 2013-137443, A JP, 2014-63156, A

  However, in recent years, coexistence of coloring power and light resistance at a still higher level is required, and the toner described in Patent Document 2 has room for improvement in coexistence of coloring power and light resistance. Therefore, an object of the present invention is to provide a toner capable of achieving both coloring power and light resistance at a high level.

（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は置換基を有していてもよいアリール基を表わす。） The present invention is a toner having toner particles including a binder resin, a crystalline resin, and a colorant, and the half-width (ΔTc) of the heat generation peak of the crystalline resin is 5.0 ° C. or less (ΔTc is In differential scanning calorimetry (DSC), after heating the crystalline resin to 150 ° C., the half-width of the exothermic peak of the spectrum obtained upon cooling at a temperature lowering rate of 10 ° C./min is shown. The present invention relates to a toner characterized in that it contains a compound represented by the following formula (1).

(In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar may have a substituent Represents an aryl group)

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

Embodiments of the present invention will be specifically described below.
As a result of intensive studies to solve the problems of the prior art described above, the inventors of the present invention have found that the toner having a crystalline resin having high crystallinity and a toner particle containing a compound represented by the above formula (1) has high coloring. It has been found that the effects of force and light resistance are exhibited. That is, in differential scanning calorimetry (DSC), the half-width (ΔTc) of the exothermic peak of the spectrum obtained upon heating to 150 ° C. and cooling at a temperature lowering 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), it is possible to achieve a balance between coloring power and light resistance at a high level.

  As described in the background, the compound of the above formula (1) has high solubility in an organic solvent, and is uniformly dispersed in a toner resin. Therefore, the compound is effective to improve 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は置換基を有していてもよい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, coloring is achieved at a high level since coloring is performed over the entire resin constituting the toner. The compound shown by Formula (1) can use the compound synthesize | combined by the method mentioned later, and can use a well-known coloring agent.
As a known coloring agent, Solvent Yellow 162, Disperse Yellow 114, 231 or the like can be used.

(In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar may have a substituent Represents an aryl group)

  On the other hand, crystalline resins having high crystallinity generally tend to have a high refractive index. Substances with high refractive index have strong scattering and absorption in the ultraviolet region. As a result, when the toner in the image after heat fixation is irradiated with light including ultraviolet light such as sunlight, it is considered that the crystallized crystalline resin scatters and absorbs the ultraviolet light. It is estimated that the light resistance is improved by protecting the coloring agent in the image from ultraviolet light as described above.

  Further, in differential scanning calorimetry (DSC), the half-width (ΔTc) of the exothermic peak of the spectrum obtained upon cooling to 150 ° C. and then cooling at a temperature lowering rate of 10 ° C./min is the crystallization rate of the crystalline resin And is considered to be an indicator of crystallinity. That is, it is suggested that the smaller the ΔTc, the faster the crystallization rate and the higher the degree of crystallization. When the crystallization rate is fast, the crystalline resin can be present in a crystallized state in the fixed image because it is rapidly crystallized immediately after heat fixation. When the degree of crystallinity is high, the crystallization site of the added crystalline resin tends to be increased, so the amount of the crystallized crystalline resin in the fixed image is increased. Therefore, as the ΔTc is smaller, protection of the colorant from ultraviolet light occurs by the mechanism described above, and the light resistance is improved. Therefore, the smaller the ΔTc of the crystalline resin, the better. However, since crystalline resins having extremely high crystallinity tend to be very expensive, it is practically preferable to use those having ΔTc of 1.0 ° C. or more.

