JP2018049195A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in coloring power, chargeability, and storage stability.SOLUTION: A toner includes toner particles each containing pigment, a resin including an ionic functional group, and a metallic compound. The resin including an ionic functional group has an acid dissociation constant pKa of 6.0 or more and 9.0 or less, and the metallic compound is either one of metal alkoxide, β-diketone metal complex, or a composite complex of these.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.

A technique for visualizing image information through an electrostatic latent image such as electrophotography is widely used in various fields such as a copying machine and a printer. With the development of technology, the fields of use have expanded and the electrophotographic apparatus has become more diverse. In addition to higher speed and higher image quality, various added values such as downsizing and cost reduction of the apparatus have been demanded.
In view of the above background, toners used in electrophotography are good at function separation structures, and toner production by a wet method that can add added value relatively easily has become mainstream. In particular, the toner particles obtained by the suspension polymerization method or the dissolution suspension method have a spherical shape or a shape close to a sphere, and the surface is uniform. In order to exhibit good development characteristics, it is preferable as a toner corresponding to high speed and high image quality.
To reduce the size and cost, a toner having higher coloring power than before has been attracting attention. By using a high coloring power toner, an image can be formed with a smaller amount of toner, and the printer main body can be reduced in size and energy can be saved. However, in the manufacturing process of toner particles manufactured by a wet method, external shares are less likely to be applied in droplets containing a toner composition formed in an aqueous medium. The pigment aggregates and the coloring power is reduced. Further, at that time, the pigment tends to be unevenly distributed on the toner surface, and adverse effects such as a decrease in chargeability and deterioration in storage stability also appear.
In order to improve the coloring power, for example, in a toner produced by granulating a solution containing a polyester resin and carbon black in an organic solvent in an aqueous medium to form toner particles, the carbon black has an aluminum coupling. A toner characterized by being dispersed by an agent has been proposed (see Patent Document 1). According to this, when the aluminum coupling agent reacts with the functional group on the surface of the carbon black and the polyester resin adsorbs to the aluminum coupling agent bonded to the carbon black, the dispersion of the carbon black is improved and the coloring power is improved. Have been described. However, although the aluminum coupling agent and carbon black interact strongly, the interaction with the polyester resin is insufficient, and there are still problems in dispersing the pigment to a high level. Therefore, the remarkable improvement of coloring power was not seen.
In addition, a toner containing a metal-containing polymer having an aromatic compound part in which a metal is bonded in a salicylic acid structure part or a salicylic acid derivative structure part and a polymer part has been proposed (see Patent Document 2). According to this, a good toner is obtained in the pigment dispersion in the toner particles, but the dispersion state is still insufficient for the whole toner, and as a result, the improvement in high coloring power is not improved. There was room.
On the other hand, the toner by the pulverization method can be obtained by using untreated pigment in a high viscosity binder resin that has been heated and melted by kneading the toner raw materials, and the toner is pulverized in a good pigment dispersion state. Since the toner is manufactured, a toner having high coloring power can be obtained. However, if the pigment is not devised even in the pulverization method, the pigment exposed to the crushed fracture surface causes deterioration in chargeability and storage stability.
In the pulverization method, a toner containing a metal alkoxide and a polyester resin has been proposed (see Patent Document 3). According to this, it is described that the cross-linking between the metal alkoxide and the polyester resin occurs, but the interaction between the polyester resin and the metal alkoxide was very weak compared to the required one. Although the metal alkoxide can strongly interact with the pigment, the interaction between the metal alkoxide and the polyester is insufficient, so that the pigment cannot be sufficiently covered with the polyester. As a result, the chargeability is lowered and the storage stability is deteriorated.
As described above, in any of the toner manufacturing methods, it is difficult to sufficiently satisfy all of the coloring power, chargeability, and storage stability with the conventional methods.

JP 2003-140395 A JP 2014-098841 A JP-A-7-98516

  The present invention is to provide a toner that solves the above background art. That is, it is to provide a toner excellent in coloring power, chargeability and storage stability.

The above object is achieved by the present invention described below. That is, the present invention is a toner having toner particles containing a pigment, a resin having an ionic functional group, and a metal compound,
The acid dissociation constant pKa of the resin having an ionic functional group is 6.0 or more and 9.0 or less, and the metal compound is any one of a metal alkoxide, a β-diketone metal complex, or a complex thereof. The present invention relates to a toner.

  According to the present invention, it is possible to provide a toner excellent in coloring power, chargeability, and storage stability.

It is the schematic of the apparatus which measures a triboelectric charge amount.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have a toner having toner particles containing a pigment, a resin having an ionic functional group, and a metal compound, and the pKa is 6.0 or more. By using in combination a resin having an ionic functional group of 9.0 or less and a metal compound (indicating either a metal alkoxide, a β-diketone metal complex, or a complex of these), coloring power, chargeability And a toner excellent in storage stability was obtained.

  The inventors presume the reason as follows.

  In the present invention, a metal compound (indicating either a metal alkoxide, a β-diketone metal complex, or a complex of these) is adsorbed on the pigment surface, and pKa is not less than 6.0 and not more than 9.0. A resin having an ionic functional group is strongly adsorbed on the metal compound. That is, the pigment modification state of “pigment-metal compound-resin having an ionic functional group” can be formed. As a result, particularly in the case of producing a toner in an aqueous medium such as a suspension polymerization method or a dissolution suspension method, it is easily generated in a liquid by imparting a steric repulsion force due to the spread of a polymer chain to the pigment. Re-aggregation of the pigment can be suppressed. As a result, a toner having improved pigment dispersibility and excellent coloring power can be obtained. Further, since the pigment dispersibility is improved, the uneven distribution of the pigment on the toner surface can be reduced particularly in the toner manufactured in an aqueous medium, so that the chargeability and the storage stability can also be improved. On the other hand, in the toner manufactured by the pulverization method, even if the pigment is exposed at the crushed fracture surface, the pigment surface is sufficiently covered with the resin having an ionic functional group, so that the polarity of the pigment surface can be sufficiently reduced. In addition, the chargeability and storage stability can be improved.

  The adsorption of “pigment-metal compound (indicating either metal alkoxide, β-diketone metal complex, or complex of these)” can be explained based on the Lewis acid-base definition. That is, the central metal of the metal compound is Lewis acid, and the lone electron pair present on the pigment surface is the Lewis base, which is due to the acid-base interaction. The greater the charge of the central metal, the stronger the force of attracting lone electron pairs on the pigment surface.