On the other hand, if ΔTc is large, it indicates that the crystallization rate is slow and the degree of crystallization is low, and the crystalline resin in the fixed image is unlikely to be crystallized and the amount of crystallization is small. Conceivable. Therefore, when a crystalline resin having a ΔTc of more than 5.0 ° C. is used, it is difficult to obtain an excellent light resistance effect. As mentioned above, in order to acquire the effect of the present invention, it is necessary for deltaTc to be 5.0 ° C or less.
Therefore, ΔTc is preferably 1.0 ° C. or more and 5.0 ° C. or less. ΔTc can be controlled by changing the composition of the monomer of the crystalline resin, the molecular weight of the crystallinity, and 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 based on the total amount of the binder resin and the crystalline resin, a sufficient amount for achieving 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 the 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 becomes high, 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 dispersibility in the image after fixing is improved, so that the light resistance is easily improved. 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) Is more preferred.
Equation _{(3) H 3 C- (CH} 2) o -COOH
(In the formula (3), o is an integer of 5 to 17.)
Equation _{(4) H 3 C- (CH} 2) p -OH
(In the formula (4), p is an integer of 6 to 18.)

  When o in the formulas (3) and (4) is 5 or more and p is 6 or more, the crystallinity of the crystalline resin becomes high, and the 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 is easy to improve the quality. More preferably, o is an integer of 5 to 11, and p is an integer of 6 to 12.

  When a crystalline resin having a structural unit represented by the above formula (2) is produced with an acid and an alcohol such as those of formulas (3) and (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 end of the crystalline resin, it acts as a nucleation site during crystallization of the long chain alkyl moiety, and the crystallization rate can be improved and ΔTc can be reduced. As a result, the light resistance is further improved.

  The melting point (Tm) of the endothermic peak of the spectrum obtained when heating from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min in differential scanning calorimetry (DSC) of the crystalline resin It is preferable that (Tm) is 50 ° C. or more and 90 ° C. or less. When the melting point is 50 ° C. or higher, the crystallinity of the crystalline resin tends to be high, and the light resistance tends to be improved. When the melting point is 90 ° C. or less, the resin is easily dissolved at the time of heat fixation, so that the compatibility becomes high and the light resistance is easily improved by dispersing the crystalline resin in the image. As a more preferable range of melting | fusing point, they are 55 degreeC or more and 85 degrees C or less. The melting point of the crystalline resin can be controlled by changing the composition of the monomer.

  The crystalline resin preferably has a weight average molecular weight (Mw) of 5,000 or more and 30,000 or less measured using size exclusion chromatography (GPC). When it is 5000 or more, the crystallinity degree is easily improved, and thus the light resistance is easily improved. When it is 30000 or less, since it is easy to be compatible with the binder resin, the dispersibility in the image is improved, and the light resistance is easily improved. The Mw of the crystalline resin can be controlled by changing the reaction time at the time of production, the reaction temperature or the monomer feed ratio. 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. By using a hydrocarbon-based release agent for the toner, the light resistance is further improved. As a result of various studies conducted by the present inventors, it was found that the crystallization rate is improved when a hydrocarbon-based releasing agent is contained in toner particles containing a crystalline resin. It is presumed that this is because the crystallization rate of the hydrocarbon-based release agent is faster than the nucleation rate of the crystal part as compared with other toner materials. As a result, it is thought that the crystallization rate is increased by crystallization of the crystalline resin with the hydrocarbon-based release agent as the nucleation site, and the light resistance is further improved.

  Low molecular weight polyethylene, low molecular weight polypropylene, an alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax etc. are mentioned as an example of the hydrocarbon type mold release agent which can be used by this invention.

Moreover, you may use together the 1 type or 2 or more types of following mold release agent 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, sazole wax, montanic acid ester wax; and deacidification What partially or entirely deoxidized fatty acid esters such as carnauba wax can be mentioned. Further, saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as pracidic acid, eleostearic acid and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnavir alcohol, seryl alcohol Long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylene biscaprin Saturated fatty acid bisamides such as acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleylearamide Unsaturated fatty acid amides such as dipinic acid amide, N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N-distearyl isophthalic acid amide; calcium stearate, lau Fatty acid metal salts such as calcium phosphate, zinc stearate and magnesium stearate (generally referred to as metal soaps), and grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid Waxes; and partially esterified products of polyalcohols with fatty acids such as behenic acid monoglyceride, and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oil and the like.
The amount of the release agent added is preferably 0.5 to 30 parts by mass, and more preferably 1.5 to 20.0 parts by mass 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 above-mentioned hydrocarbon-based mold 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 to be 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, sodium laurate, calcium laurate, zinc laurate, barium laurate and lithium laurate, etc. Be

  The amount of fatty acid metal salt added is preferably 0.05% by mass or more and 3.0% by mass or less based on the total amount of the binder resin and the crystalline resin.

  The content of the compound represented by 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 the content 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 it is 10.0 mass% or less, the effect of the deterioration of the light resistance by the compound represented by Formula (1) is reduced, and the light resistance is likely to be 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 each independently represent Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms)

  If it is a compound (structure) represented by said Formula (5), in order that the light resistance of coloring agent itself may improve, light resistance will improve further.

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

In the present invention, “crystalline” refers to having a distinct endothermic peak, not a stepwise endothermic change in differential scanning calorimetry (DSC).
Even when the crystalline resin is an embodiment of a graft or block having a crystalline site and an amorphous site, it has a clear endothermic peak in differential scanning calorimetry (DSC). Is also contained in the crystalline resin.

  The "binding resin" in the present invention refers to one having a molecular weight of 2000 or more in the molecular weight distribution measured using size exclusion chromatography (GPC).

  As the binder resin used for the toner of the present invention, known resins such as styrene-based vinyl resin, maleic acid copolymer, polyester resin, epoxy resin can be used.

  As a polymerizable monomer which comprises a styrene-type vinyl resin, it is possible to use the vinyl-type polymerizable monomer in which radical polymerization is possible. Examples of the vinyl-based polymerizable monomer include monofunctional polymerizable monomers and polyfunctional polymerizable monomers.

As a monofunctional polymerizable monomer, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butyl Styrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, 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 And n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as 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, divinyl naphthalene, and divinyl ether.

  Monofunctional polymerizable monomers may be used alone or in combination of two or more, or a combination of a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer, or a multifunctional polymerizable The monomers can be used alone or in combination of two or more.

  A polyvalent carboxylic acid and a polyol can be used as a condensation polymerization monomer which comprises a polyester resin.

As polyvalent carboxylic acid,
Oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, 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. Further, as polyvalent carboxylic acids other than dicarboxylic acids, for example, trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid and the like can be mentioned.

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-pig Triol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, ethylene oxide of hydrogenated bisphenol A And hydrogenated bisphenol A propylene oxide adducts.

  It is preferable that the crystalline resin which can be used by this invention is polyester which has a structural unit shown by Formula (2) by polycondensing bivalent acid and dihydric alcohol. When the crystalline resin is a polyester, preferred dihydric acids include, for example, alkanedicarboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid , Octadecanedicarboxylic acid, decylsuccinic acid, dodecylsuccinic acid, octadecylsuccinic acid, etc., alkene dicarboxylic acids (eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, octadecenyl) Succinic acid, dimer acid and the like), aromatic dicarboxylic acid (eg, phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid etc.) and the like can be mentioned. These may be used in the form of acid anhydrides and alkyl esters.

  As preferred dihydric alcohols, alkylene glycols such as 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 spiro glycol, etc., alkylene ether glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol etc.), bisphenols (bisphenol A, biphenyl) Phenol F, bisphenol S, bisphenol A · ethylene oxide 2 mole adduct, bisphenol A · propylene oxide 2.5 mol adduct), and the like.

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

  Moreover, you may use terminal blocking agent for crystalline resin. By using a terminal blocking agent, it becomes possible to adjust the molecular weight, acid value, hydroxyl value, crystallinity degree and the like of the crystalline polyester. For example, as an end capping agent, a monobasic acid, its derivative, monohydric alcohol etc. are mentioned.