  Adsorption of “metal compound (metal alkoxide, β-diketone metal complex, or any of these complex complexes) —resin having an ionic functional group” also occurs based on the Lewis acid-base definition I believe. That is, an ionic functional group having an acid dissociation constant pKa of 6.0 or more and 9.0 or less is adsorbed to the metal in the metal compound as a Lewis base. At this time, it is considered that the higher the complex stability between the metal compound and the resin having an ionic functional group, the stronger the adsorption force of the resin having the metal compound-ionic functional group. Since the resin having an ionic functional group works as a Lewis base, the larger the acid dissociation constant pKa, the higher the complex stability. If the pKa is smaller than 6.0 (for example, a polyester having a carboxylic acid and a hydroxyl group at the end), the adsorptivity to the metal is not sufficient and the effect cannot be obtained. On the other hand, if pKa is larger than 9.0, acid dissociation of hydrogen ions in the ionic functional group is difficult to occur and the adsorption to the metal is inhibited.

  The metal compound used in the present invention has a large central metal charge, and any metal alkoxide, β-diketone metal complex, or complex of these can be used without particular limitation.

  As the metal alkoxide, specifically, a compound represented by the following formula (3) can be used.

［式（３）中、Ｍは金属イオンを示し、Ｒ³はアルキル基を示し、ｍは金属イオンの酸化数を示す。］

[In Formula (3), M represents a metal ion, R ³ represents an alkyl group, and m represents the oxidation number of the metal ion. ]

The alkyl group in R ³ is not particularly limited, but a binder resin for toner, a polymerizable monomer for forming the binder resin, or one having an affinity for an organic solvent can be preferably used. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

  As the β-diketone complex, specifically, a compound represented by the following formula (4) can be used.

［式（４）中、Ｍは金属イオンを示し、Ｒ⁴およびＲ⁵はそれぞれ独立して、水素原子、ハロゲン原子、アルコキシ基、アルキル基、またはアルキル基の水素原子の一部または全部をフッ素原子に置換したアルキル基を示し、ｎは金属イオンの酸化数を示す。］

[In the formula (4), M represents a metal ion, and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or a part or all of the hydrogen atoms of the alkyl group as fluorine. The alkyl group substituted by the atom is shown, n shows the oxidation number of a metal ion. ]

The alkyl group in R ⁴ and R ⁵ is not particularly limited, but a toner binder resin, a polymerizable monomer that forms the binder resin, or a substance having an affinity for an organic solvent is preferably used. Can do. Specific examples include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a sec-butyl group.

The alkoxy group in R ⁴ and R ⁵ is not particularly limited, but a binder resin for the toner, a polymerizable monomer that forms the binder resin, or one having an affinity for an organic solvent is preferably used. Can do. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

  As a complex complex of a metal alkoxide and a β-diketone metal complex, specifically, a compound represented by the following formula (5) can be used.

［式（５）中、Ｍは金属イオンを示し、Ｒ⁶乃至Ｒ⁸はそれぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基を示し、ｋおよびｌは、それぞれ１以上の整数を示し、ｋおよびｌの和が金属イオンの酸化数となる。］

[In Formula (5), M represents a metal ion, R ^{6 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and k and l each represents an integer of 1 or more. The sum of k and l is the oxidation number of the metal ion. ]

  The alkyl group in formula (5) is not particularly limited, but it is preferable to use a binder resin for the toner, a polymerizable monomer that forms the binder resin, or one having an affinity for an organic solvent. it can. Specific examples include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a stearyl group, and an oleyl group.

  The alkoxy group in the formula (5) is not particularly limited, but it is preferable to use a toner binder resin, a polymerizable monomer that forms the binder resin, or one having an affinity for an organic solvent. it can. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

  As described above, the central metal having a large charge has a high effect in the present invention. Among typical elements, Al, Ba, Ca, Mg, and Zn are preferable because those having a high valence and a small ionic radius have higher complex stability. In addition, transition elements such as Fe, Ti, Co, and Zr are preferable because they can have stable unpaired electrons in the d orbital and have high complex stability. Among these, in particular, Al, Zn, Fe, Co, and Zr can be suitably used in the present invention from the viewpoint of material availability.

  The amount of the metal compound added to the toner of the present invention is preferably 1.0% by mass or more and 50.0% by mass or less with respect to the pigment. When the amount is 1.0% by mass or more, the amount of adsorption to the pigment is sufficient, and when the amount is 50.0% by mass or less, the interaction between metal compounds can be reduced. More preferably, it is 3.0 mass% or more and 30.0 mass% or less.

  Any resin having an ionic functional group may be used as long as it satisfies the acid dissociation constant pKa. Although how to obtain the acid dissociation constant pKa will be described later, it can be obtained from the neutralization titration result.

  For example, a resin having a hydroxyl group bonded to an aromatic ring or a carboxy group bonded to an aromatic ring can have an acid dissociation constant pKa in the above range. For example, those obtained by polymerizing vinyl salicylic acid, 1 vinyl phthalate, vinyl benzoic acid, 1-vinyl naphthalene-2-carboxylic acid are preferable.

  Moreover, it is more preferable to include a polymer having an ionic functional group represented by the following structural formula (6) as a molecular structure.

［式（６）中、Ｒ⁹はヒドロキシ基、カルボキシ基、炭素数が１以上１８以下のアルキル基、または、炭素数が１以上１８以下のアルコキシ基を示し、Ｒ¹⁰は水素原子、ヒドロキシ基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシ基を示し、ｇは１以上３以下の整数であり、ｈは０以上３以下の整数であり、ｈが２または３の場合、ｈ個のＲ⁹は同一であってもよいし、異なっていてもよい。］

[In the formula (6), R ⁹ represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom or a hydroxy group. Represents an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g is an integer of 1 to 3, h is an integer of 0 to 3, and h is 2 Or in the case of 3, h R < ⁹ > may be the same and may differ. ]

Examples of the alkyl group in R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxy group Includes a methoxy group, an ethoxy group, a propoxy group, and the like.

  Among these, the case represented by the following formula (1) is preferable from the viewpoint of manufacturability and exhibits a remarkable effect in the present invention.