  Specifically, examples of 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 the like The acid anhydride etc. of those are mentioned. Among them, preferred are hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, stearic acid and their acid anhydrides represented by the formula (3). The acid anhydride may be an acid anhydride in which monovalent acids are condensed, or a mixed acid anhydride in which two types of acids form an acid anhydride.

  The monohydric alcohol includes methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, stearyl alcohol and the like. Among them, heptanol, octanol, nonanol, decanol, lauryl alcohol and stearyl alcohol represented by the formula (4) are preferable.

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

  In the present invention, any method may be used as a method of producing toner particles. For example, a suspension polymerization method in which a polymerizable monomer for obtaining a binder resin and a solution of a coloring agent, a releasing agent and the like are suspended in an aqueous solvent and polymerized; kneading and pulverizing various toner constituent materials Classification and kneading method: A dispersion obtained by emulsifying and dispersing a binder resin and a dispersion of a coloring agent, a releasing agent, etc. are mixed, coagulated and heat-fused, and an emulsion aggregation method to obtain toner particles; A dispersion liquid formed by emulsion polymerization of a polymerizable monomer of a binder resin and, if necessary, a dispersion liquid such as a colorant and a releasing agent is mixed, coagulated, heat-fused, and toner particles are obtained. An emulsion polymerization / aggregation method to be obtained; a solution suspension method in which a binder resin and a solution of a coloring agent, a releasing agent and the like are suspended in an aqueous solvent and granulated can be used.

  Hereinafter, methods of measuring various physical properties according to the present invention will be described.

<Measuring method of molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin and the polymer are measured using gel permeation chromatography (GPC) as follows.
First, the resin or polymer is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Misholy Disc" (manufactured by Tosoh Corp.) 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. It measures on condition of the following using this sample solution.
Device: High-speed GPC device "HLC-8220GPC" (manufactured by Tosoh Corp.)
Column: LF-604, 2 stations [Showa Denko KK]
Eluent: THF
Flow rate: 0.6 ml / min. Oven temperature: 40 ° C.
Sample injection volume: 0.020 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "(manufactured by Tosoh Co., Ltd.) are used to obtain molecular weight calibration curves.

<Method of measuring the half width (ΔTc) of the exothermic peak and the melting point (Tm)>
The half width (ΔTc) and the melting point (Tm) of the 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 heat of fusion uses the heat of fusion of indium.
Specifically, 5 mg of the sample is precisely weighed and placed in an aluminum pan, using an empty aluminum pan as a reference. In the measurement, the temperature is once raised from room temperature to 150 ° C. at a heating rate of 10 ° C./min, and then cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. At that time, the half-width (ΔTc) of the exothermic peak of the obtained DSC curve is obtained. After that, 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 taken as the melting point (Tm).

<Method of measuring weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is connected using Coulter Multisizer (manufactured by Coulter) with an interface (manufactured by Nikkaki Co., Ltd.) for outputting number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC). Measure according to the operation manual of. Specifically, 1% NaCl aqueous solution is prepared using first grade sodium chloride as an electrolytic solution. A commercially available ISOTON R-II (manufactured by Coulter Scientific Japan Co., Ltd.) can also be used as the electrolytic solution. 5 mg of a measurement sample (toner) and 0.1 ml of contaminon aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) are added to 100 ml of the electrolytic aqueous solution. The electrolytic solution 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 using a Coulter multisizer using a 100 μm aperture, and the number average particle diameter Determine (D4).

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples. In the following description, "part" and "%" are based on mass unless otherwise noted.

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
The coloring agent 1 of the structure of following formula (S1) was obtained.

A 20 mL solution of 0.721 g of an amine compound (A1) in methanol (MeOH) was cooled to 5 ° C. according to the above scheme, and 2 mL of concentrated sulfuric acid and 1.4 mL of nitrosyl sulfuric acid (40% by mass) were added dropwise (diazotized solution A). Separately, a solution of 0.496 g of pyridone compound (P1) in 20 mL of methanol (MeOH) is cooled to 5 ° C., and diazotized solution A is slowly added dropwise to this to keep the temperature at 5 ° C. or less. The mixture was stirred for 20 minutes. After completion of the reaction, aqueous sodium carbonate solution was added dropwise to neutralize pH to 6, and then extracted with chloroform. Thereafter, the solvent is distilled off and the solid obtained is purified by column chromatography (developing solvent: heptane / ethyl acetate) and further recrystallized with a heptane solution to obtain 0.8 g of a colored structure of the above formula (S1) Agent 1 was obtained.
In addition, identification of the obtained coloring agent 1 was performed by the analysis method using MALDI MS (autoflex apparatus, manufactured by Bruker Daltonics). The detection ion adopted negative mode in MALDI MS.
Mass spectrometry by MALDI MS: m / z = 618.612 (M-H)-

Synthesis Example of Colorant 2
The coloring agent 2 of the structure of a following formula (S2) was obtained like the synthesis example of the coloring agent 1 except having changed the pyridone compound (P1) into the pyridone compound (P2) shown below.

Synthesis Example of Colorant 3
The following formula is the same as the synthesis example of the colorant 1 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 coloring agent 3 of the structure of (S3) was obtained.

Synthesis Example of Colorant 4
The following formula is the same as the synthesis example of the colorant 1 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 coloring agent 4 of the structure of (S4) was obtained.

Synthesis Example of Colorant 5
The following formula is the same as the synthesis example of Colorant 1 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 coloring agent 5 of the structure of (S5) was obtained.

<Production Example of Crystalline Resin 1>
100.0 parts by mass of sebacic acid and 87.2 parts by mass of 1,9-nonanediol are added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction pipe, a dehydration pipe, and a decompression device, and the mixture is stirred. While heating to a temperature of 130.degree. After 0.7 parts by mass of titanium (IV) isopropoxide was added as an esterification catalyst, the mixture was heated to a temperature of 160 ° C. and subjected to condensation polymerization for 5 hours. Thereafter, the temperature was raised to 180 ° C., and reaction was performed while reducing pressure until the desired molecular weight was obtained. Thereafter, 6.6 parts by mass of lauryl alcohol was added, and the mixture was 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 23,000, the melting point (Tm) was 68 ° C., and the half 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 Resin 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>
[Step of Preparing Colorant Dispersion 1]
-Styrene (St) monomer 270 parts by mass-Acrylic acid n-butyl (BA) monomer 90 parts by mass-Polar resin 20 parts by mass (copolymer of styrene, methacrylic acid, methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 14,800, Tg = 89 ° C., acid value AV = 22 mg KOH / g, hydroxyl value OH v = 8 mg KOH / g)
・ Colorant 1 16 parts by mass ・ Pigment Yellow 155 (PY 155) 20 parts by mass (Toner Yellow 4G: Clariant)
The above material is introduced into Attritor (Mitsui Miike Kako Co., Ltd.) and stirred at 200 rpm and 25 ° C. for 180 minutes using zirconia beads (200 parts) with a radius of 2.5 mm to prepare a colorant dispersion 1. did.

[Step of Preparing Toner Composition Solution]
Colorant dispersion 1 312 parts by mass Crystalline resin 1 15 parts by mass Hydrocarbon-based wax 21 parts by mass (Fisher-Tropsch wax; HNP-9)
-3 parts by mass of aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E 88 (manufactured by Orient Chemical Industries, Ltd.)]
The above materials are mixed, heated to 65 ° C., and uniformly dissolved and dispersed for 60 minutes at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and the toner composition dissolved. I got a liquid.