［式（１）中、Ｒ¹はヒドロキシ基、アルキル基、または、アルコキシ基を示す。］

[In Formula (1), R < ¹ > shows a hydroxy group, an alkyl group, or an alkoxy group. ]

  The content of the ionic functional group is preferably 1 mol% or more and 20 mol% or less in one molecule of the resin having the ionic functional group. When the ionic functional group is 1 mol% or more, a sufficient amount of the ionic functional group is adsorbed to the metal, and when the ionic functional group is 20 mol% or less, the interaction between the ionic functional groups is suppressed. Therefore, dispersibility and coloring power are easily improved. More preferably, it is 3 mol% or more and 8 mol% or less.

  The hydrophobic parameter HP of the resin having an ionic functional group is preferably 0.50 or more (HP is a solution containing 0.01 part by weight of a resin having an ionic functional group and 1.48 parts by weight of chloroform. This is the volume fraction of heptane at the precipitation point of the resin having an ionic functional group when heptane is added. The hydrophobicity parameter can be measured by the method described later. The hydrophobicity parameter is obtained by quantifying the degree of hydrophobicity of a resin having an ionic functional group, and a larger numerical value indicates higher hydrophobicity. When the hydrophobicity parameter HP is 0.50 or more, the ability to impart hydrophobicity to the pigment is increased, and in the case of a toner manufactured with an aqueous medium, it is possible to further reduce the uneven surface distribution of the pigment. As a result, the chargeability and storage stability can be significantly improved. In addition, in the toner manufactured by the pulverization system, the pigment exposed on the pulverized fracture surface is highly hydrophobic, so that the chargeability and the storage stability can be highly improved.

  For the purpose of controlling the hydrophobic parameter HP, the resin having an ionic functional group preferably has a carboxylic acid ester group represented by the following formula (2) in the molecule.

［式（２）中のｎは３以上２７以下の整数を表す。］

[N in the formula (2) represents an integer of 3 to 27. ]

  The carboxylic acid ester group represented by the formula (2) per molecule of the resin having an ionic functional group is preferably 1 mol% or more and 32 mol% or less from the balance of hydrophobicity imparting ability and metal adsorption performance. More preferably, 4 mol% or more and 16 mol% or less are preferable. The number of carboxylic acid ester groups can be controlled by adjusting the monomer charge ratio and molecular weight during the synthesis of the resin having an ionic functional group. Further, n in the formula (2) is preferably 3 or more and 26 or less for the same reason. In order to efficiently impart hydrophobicity to the pigment in the present invention, n is more preferably 7 or more and 27 or less.

  The content of the ionic functional group and the carboxylic acid ester group per molecule of the resin having the ionic functional group is determined by measuring NMR and calculating the integral value derived from the characteristic chemical shift value of each monomer component. The molar ratio of the components can be calculated.

  The main chain structure of the resin having an ionic functional group is not particularly limited. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Of these, vinyl polymers are preferred.

  The weight average molecular weight Mw of the resin having an ionic functional group is preferably 10,000 or more and 70,000 or less. When it is 10,000 or more, the pigment dispersion effect due to the spread of the polymer chain is exhibited, and when it is 70,000 or less, the number of polymers when the same amount is added is sufficient and the pigment dispersion effect is exhibited. More preferably, it is 10,000 or more and 50000 or less. The weight average molecular weight Mw of the resin having an ionic functional group can be controlled by changing the reaction temperature, the reaction time, the monomer charge ratio, the initiator amount, and the like during polymerization.

  The addition amount of the resin having an ionic functional group in the toner of the present invention is preferably 50% by mass or more with respect to the metal compound. In this case, the amount of adsorption to the metal is sufficient, and the effect of pigment dispersion is high. Moreover, it is preferable that it is 50 mass parts or less with respect to 100 mass parts of binder resin.

  The effect of the present invention is manifested in all toner production methods such as suspension polymerization, dissolution suspension, emulsion aggregation, and pulverization. Hereinafter, a toner production method that can be carried out in the present invention will be described. Here, a toner manufacturing method that can be manufactured with an aqueous medium such as a suspension polymerization method or a dissolution suspension method will be described in detail. However, since the effect is expressed based on the mechanism as described above, the toner can be manufactured with an aqueous medium. The present invention is not limited to toner and can be applied to any other manufacturing method.

Specifically, the production method including the step of granulating in an aqueous medium,
i) Polymerizable monomer, pigment, metal compound (indicating any of metal alkoxide, β-diketone metal complex, or complex of these) and a resin having an ionic functional group A so-called suspension polymerization method comprising a step of obtaining toner particles by granulating the composition in an aqueous medium and polymerizing a polymerizable monomer contained in the granulated particles;
ii) dissolving or dissolving a toner composition containing a pigment, a metal compound (metal alkoxide, β-diketone metal complex, or a complex of these) and a resin having an ionic functional group in an organic solvent; This is a so-called dissolution suspension method including a step of obtaining toner particles by granulating a dispersed mixed solution in an aqueous medium and removing an organic solvent contained in the granulated particles.

  The polymerizable monomer used in the suspension polymerization method is preferably a monovinyl monomer. Specifically, as the polymerizable monomer, for example, aromatic vinyl monomers such as styrene, vinyl toluene, and α-methylstyrene; α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate , Ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacryl Acrylic acid or methacrylic acid derivatives such as 2-ethylhexyl acid, cyclohexyl methacrylate, isobornyl methacrylate, dimethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide; ethylene, Ethylenically unsaturated monoolefins such as propylene and butylene; vinyl halides such as vinyl chloride, vinylidene chloride and vinyl fluoride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl Examples thereof include vinyl ketones such as methyl ketone and methyl isopropenyl ketone; nitrogen-containing vinyl compounds such as 2-vinyl pyridine, 4-vinyl pyridine and N-vinyl pyrrolidone; The polymerizable monomers can be used alone or in combination of two or more. Among monovinyl monomers, it is preferable to use an aromatic vinyl monomer in combination with an acrylic ester or a methacrylic ester.

  As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexano Ate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4 -Initiated peroxide polymerization of dichlorobenzoyl peroxide, lauroyl peroxide, etc. And the like. Further, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization. The following are mentioned as a crosslinkable monomer. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates were changed to methacrylate The.

  The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferable addition amount is 0.001% by mass or more and 15.000% by mass or less with respect to the polymerizable monomer.

  In the suspension polymerization method, the effect of the present invention is exhibited even in a toner obtained by adding a macromonomer to the polymerizable monomer composition in order to achieve both the storage stability and the fixing property of the obtained toner. The macromonomer forms a graft polymer by copolymerization with the polymerizable monomer in droplets suspended in an aqueous medium.

  A macromonomer (also referred to as a macromer) is a relatively long linear molecule having a polymerizable functional group (for example, an unsaturated group such as a carbon-carbon double bond) at the end of a molecular chain. As the macromonomer, an oligomer or polymer having a vinyl polymerizable functional group at the end of the molecular chain and having a number average molecular weight of usually 1,000 or more and 30,000 or less is preferable. When a macromonomer having a small number average molecular weight is used, the surface portion of the polymerized toner becomes soft, and the storage stability tends to be lowered. On the other hand, when a macromonomer having a large number average molecular weight is used, the fluidity of the macromonomer is deteriorated, and the fixability and storage stability are lowered. Examples of the vinyl polymerizable functional group at the end of the molecular chain of the macromonomer include an acryloyl group and a methacryloyl group, and a methacryloyl group is preferred from the viewpoint of ease of copolymerization.

  Examples of the macromonomer used in the present invention include polymers obtained by polymerizing styrene, styrene derivatives, methacrylic acid esters, acrylic acid esters, acrylonitrile, methacrylonitrile, etc., alone or in combination of two or more; polysiloxane skeleton And the like.

  The amount of the macromonomer used is usually 0.01 parts by mass or more and 10 parts by mass or less, preferably 0.03 parts by mass or more and 5 parts by mass or less, more preferably 0 with respect to 100 parts by mass of the polymerizable monomer for core. .05 parts by mass or more and 1 part by mass or less. When the amount of the macromonomer used is within this range, the storage stability and the fixing property can be improved in a balanced manner.

  The organic solvent used in the dissolution suspension method is not particularly limited as long as it can dissolve and / or disperse the toner composition. As a preferable thing, it is preferable that the boiling point of this solvent is less than 150 degreeC from the point of being easy to remove. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone. , Tetrahydrofuran and the like can be used alone or in combination of two or more.

  In this case, as the binder resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like, and polymers of the substitution products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Methyl ketone copolymer, styrene-butadiene Styrene copolymers such as polymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, and the like, which can be used alone or in combination.

  In the solution suspension method, the toner obtained by adding a toner binder component made of a modified polyester resin capable of reacting with active hydrogen to a mixed solution of the organic solvent to achieve both storage stability and fixing property of the obtained toner is also used. The effects of the invention are manifested. The modified polyester is stretched in droplets suspended in an aqueous medium.

  Examples of the modified polyester capable of reacting with active hydrogen include a polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) obtained by reacting a polyester having an active hydrogen group with a polyisocyanate (PIC). Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred. Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and DIO alone or a mixture of DIO and a small amount of TO is preferable. Examples of the diol include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Adducts of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) of the above alicyclic diols; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene having 2 to 12 carbon atoms. Concomitant use with glycol. Examples of the trihydric or higher polyol include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol) PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

  As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. .2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] is 5 or less, the low-temperature fixability is improved. When the molar ratio of [NCO] is 1 or more, the urea content in the modified polyester is sufficient, and the hot offset resistance is improved. The content of the polyisocyanate component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 2 to 20% by mass. When it is 0.5% by mass or more, the hot offset resistance is improved, and it is advantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, when it is 40% by mass or less, the low-temperature fixability is improved. The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. . When the number is 1 or more per molecule, the molecular weight of the modified polyester such as urea-modified polyester is increased, and the hot offset resistance is improved.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of a modified polyester such as urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is within this range, the molecular weight of the modified polyester is increased, and the hot offset resistance is improved. In the present invention, the polyester modified with a urea bond (UMPE) may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is 10% or more, the hot offset resistance is improved.

  As the crosslinking agent and / or extender for the modified polyester capable of reacting with active hydrogen, the amines (B) are used.

  An inorganic or organic dispersion stabilizer is preferably added to the aqueous medium. The types of inorganic compounds used as the dispersion stabilizer include hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, Examples thereof include aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound used as the dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. Further, a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the initial action of the dispersion stabilizer. Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like. When an inorganic compound is used as the dispersion stabilizer, a commercially available product may be used as it is. However, in order to obtain finer particles, the above inorganic compound may be generated and used in an aqueous medium. For example, in the case of calcium phosphates such as hydroxyapatite and tricalcium phosphate, an aqueous phosphate solution and an aqueous calcium salt solution may be mixed with high stirring.

  When a toner is obtained by suspension polymerization, an oil-soluble initiator and / or a water-soluble initiator is used as the polymerization initiator. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer, a polymer having a peak molecular weight of 10,000 to 100,000 is usually obtained. A toner having melting characteristics can be obtained.

  The pigment used in the toner produced by the production method of the present invention is not particularly limited, and the following known pigments can be used.

  Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 180.

  Examples of the orange pigment include the following. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

  Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, and those that are toned to black using the yellow pigment, red pigment, and blue pigment. These pigments can be used alone or in combination and further in a solid solution state.

  In addition, it is preferable that content of a pigment is 3.0 to 10.0 mass parts with respect to 100 mass parts of binder resin or a polymerizable monomer.

  In the toner of the present invention, in addition to the resin having an ionic functional group, the following resins can be used as long as the effects of the present invention are not affected. Styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethyl methacrylate ethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene , Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These can be used alone or in combination.

  The toner of the present invention may contain a charge control agent. Examples of charge control agents include metal compounds of aromatic carboxylic acids represented by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc .; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds And calixarene. Examples of the positive charge control agent include the following quaternary ammonium salts and polymer compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds. The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and a dispersion method, and is not uniquely limited.

  The toner of the present invention may contain a wax as a release agent. The types of wax include petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes such as polyethylene wax and polypropylene wax; Derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof; higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and derivatives thereof; Include waxes. Of these, paraffin wax, ester wax and hydrocarbon wax are particularly preferred from the viewpoint of excellent releasability.

  In the toner of the present invention, a fluidity improver may be added for the purpose of improving fluidity. Types of fluidity improvers include: fluororesin powders such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate, zinc stearate; titanium oxide powder, aluminum oxide Powders, metal oxides such as zinc oxide powders, or powders obtained by hydrophobizing the above metal oxides; and fine silica powders such as wet-process silica and dry-process silica, or silane coupling agents and titanium coupling agents on these silicas And surface-treated silica fine powder that has been surface-treated with a treating agent such as silicone oil.

  Hereinafter, various measurement methods related to the present invention will be described.

<NMR (composition analysis of resin having ionic functional group)>
The structure of the pigment dispersant is determined using nuclear magnetic resonance spectroscopy ( ¹ H-NMR) [400 MHz, CDCl 3, room temperature (25 ° C.)].
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times

  The molar ratio of each monomer component is obtained from the integral value of the obtained spectrum, and the composition ratio (mol%) is calculated based on this.

<PKa>
0.100 g of the measurement sample is precisely weighed in a 250 ml tall beaker, 150 ml of THF is added and dissolved over 30 minutes. A pH electrode is placed in this solution, and the pH of the sample THF solution is read. Thereafter, 10 μl of 0.1 mol / l potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.) is added, and the pH is read and titrated each time. A 0.1 mol / l potassium hydroxide ethyl alcohol solution is added until the pH becomes 10 or more and there is no change in pH even when 30 μl is added. From the obtained results, the pH is plotted against the addition amount of 0.1 mol / l potassium hydroxide ethyl alcohol solution to obtain a titration curve. pKa is obtained as follows. From the obtained titration curve, the point where the slope of the pH change is the largest is taken as the neutralization point, and the pH at half the amount of the 0.1 mol / l potassium hydroxide ethyl alcohol solution required up to the neutralization point is titrated. The pH value read from the curve is taken as pKa.

<Measurement method of hydrophobic parameter HP>
The hydrophobicity parameter HP is measured as follows.

  Take 10 mg of resin having an ionic functional group in an 8 ml sample bottle, dissolve in 1.48 g of chloroform, and measure the initial mass (W1). While stirring with a magnetic stirrer, (a) 100 mg of heptane is added dropwise to the sample bottle and stirring is continued for 20 seconds. (B) Confirm whether it is cloudy visually. If it is not cloudy, repeat the operations (a) and (b). The operation is stopped at the point where the cloudiness is confirmed (precipitation point), and the mass (W2) is measured. All measurements are performed at 25 ° C.

HP is calculated according to the following equation. The specific gravity of heptane at 25 ° C. is 0.684 g / ml, and the specific gravity of chloroform is 1.48 g / ml.
Hydrophobic parameter = {(W2-W1) /0.684} / {(W2-W1) /0.684) +1}

  The same measurement is performed three times, and the average value is HP.

<Molecular weight measurement of resin>
The molecular weight and molecular weight distribution of the resin used in the present invention are calculated in terms of polystyrene by gel permeation chromatography (GPC). When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group. Therefore, it is necessary to prepare a sample in which the acid group is capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

The molecular weight is measured by GPC as follows. The above resin was added to THF (tetrahydrofuran), and the solution which was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter having a pore size of 0.2 μm “Mysholy Disc” (manufactured by Tosoh Corporation) to obtain a sample solution. Measure under the following conditions. In addition, sample solution preparation adjusts the quantity of THF so that the density | concentration of resin may be 0.8 mass%. If the resin is difficult to dissolve in THF, a basic solvent such as DMF can be used.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin column listed below is used. Specifically, trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, manufactured by Tosoh Corporation,
F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

  Hereinafter, the present invention will be described in more detail with specific production methods, examples, and comparative examples, but this does not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

<Synthesis Example of Polymerizable Monomer M-1>
1,4-dihydroxybenzoic acid 18.0g was dissolved in methanol 150mL, potassium carbonate 36.9g was added, and it heated at 65 degreeC. To this reaction solution, a mixed solution of 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise, and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH = 2 and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of a polymerizable monomer M-1 represented by the following structural formula (7).

<Synthesis Example of Polymerizable Monomer M-2>
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. To this dispersion, 144 g of tert-butyl alcohol was added and stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this dispersion and stirring was performed for 30 minutes three times. The reaction solution was cooled to room temperature and poured slowly into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, 74.9 g of a salicylic acid intermediate represented by the following structural formula (8) was obtained by drying at 80 ° C.

  Except for changing 18.0 g of 2,4-dihydroxybenzoic acid to 25.0 g of the salicylic acid intermediate of the structural formula (8), the following structural formula (9) 20.1 g of the polymerizable monomer M-2 shown was obtained.

<Synthesis Example of Polymerizable Monomer M-3>
A salicylic acid intermediate was obtained in the same manner as the synthesis of the polymerizable monomer M-2 except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. A polymerizable monomer M-3 represented by the following structural formula (10) was obtained by the same method as the synthesis example of the polymerizable monomer M-1 except that 32 g of the obtained salicylic acid intermediate was used.

<Synthesis Example of Polymerizable Monomer M-4>
Except for changing 18.0 g of 2,4-dihydroxybenzoic acid to 18 g of 2,3-dihydroxybenzoic acid, the polymerizability of the following structural formula (11) is the same as the synthesis example of the polymerizable monomer M-1. Monomer M-4 was obtained.

<Synthesis Example of Polymerizable Monomer M-5>
Except for changing 18.0 g of 2,4-dihydroxybenzoic acid to 18 g of 2,6-dihydroxybenzoic acid, the polymerizability of the following structural formula (12) is the same as the synthesis example of the polymerizable monomer M-1. Monomer M-5 was obtained.

<Synthesis Example of Polymerizable Monomer M-6>
Except for changing 18.0 g of 2,4-dihydroxybenzoic acid to 18 g of 2,5-dihydroxy-3-methoxybenzoic acid, the same method as in the synthesis example of polymerizable monomer M-1, the following structural formula (13 ) Polymerizable monomer M-6 was obtained.

<Synthesis Example of Polymer A-1>
The polymerizable monomer M-1 (4.5 g) represented by the formula (7), styrene (52.3 g), and stearyl methacrylate (13.2 g) are dissolved in 42.0 ml of DMF, and 1 hour with nitrogen bubbling. After stirring, it was heated to 110 ° C. To this reaction solution, a mixture of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) (2.1 g) and 42 ml of toluene was added dropwise as an initiator. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at methanol 1L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure, thereby polymer A-1 (66.5 g). Got. The obtained polymer A-1 was subjected to NMR analysis, and the composition ratio of each monomer component was calculated. In addition, molecular weight, pKa, and hydrophobicity parameters were measured. The results are shown in Table 1.

<Synthesis Example of Polymers A-2 to A-8>
The polymer A-1 except that the polymerizable monomer M-1 was changed to polymers M-2 to M-6, 5-vinylsalicylic acid and 1-vinylnaphthalene-2-carboxylic acid, respectively, and the amount was adjusted. The same operations as in Example 1 were performed to obtain polymers A-2 to A-8. The obtained polymers A-2 to A-8 were subjected to NMR analysis, and the composition ratio of each monomer component was calculated. In addition, molecular weight, pKa, and hydrophobicity parameters were measured. The results are shown in Table 1.

<Synthesis Example of Polymer A-9>
Polymer A having the physical properties shown in Table 1 below was carried out in the same manner as Polymer A-1, except that the amounts of styrene, stearyl methacrylate, and polymerizable monomer M-1 were adjusted. -9 was obtained.

<Synthesis Example of Polymers A-10 to A-12>
Polymer A having the physical properties shown in Table 1 below, except that stearyl methacrylate was changed to octyl methacrylate, octacosyl methacrylate, and butyl acrylate, and the amount was adjusted. -10 to A-12 were obtained.

<Synthesis Example of Polymer A-13>
A polymer A-13 having the physical properties shown in Table 1 was obtained in the same manner as in Polymer A-1, except that stearyl methacrylate was not added.

<Synthesis Example of Comparative Polymer A-14>
A comparative polymer A-14 [aluminum complex of formula (1), R ¹ = hydrogen atom] in the effect of the present invention was synthesized as follows with reference to Patent Document 2.

  A 25.7% aqueous solution of aluminum sulfate (90.6 g) was added to 519 mL of water and heated to 95 ° C. To this solution, 20% sodium hydroxide solution (73.7 g) was added to 500 mL of water, then polymerizable monomer M-1 (50.0 g) was added, and the solution heated to 95 ° C. was added over 25 minutes. The mixture was heated and stirred for 3 hours. Then, it filtered, washed with water, and dried at 80 degreeC for 48 hours, and 57.2g of aluminum containing polymerizable monomers M-7 were obtained.

Next, 60.0 parts of toluene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and refluxed under a nitrogen stream. Next, the following raw materials and solvent were mixed to prepare a monomer mixture.
Polymerizable monomer M-7 4.00 parts Styrene 96.0 parts Xylene 60.0 parts

  To this monomer mixture, 10.0 parts of t-butylperoxyisopropyl monocarbonate (75% hydrocarbon solvent diluted product) as a polymerization initiator was further mixed and added dropwise to the reaction vessel over 30 minutes. . The mixture was stirred at 125 ° C. for 4 hours, and cooled to room temperature after completion of the reaction. The obtained polymer-containing composition was dropped into a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 200 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain polymer A-14 containing aluminum. It was pKa = 7.3 and HP = 0.44 of polymer A-14.

  Examples of toner production by the suspension polymerization method in the present invention will be illustrated below.

<Manufacture of toner 1>
(Preparation of aqueous medium)
To 1300.0 parts of ion-exchanged water heated to a temperature of 60 ° C., 9.0 parts by weight of tricalcium phosphate is added. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at a stirring speed of 15,000 rpm to prepare an aqueous medium.

(Preparation of polymerizable monomer composition including toner composition)
A polymerizable monomer composition was prepared using the following raw materials.
-Styrene monomer: 78.0 parts-n-butyl acrylate: 22.0 parts-Carbon black: 7.5 parts-Polyester resin; Polymer B-1 [(Polycondensate of propylene oxide modified bisphenol A and phthalic acid , Tg = 75.9 ° C., Mw = 11000, Mn = 4200, acid number 11, pKa = 4.5, HP = 0.57)]: 5.0 parts hydrocarbon wax (Tm = 78 ° C.): 9 0.03 part, zinc compound of 3,5-di-tert-butylsalicylic acid [Bontron E84 (manufactured by Orient Chemical Industries)]: 3.00 part Polymer A-1: 0.7 part Aluminum ethoxide (river Ken Fine Chemical Co., Ltd.): 1.0 part

  The above raw materials were dissolved and dispersed for 3 hours with an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain a polymerizable monomer composition.

(Manufacture of toner particles 1)
Subsequently, the polymerizable monomer composition was put into the aqueous medium, and perbutyl PV [10 hour half-life temperature 54.6 ° C. (manufactured by NOF)]: 9.0 parts was added as a polymerization initiator. High-speed stirring device T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 20 minutes at a stirring speed of 10,000 rpm and granulated.

  Then, it moved to the propeller-type stirring apparatus, and it was made to react at the temperature of 70 degreeC for 5 hours, stirring at 100 rpm, Then, it heated up to the temperature of 80 degreeC, and also reacted for 2 hours.

  Next, 200.0 parts of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the vessel was performed for 5 hours. The distillation fraction was 700.0 parts. After completion of distillation, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the vessel to lower the pH to 1.5, and the dispersion stabilizer was dissolved. Further, the toner particles 1 were obtained by filtration, washing, and drying.

(Manufacture of toner 1)
100.0 parts of the above toner particles 1 are mixed with 1.0 part of hydrophobic silica fine particles (number average primary particle size: 7 nm) treated with dimethyl silicone oil as an external additive, using an FM mixer (Nippon Coke Kogyo Co., Ltd.). The toner 1 was obtained for 10 minutes.

<Manufacture of toners 2 to 8>
Toners 2 to 8 were obtained in the same manner as in the production of the toner 1 except that the polymer A-1 was changed to the polymers A-2 to A-8.

<Manufacture of toners 9 to 15>
Aluminum etoxide is ALCH-TR (manufactured by Kawaken Fine Chemical Co., Ltd.), Plenact AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.), zinc (II) acetylacetonate, iron (III) acetylacetonate, titanium (IV) Toners 9 to 15 were obtained in the same manner as in the production of the toner 1 except that each of them was changed to acetylacetonate, cobalt (III) acetylacetonate, or zirconium (IV) acetylacetonate.

<Manufacture of toners 16 to 20>
Toners 16 to 20 were obtained in the same manner as in the production of the toner 1 except that the polymer A-1 was changed to the polymers A-9 to A-13.

<Manufacture of toners 21 to 23>
Carbon black is added to C.I. I. Pigment blue 15: 3, C.I. I. Pigment red 122, C.I. I. Toners 21 to 23 were obtained in the same manner as in the production of the toner 1 except that the pigment yellow 155 was used.

<Manufacture of Comparative Toners C1 to C4>
Except that the polymer A-1 and aluminum ethoxide were not added, the same operations as in the production of the toner 1 and 21 to 23 were performed to obtain toners C1 to C4.

<Production of Comparative Toner C5>
A toner C5 was obtained in the same manner as in the production of the toner 1 except that the polymer A-1 was not added.

<Production of Comparative Toner C6>
A toner C6 was obtained in the same manner as in the production of the toner 1 except that aluminum ethoxide was not added.

<Production of Comparative Toner C9>
A toner C9 was obtained in the same manner as in the production of the toner 1 except that the polymer A-1 was changed to the polymer A-14.

  Examples of toner production by the dissolution suspension method in the present invention will be illustrated below.

<Manufacture of Toner 24>
With reference to Patent Document 1, the toner 24 was produced as follows. The toner 24 is obtained by adding the polymer A-1 to the toner described in Patent Document 1.

(Preparation of aqueous medium)
To 1300.0 parts of ion-exchanged water heated to a temperature of 60 ° C., 9.0 parts of tricalcium phosphate is added. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at a stirring speed of 15,000 rpm to prepare an aqueous medium.

(Low molecular polyester; synthesis of polymer B-2)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. It reacted for 2 hours and obtained the polymer B-1. Polymer B-2 had a number average molecular weight of 2700, a weight average molecular weight of 6300, Tg of 44 ° C., an acid value of 24, pKa = 4.3, and HP = 0.38.

(Synthesis of intermediate polyester)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain an intermediate polyester 1. The intermediate polyester 1 had a number average molecular weight of 2400, a weight average molecular weight of 10900, Tg of 57 ° C., an acid value of 1.0, and a hydroxyl value of 44. Next, 411 parts of intermediate polyester 1, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Got.

(Synthesis of ketimine)
A reaction vessel equipped with a stir bar and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and reacted at 50 ° C. for 5 hours to obtain ketimine compound 1. The amine value of ketimine compound 1 was 403.

(Preparation of organic solvent composition containing toner composition)
-Ethyl acetate: 150 parts-Carbon black: 7.5 parts-Low molecular weight polyester (Polymer B-2): 67.0 parts-Carnauba WAX: 4.4 parts-CCA (salicylic acid metal complex E-84: Orient Chemistry) Industry): 0.90 part Preneact AL-M (Ajinomoto Fine Techno Co., Ltd.): 0.38 part Polymer A-1: 0.7 part

  The above raw materials were dissolved and dispersed for 3 hours with an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain an organic solvent composition.

(Manufacture of toner particles 24)
Subsequently, 224 parts of the organic solvent composition, 42.8 parts of the prepolymer 1 and 1.8 parts of the ketimine compound 1 were charged into the aqueous medium. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 20 minutes at a stirring speed of 10,000 rpm and granulated.

  Thereafter, the mixture was transferred to a propeller type stirring device and stirred at 100 rpm while removing the solvent at 30 ° C. for 8 hours, and then aged at 45 ° C. for 4 hours.

  Thereafter, dilute hydrochloric acid was added to the container to lower the pH to 1.5, and the dispersion stabilizer was dissolved. Further, the toner particles 24 were obtained by filtration, washing, and drying.

(Manufacture of toner 24)
To 100.0 parts of the toner particles 24, 1.0 part of hydrophobic silica fine particles (number average primary particle size: 7 nm) treated with dimethyl silicone oil as an external additive was mixed with FM mixer (Nippon Coke Kogyo Co., Ltd.). The toner 24 was obtained for 10 minutes.

<Manufacture of Comparative Toner C7>
A comparative toner C7 was obtained in the same manner as in the production of the toner 24 except that the polymer A-1 was not added.

  Examples of toner production by the pulverization method in the present invention will be illustrated below.

<Manufacture of toner 25>
Toner 25 was manufactured as follows with reference to Patent Document 3. The toner 25 is obtained by adding the polymer A-1 to the toner described in Patent Document 3.

(Manufacture of toner particles 25)
Polyester resin; Polymer B-3 (trade name NCP-11, manufactured by Nippon Carbide Industries, Ltd., acid value of 1 or less, hydroxyl value of 55, pKa = 4.6, HP = 0.40): 90 parts Metal dye (trade name Bontron S-34, manufactured by Orient Chemical Co., Ltd.): 1.5 parts, carbon black: 6.0 parts, metal alkoxide Ti (OC ₄ H ₉ ) ₄ : 1.0 part, polypropylene (product) Name Viscol 330P, manufactured by Sanyo Chemical Industries, Ltd.): 3.0 parts, Polymer A-1: 0.7 parts After mixing the raw materials having the above blending ratio with a super mixer and hot melt kneading with a biaxial kneader The toner particles 25 were obtained by pulverizing with a jet mill and then classifying with a dry air classifier.

(Manufacture of toner 25)
100 parts of toner particles 25 and 0.4 part of hydrophobic silica (trade name: Cabosil TS-530, manufactured by Cabot Corporation) are stirred for 1 minute in an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), A toner having hydrophobic silica adhered thereto was obtained. Further, 4 parts of the toner and 96 parts of a ferrite carrier (trade name: FL-1020, manufactured by Powder Tech Co.) without resin coating were mixed to prepare a two-component developer, and toner 25 was obtained.

<Production of Comparative Toner C8>
A comparative toner C8 as a two-component developer was obtained in the same manner as in the production of the toner 25 except that the polymer A-1 was not added.

[Examples 1 to 25 and Comparative Examples 1 to 9]
The following evaluations were performed using the toners 1 to 25 and the toners C1 to C9. Table 3 shows the results.

<Coloring power evaluation method (evaluation of toner by suspension polymerization method and dissolution suspension method)>
The toner contained therein was extracted from a cartridge for a commercially available color laser printer, Satera LBP7700C (manufactured by Canon Inc.), the inside was cleaned by air blow, and then the test toner was filled. In addition, a part of the Satera LBP7700C (manufactured by Canon Inc.) was remodeled so that the image density could be adjusted by a controller. Furthermore, it has been modified to work even when only one color process cartridge is installed.

Install the cartridge in the printer, set the controller so that the toner loading is 0.35 mg / cm ^2, and output a 6.5 cm x 14.0 cm rectangular solid image at the center of the transfer material to evaluate the image It was. As the transfer material, letter size HP LASERJET PAPER (manufactured by Hewlett-Packard, 90.0 g / m ² ) was used.

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 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.
Rank A: Image density is 1.45 or more B Rank: Image density is 1.35 or more and less than 1.45 C Rank: Image density is 1.20 or more and less than 1.35 D Rank: Image density is less than 1.20

<Coloring power evaluation method (evaluation of toner by pulverization method)>
A commercially available copying machine (trade name: SF-9800, manufactured by Sharp Corporation) is filled with test toner, and a controller is set so that the applied toner amount is 0.35 mg / cm ² . A rectangular solid image of 5 cm × 14.0 cm was output as an evaluation image. As the transfer material, letter size HP LASERJET PAPER (manufactured by Hewlett-Packard, 90.0 g / m ² ) was used.

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 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.
Rank A: Image density is 1.45 or more B Rank: Image density is 1.35 or more and less than 1.45 C Rank: Image density is 1.20 or more and less than 1.35 D Rank: Image density is less than 1.20

<Evaluation of chargeability (evaluation of toner by suspension polymerization method and dissolution suspension method)>
The chargeability (tribo) was evaluated using the triboelectric charge amount of the toner. A method for measuring the triboelectric charge amount of the toner will be described below.

First, a predetermined carrier (spherical carrier N-01, which is a standard carrier of the Imaging Society of Japan, surface-treated with a ferrite core) and toner are put in a plastic bottle with a lid, and a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) Shake for 1 minute at a speed of 4 reciprocations per second to charge the developer consisting of toner and carrier. Next, the triboelectric charge amount is measured by the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 1, about 0.5 to 1.5 g of the developer described above is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated from the following equation.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)

The evaluation criteria are as follows.
Rank A: Tribo is -20.0 mC / kg or more B Rank: Tribo is -10.0 mC / kg or more and less than -20.0 mC / kg Rank C: Tribo is -5.00 mC / kg or more and less than -10.0 mC / kg D rank: Tribo is 0.0 or more and less than -5.0 mC / kg

<Evaluation of chargeability (evaluation of toner by pulverization method)>
In the evaluation of chargeability (evaluation of toner by suspension polymerization method and dissolution suspension method), when evaluating a pulverized toner, the toner before mixing with the ferrite carrier (FL-1020) is used. Evaluation was performed by shaking with carrier (N-01).

The evaluation criteria are as follows.
Rank A: Tribo is -20.0 mC / kg or more B Rank: Tribo is -10.0 mC / kg or more and less than -20.0 mC / kg Rank C: Tribo is -5.00 mC / kg or more and less than -10.0 mC / kg D rank: Tribo is 0.0 or more and less than -5.0 mC / kg

<Testing method for heat-resistant storage stability>
10 g of toner is weighed into a 100 ml capacity polycup and placed in a thermostat with an internal temperature of 55 ° C. and left for 3 days. Thereafter, the polycup is taken out, and the state change of the toner inside is visually evaluated. The evaluation criteria are as follows.
A: No change B: There is an aggregate, but loosens immediately C: Many aggregates are not easily loosened D: Not loosened at all

  From the evaluation results of Examples 1 and 25 with respect to Comparative Examples 1 to 9, the combination of an ionic resin having a specified pKa and a metal compound exhibits good performance in terms of coloring power, chargeability, and storage stability. I understood.

  From the evaluation results of Examples 1 and 21 to 23 with respect to Comparative Examples 1 to 4, it was shown that the effect of the present invention was obtained for various pigments.

  From the evaluation results of Example 1 and 9 to 15, it was shown that a metal alkoxide, a β-diketone complex, or a complex thereof was effective as a metal compound.

  From the evaluation results of Examples 1, 24, and 25, it was shown that the effects of the present invention are effective in all toner production methods.

  In particular, the evaluation results of Examples 1 to 19 with respect to Examples 19 to 20 showed that the hydrophobic parameter HP was significantly effective when the hydrophobic parameter HP was 0.50 or more.

  In particular, the evaluation results of Examples 1 to 6 with respect to Examples 7 and 8 showed that the polymer had a remarkable effect when the polymer had the structure of the formula (1).

  In particular, the evaluation results of Examples 1, 17, and 18 with respect to Example 19 showed that there was a remarkable effect when n in Formula (2) was 7 to 27.

  From the evaluation results of Comparative Examples 7 and 8 (Patent Documents 1 and 3), the pKa of the polyester resin (Polymer B-1 and Polymer B-2) has little interaction with the metal compound and good performance is obtained. In contrast, the evaluation results of Examples 24 and 25 showed that the performance was greatly improved by the addition of an ionic resin having a specified pKa.

  In the evaluation results of Comparative Example 9 (Patent Document 2), although the chargeability was good, it was impossible to achieve both coloring power and storage stability.

  1 Suction machine (at least the part in contact with the measurement container 2 is an insulator), 2 metal measurement container, 3 500 mesh screen, 4 metal lid, 5 vacuum gauge, 6 air volume control valve, 7 suction port, 8 condenser 9 Electrometer

Claims (5)

A toner having toner particles containing a pigment, a resin having an ionic functional group, and a metal compound,
The acid dissociation constant pKa of the resin having an ionic functional group is 6.0 or more and 9.0 or less, and the metal compound is any one of a metal alkoxide, a β-diketone metal complex, or a complex thereof. Toner. The toner according to claim 1, wherein the hydrophobic parameter HP of the resin having an ionic functional group is 0.50 or more.
(However, HP is the amount of heptane at the precipitation point of the resin having the ionic functional group when heptane is added to a solution containing 0.01 part by weight of the resin having the ionic functional group and 1.48 parts by weight of chloroform. Indicates volume fraction.)   The toner according to claim 1, wherein the metal compound contains any one of Al, Zn, Fe, Ti, Co, and Zr. The toner according to claim 1, wherein the resin having an ionic functional group has at least a structure represented by the following formula (1).

[In Formula (1), R < ¹ > shows a hydroxy group, an alkyl group, or an alkoxy group. ] The toner according to claim 1, wherein the resin having an ionic functional group has at least a unit represented by the following formula (2).

[N in the formula (2) represents an integer of 7 to 27. ]

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