[Process for adjusting toner particle dispersion]
900 parts by mass of ion-exchanged water, 150 parts by mass of 0.5 M Na ₃ PO ₄ aqueous solution in a 2-liter four-necked flask equipped with a high-speed stirring device TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) After charging 6.5 parts by mass of a 10% hydrochloric acid aqueous solution, the T. K. 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 a toner composition solution, and after sufficient mixing Charged to aqueous medium. This, temperature 62 ° C., under _{N 2} atmosphere, T. K. The polymerizable monomer composition was granulated by stirring for 10 minutes at 12,000 rpm with a homomixer. Then, the reaction was completed by heating to a temperature of 75 ° C. while stirring with a paddle stirring blade and conducting polymerization for 7.5 hours. Then, the remaining solvent was distilled off under reduced pressure, and the aqueous medium was cooled to obtain a toner particle dispersion. The weight average particle diameter (D4) of the obtained toner particles was 6.3 μm.

Hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.4, and stirring was performed 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 the water was full, and washing was performed by solid-liquid separation at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles. To 100 parts by mass of the obtained toner particles, 1.5 parts by mass (number average primary particle diameter: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added, and Mitsui Henschel mixer (Mitsui Miike Koko) Toner 1 was obtained through a 300-second mixing process using K.K.
The toner particle composition of Toner 1 is shown in Tables 2 and 3. The polar resin used in the production example of the toner 1 is included as a binder resin.

<Production Example of Toners 2 to 22 and Comparative Toners 1 to 3>
Toners 2 to 22 and Comparative Toners 1 to 3 were obtained in the same manner as in Production Example of Toner 1, except that the composition of Toner 1 was changed as shown in Tables 2 and 3. 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 producing the toner particles 5 in Table 3, is a coal-based Fischer-Tropsch wax having an endothermic peak temperature of 105 ° C. manufactured by Sazor.

<Production Example of Toner 23>
[Synthesis of Amorphous Resin A]
76.9 parts (0.167 mol%) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 24.1 parts (0.145 mol%) of terephthalic acid, and titanium tetramer 0.5 parts of butoxide was placed in a 4-liter, four-neck glass flask, fitted with a thermometer, a stirrer, a condenser and a nitrogen inlet tube and placed in a heating mantle. Next, after the inside of the flask was replaced with nitrogen gas, it was gradually heated with stirring, and reacted for 4 hours while stirring at a temperature of 180 ° C. (first reaction step). Thereafter, 1.0 part (0.010 mol%) of trimellitic anhydride was added, and the mixture was 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 the softening point was 90.degree.

[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 tetramer 0.6 parts of butoxide was placed in a 4-liter, four-neck glass flask, fitted with a thermometer, a stirrer, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, it was gradually heated with stirring, and reacted for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Then, 5.8 parts (0.030 mol%) of trimellitic anhydride was added, and reaction was carried out 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) 200,000, a number average molecular weight (Mn) 5,000, a peak molecular weight (Mp) 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)
-Aluminum compound of 3,5-di-tert-butylsalicylic acid 1.0 part by mass (Bontron E 88 (manufactured by Orient Chemical Industry Co., Ltd.))
Hydrocarbon-based wax 5.0 parts by mass (Fisher-Tropsch wax; HNP-9)
The materials of the above formulation were thoroughly mixed with Mitsui Henschel Mixer (manufactured by Mitsui Miike Kako Co., Ltd.), and then kneaded with a twin-screw kneader set to a temperature of 130 ° C. The obtained kneaded product was cooled and roughly crushed to 2 mm or less with a hammer mill to obtain a roughly pulverized product.

The resulting coarsely pulverized product is internally pulverized to a weight average particle diameter of 100 μm using ACM 10 manufactured by Hosokawa Micron Corporation, and the resultant internally pulverized product is mechanically crushed (manufactured by Turbo Kogyo Co., Ltd .; Turbomill T250-RS type). It was finely ground using. Thereafter, the finely pulverized product obtained was subjected to coarse particle classification using Turboplex 100 ATP manufactured by Hosokawa Micron Corporation to obtain toner particles. The weight average particle diameter (D4) of the obtained toner particles was 7.2 μm. To 100 parts by mass of the obtained toner particles, 1.5 parts by mass (number average primary particle diameter: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added, and Mitsui Henschel mixer (Mitsui Miike Koko) Toner 23 was obtained by performing a mixing process for 300 seconds using a machine company.
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 Production Example of Toner 23, except that the composition of Toner 23 was changed as shown in Tables 2 and 3.

Example 1
According to the following evaluation procedure, the toner 1 was evaluated for coloring power and light resistance. The evaluation results are shown in Table 4. Good results were obtained for all items.

<Output of evaluation image>
The toner contained in the cartridge for a commercially available color laser printer Satera LBP 7700C (manufactured by Canon Inc.) was removed, the inside was cleaned by air blow, and then toner 1 (150 g) was filled. In addition, Satera LBP 7700C (manufactured by Canon Inc.) was partially modified, and the fixing device was removed so as to output an unfixed image, and the image density was made adjustable by the controller. Furthermore, it has been remodeled to operate with only one process cartridge installed. The above cartridge is mounted on a printer, and the controller is set so that the toner loading 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 to make an evaluation image. And A letter-sized HP LASER JET PAPER (manufactured by Hewlett Packard, 90.0 g / m ² ) was used as the transfer material.

<Evaluation method of coloring power>
The image density in the evaluation image was measured to evaluate the tinting strength. 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 part and solid image part of original density 0.00, and measure the density of 5 points of upper right, upper left, center, lower right and lower left of solid image part, and use the average value as image density evaluated. Evaluation criteria are as follows.
A: The image density is 1.60 or more, and the coloring power is very excellent.
B: Excellent in tinting power at an image density of 1.50 or more and less than 1.60.
C: Good tinting strength at an image density of 1.40 or more and less than 1.50.
D: The image density is less than 1.40 and the coloring power is poor.

<Evaluation method of light resistance>
In a super fluorescent light fade meter FL (manufactured by Suga Test Instruments Co., Ltd.), light with 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 retention rate is 90% or more, and the light resistance is very excellent.
B: The image density retention rate is 85% or more and less than 90%, and is excellent in light resistance.
C: The image density retention rate is 75% or more and less than 85%, and the light resistance is good.
D: The image density retention rate is less than 75%, and the light resistance is poor.
The evaluation results obtained for Toner 1 are shown in Table 4. As is clear from Table 4, good results were obtained for all items.

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

Claims (10)

A toner comprising toner particles comprising a binder resin, a crystalline resin and a colorant,
The half value width (ΔTc) of the exothermic peak of the crystalline resin is 5.0 ° C. or less,
(ΔTc indicates the half-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).
A toner comprising the compound represented by the following formula (1):

(In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ar may have a substituent 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 with respect to 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 carboxylic acid represented by the following formula (3) or an aliphatic alcohol represented by the following formula (4).
Equation _{(3) H 3 C- (CH} 2) o -COOH
(In the formula (3), o is an integer of 5 to 17.)
Equation _{(4) H 3 C- (CH} 2) p -OH
(In the formula (4), p is an integer of 6 to 18.)   In the differential scanning calorimetry (DSC) of the crystalline resin, the endothermic peak of the spectrum obtained when the temperature is raised from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min is the melting point (Tm) The toner according to any one of claims 1 to 4, wherein Tm) is 50 ° C or more and 90 ° C or less.   The toner according to any one of claims 1 to 5, wherein the weight average molecular weight (Mw) of the crystalline resin measured using size exclusion chromatography (GPC) is 5,000 or more and 30,000 or less.   The toner according to any one of claims 1 to 6, wherein the toner further contains a hydrocarbon-based release agent.   The toner according to any one of claims 1 to 7, wherein the toner further contains a fatty acid metal salt.   The coloring agent represented by the said General formula (1) is 0.5 mass% or more and 10.0 mass% or less with respect to the total amount of the said binder resin and the said crystalline resin. The toner according to claim 1 or 2. The toner according to any one of claims 1 to 9, 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 each independently represent Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms)