JP2020173414A - toner - Google Patents

Abstract

To provide a toner which is excellent in low temperature fixability and heat-resistant storage property, and is excellent in durability and releasability.SOLUTION: A toner has toner particles containing a binder resin and a release agent, in which the binder resin contains a polymer A having a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer, the first polymerizable monomer is selected from (meth)acrylate having an alkyl group having 18 to 36 carbon atoms, content ratios of the first monomer unit and the second monomer unit in the polymer A are specific ranges, when an SP value of the first monomer unit is represented by SP11 and an SP value of the second monomer unit is represented by SP21, the following expression (1): 3.00≤SP21-SP11≤25.00 is satisfied, and a molecular weight of the release agent is 1,000 or more.SELECTED DRAWING: None

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, and toner jet recording methods.

In recent years, energy saving has been considered as a major technical issue in electrophotographic devices, and a significant reduction in the amount of heat required for the fixing device has been studied. In particular, in toner, there is an increasing need for so-called "low temperature fixability", which enables fixing with lower energy.
As a method for enabling fixing at a low temperature, lowering the glass transition point (Tg) of the binder resin in the toner can be mentioned. However, since lowering Tg leads to lowering the heat-resistant storage stability of the toner, it is said that it is difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner in this method.
Therefore, in order to achieve both low-temperature fixability and heat-resistant storage stability of the toner, a method of using a crystalline vinyl resin as the binder resin has been studied. Amorphous resins commonly used as binders for toner do not show a clear endothermic peak in differential scanning calorimetry (DSC) measurements, but when they contain crystalline resin components, they are used in DSC measurements. An endothermic peak appears. Crystalline vinyl resin has the property that it hardly softens to the melting point due to the regular arrangement of side chains in the molecule.
In addition, the crystal melts rapidly at the melting point, and the viscosity drops sharply with it. For this reason, it is attracting attention as a material that has excellent sharp meltability and has both low-temperature fixability and heat-resistant storage stability. Normally, a crystalline vinyl resin has a long-chain alkyl group as a side chain in the main chain skeleton, and the long-chain alkyl groups in the side chains crystallize to exhibit crystallinity as a resin.

Patent Document 1 proposes a toner that uses a crystalline vinyl resin having a crosslinked structure and is said to have excellent low-temperature fixability.
Patent Document 2 proposes a toner in which a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer is used as a core. As a result, both low-temperature fixability and heat-resistant storage stability can be achieved.

JP-A-2009-265644 Japanese Unexamined Patent Publication No. 2014-130243

However, the toner of Patent Document 1 is a crystalline vinyl resin obtained by copolymerizing only a polymerizable monomer having a long-chain alkyl group and a cross-linking agent, and has low elasticity near room temperature, so that the durability is inferior. I understood. In addition, it was found that the configuration does not use a mold release agent, and wrapping around the fuser occurs during fixing.
In Patent Document 2, it was found that the durability is inferior because the proportion of the polymerizable monomer having a long-chain alkyl group is high and the elasticity at around room temperature is low. It was also found that when printing with a high printing rate is performed, wrapping around the fuser is likely to occur. The reason for this is that crystalline vinyl resins are generally highly hydrophobic and use a mold release agent with a small molecular weight, so the mold release agent dissolves in the crystalline vinyl resin, resulting in mold release during fixing. It is presumed that it could not be demonstrated. It was also found that when the release agent dissolves in the crystalline vinyl resin, the crystallinity of the crystalline vinyl resin is destroyed, so that the heat-resistant storage stability is lowered.
From the above, further improvement is required to realize a toner having excellent low-temperature fixability and heat-resistant storage stability, as well as excellent durability and releasability.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner having excellent low-temperature fixability and heat-resistant storage stability, as well as excellent durability and releasability.

The present invention for solving the above problems is as follows.
A toner having toner particles containing a binder resin and a mold release agent.
The binding resin
A polymer having a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Contains A,
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the polymer A.
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfy (1)
A toner characterized by having a molecular weight of the release agent of 1000 or more.
3.00 ≤ (SP _21- SP ₁₁ ) ≤ 25.00 ... (1)
Further, the present invention is a toner having toner particles containing a binder resin and a mold release agent.
The binding resin
It contains polymer A, which is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer.
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. Yes,
The SP value of the first polymerizable monomer is SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is SP ₂₂ (J / cm ³ ) ^0.5. When, the following formula (2) is satisfied,
The release agent has a molecular weight of 1000 or more.
0.60 ≤ (SP _22- SP ₁₂ ) ≤ 15.00 ... (2)

According to the present invention, it is possible to provide a toner having excellent low-temperature fixability and heat-resistant storage stability, as well as excellent durability and releasability.

［式（Ｃ）中、Ｒ_Ａは水素原子、又はアルキル基（好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_Ｂは任意の置換基を表す。］
結晶性樹脂とは、示差走査熱量計（ＤＳＣ）測定において明確な吸熱ピークを示す樹脂を指す。 In the present invention, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In the present invention, the (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.
In the present invention, the "monomer unit" is defined as one carbon-carbon bond section in the main chain in which the vinyl-based monomer in the polymer is polymerized. The vinyl-based monomer can be represented by the following formula (C).

Wherein (C), R _A is a hydrogen atom, or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably methyl group) represents, R _B represents an optional substituent. ]
Crystalline resin refers to a resin that exhibits a clear endothermic peak in differential scanning calorimetry (DSC) measurements.

Normally, a crystalline vinyl resin has a long-chain alkyl group as a side chain in the main chain skeleton, and the long-chain alkyl groups in the side chains crystallize to exhibit crystallinity as a resin. Therefore, when a crystalline vinyl resin having a long-chain alkyl group is used, the higher the proportion of the long-chain alkyl group, the higher the crystallinity and the higher the melting point. In addition, sharp meltability is exhibited and low temperature fixability is excellent. However, when the proportion of long-chain alkyl groups increases, the elasticity of the crystalline vinyl resin decreases near room temperature, which makes the toner brittle and reduces its durability.
Therefore, in order to improve this decrease in durability, if copolymerization with another monomer is carried out and the proportion of long-chain alkyl groups is decreased, the crystallinity is extremely decreased and the melting point is decreased. As a result, the heat-resistant storage stability tends to decrease. In addition, the sharp melt property is lowered, and the low temperature fixability is lowered.

Further, a crystalline vinyl resin having many long-chain alkyl groups generally has a low polarity and a high affinity with a normal mold release agent, so that the mold release agent is compatible with the crystalline vinyl resin. It becomes easy to melt. Therefore, there is a drawback that the release agent is less likely to seep out to the surface of the toner particles at the time of fixing, and the release property is lowered.
In order to solve the above problems, the present inventors have determined the types and amounts of monomer units having long-chain alkyl groups in polymers used for binder resins, types and amounts of other monomer units, and theirs. The present invention was found as a result of diligent studies on the difference in SP value of the monomer unit and the molecular weight of the release agent.

The present invention is a toner having toner particles containing a binder resin and a mold release agent.
The binding resin
A polymer having a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Contains A,
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the polymer A.
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfy (1)
The release agent has a molecular weight of 1000 or more.
3.00 ≤ (SP _21- SP ₁₁ ) ≤ 25.00 ... (1)

Further, the present invention is a toner having toner particles containing a binder resin and a mold release agent.
The binding resin
It contains polymer A, which is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer.
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. Yes,
The SP value of the first polymerizable monomer is SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is SP ₂₂ (J / cm ³ ) ^0.5. When, the following formula (2) is satisfied,
The release agent has a molecular weight of 1000 or more.
0.60 ≤ (SP _22- SP ₁₂ ) ≤ 15.00 ... (2)
Here, the SP value is an abbreviation for the solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.

In the present invention, the binder resin contains the polymer A. The polymer A is a first monomer unit derived from the first polymerizable monomer, and a second monomer derived from a second polymerizable monomer different from the first polymerizable monomer. Has a unit. The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms. By having the first monomer unit, the polymer A becomes a resin exhibiting crystallinity.

The polymer A is a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. It has a monomer unit, the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5, and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5. Then, the following equation (1) is satisfied.
Further, in the polymer A, the SP value of the first polymerizable monomer is SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is SP ₂₂ (J). / Cm ³ ) When ^0.5 , the following equation (2) is satisfied.
3.00 ≤ (SP _21- SP ₁₁ ) ≤ 25.00 (1)
0.60 ≤ (SP _22- SP ₁₂ ) ≤ 15.00 (2)
The unit of the SP value in the present invention is (J / m ³ ) ^0.5 , but by 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ³ (J / m ³ ) ^0.5 ( cal / cm ³ ) Can be converted to a unit of ^0.5 .

By satisfying the above formula (1) or (2), the melting point is maintained without lowering the crystallinity of the polymer A. As a result, both low-temperature fixability and heat-resistant storage stability can be achieved. This mechanism is inferred as follows.
The first monomer unit is incorporated into a polymer, and crystallinity is exhibited by assembling the first monomer units with each other. Normally, when another monomer unit is incorporated, crystallization occurs. Since it inhibits, it becomes difficult to develop crystallinity as a polymer. This tendency becomes remarkable when the first monomer unit and the other monomer unit are randomly bonded in one molecule of the polymer.
On the other hand, in the present invention, by using a polymerizable monomer in which SP _{22 to} SP ₁₂ is in the range of the above formula (2), the first polymerizable monomer and the second polymerization are polymerized at the time of polymerization. It is considered that the sex monomers can be bonded continuously to some extent rather than randomly. As a result, the polymer A can be assembled with the first monomer units, and the crystallinity can be increased even if other monomer units are incorporated, so that the melting point can be maintained. Conceivable. That is, the polymer A preferably has a crystalline moiety containing a first monomer unit derived from the first polymerizable monomer. Further, the polymer A preferably has an amorphous moiety containing a second monomer unit derived from the second polymerizable monomer.
Further, when SP _{21 to} SP ₁₁ are in the range of the above formula (1), a clear phase separation state is formed in the polymer A without the first monomer unit and the second monomer unit being compatible with each other. It is considered that the melting point is maintained without lowering the crystallinity.

When SP _22- SP ₁₂ is smaller than 0.60, the melting point of the polymer A is lowered and the heat-resistant storage stability is lowered. Further, if it is larger than 15.00, it is considered that the copolymerizability of the polymer A is inferior, non-uniformity occurs, and the low temperature fixability is lowered. The lower limit of SP _22- SP ₁₂ is preferably 2.00 or more, and more preferably 3.00 or more. The upper limit is preferably 10.00 or less, and more preferably 7.00 or less.
Similarly, when SP _21- SP ₁₁ is smaller than 3.00, the melting point of the polymer A is lowered, and the heat-resistant storage stability is lowered. Further, if it is larger than 25.00, it is considered that the copolymerizability of the polymer A is inferior, non-uniformity occurs, and the low temperature fixability is lowered. The lower limit of SP _21- SP ₁₁ is preferably 4.00 or more, and more preferably 5.00 or more. The upper limit is preferably 20.00 or less, and more preferably 15.00 or less.

In the present invention, when a plurality of types of monomer units satisfying the requirements of the first monomer unit are present in the polymer A, the value of SP ₁₁ in the formula (1) is a weighted average of the SP values of each monomer unit. Use as a value. For example, the monomer unit A having an SP value of SP ₁₁₁ is contained in A mol% based on the number of moles of the entire monomer unit satisfying the requirements of the first monomer unit, and the monomer unit B having an SP value of SP ₁₁₂ is included in the first monomer unit. The SP value (SP ₁₁ ) when (100-A) mol% is included based on the total number of moles of the monomer unit satisfying the requirements of
SP ₁₁ = (SP ₁₁₁ x A + SP ₁₁₂ x (100-A)) / 100
Is. The same calculation is performed when three or more monomer units satisfying the requirements of the first monomer unit are included. On the other hand, SP ₁₂ also represents an average value calculated by the molar ratio of each first polymerizable monomer.
On the other hand, the monomer unit derived from the second polymerizable monomer corresponds to all the monomer units having SP ₂₁ satisfying the formula (1) with respect to SP ₁₁ calculated by the above method. Similarly, the second polymerizable monomer corresponds to all the polymerizable monomers having SP ₂₂ satisfying the formula (2) with respect to SP ₁₂ calculated by the above method.
That is, when said second polymerizable monomer is 2 or more polymerisable monomers, SP ₂₁ denotes a SP value of the monomer units derived from each of the polymerizable monomer, SP ₂₁ -SP ₁₁ is determined for the monomer unit derived from each second polymerizable monomer. Similarly, SP ₂₂ represents the SP value of each polymerizable monomer, and SP _22- SP ₁₂ is determined for each second polymerizable monomer.

The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A, and is in the polymer A. The content ratio of the second monomer unit is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the polymer A.
Further, the polymer A is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60. Based on the total number of moles of the total polymerizable monomer in the composition.
It is 0 mol%, and the content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 20.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. It is 95.0 mol%.

When the content ratio of the first monomer unit in the polymer A and the content ratio of the first polymerizable monomer in the composition are within the above ranges, the sharp melt property of the polymer A is exhibited. A toner with excellent low-temperature fixability. When the content ratio is smaller than 5.0 mol%, the amount of crystals of the polymer A decreases, and the sharp meltability deteriorates. As a result, the low temperature fixability is lowered. On the other hand, if the content ratio is larger than 60.0 mol%, the elasticity near room temperature decreases, and the durability of the toner decreases.
The content ratio of the first monomer unit in the polymer A and the content ratio of the first polymerizable monomer in the composition are preferably 10.0 mol% to 60.0 mol%, and more. It is preferably 20.0 mol% to 40.0 mol%.
When the polymer A has a monomer unit derived from a (meth) acrylic acid ester having two or more kinds of alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit is the total of them. Represents the molar ratio. Similarly, when the composition used for the polymer A contains two or more kinds of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms, the content ratio of the first polymerizable monomer is similarly set. Represents the total molar ratio of them.

When the content ratio of the second monomer unit in the polymer A and the content ratio of the second polymerizable monomer in the composition are within the above ranges, the elasticity of the polymer A near room temperature is improved. However, it becomes a toner with excellent durability. In addition, since the polymer A does not inhibit the crystallization of the first monomer unit, the melting point can be maintained.
If the content ratio is less than 20.0 mol%, the elasticity of the polymer A is lowered and the durability of the toner is lowered. Further, when the content ratio is larger than 95.0 mol%, the sharp melt property of the polymer A is lowered and the low temperature fixability is lowered. The preferable range of the content ratio of the second monomer unit in the polymer A and the content ratio of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 mol%. More preferably, it is 40.0 mol% to 70.0 mol%.
When there are two or more types of monomer units derived from the second polymerizable monomer satisfying the formula (1) in the polymer A, the ratio of the second monomer unit represents the total molar ratio thereof. .. Similarly, when the composition used for the polymer A contains two or more kinds of second polymerizable monomers, the content ratio of the second polymerizable monomer represents the total molar ratio thereof. ..

The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
Examples of the (meth) acrylic acid ester having an alkyl group having 18 to 36 carbon atoms include a (meth) acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms [(meth) stearyl acrylate, (meth). ) Nonadesyl acrylate, Eikosyl acrylate, Heneikosanyl acrylate, Behenyl acrylate, Lignoceryl acrylate, Ceryl acrylate, Octacosa acrylate, (meth) Myricyl acrylate, dodria contour (meth) acrylate, etc.] and (meth) acrylic acid ester having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate, etc.] can be mentioned.
Of these, at least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms is preferable from the viewpoint of storage stability of the toner, and more preferable. At least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 30 carbon atoms, more preferably linear stearyl (meth) acrylate and (meth) acrylic. At least one selected from the group consisting of behenyl acid acid.
The first polymerizable monomer may be used alone or in combination of two or more.

Examples of the second polymerizable monomer include polymerizable monomers satisfying the formula (1) or the formula (2) among the polymerizable monomers listed below.
The second polymerizable monomer may be used alone or in combination of two or more.
Monomer having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.
A monomer having a hydroxy group; for example, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate and the like.
A monomer having an amide group; for example, acrylamide, an amine having 1 to 30 carbon atoms and a carboxylic acid having an ethylenically unsaturated bond having 2 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) are reacted by a known method. Monomer.

Monomer having a urethane group: For example, an alcohol having 2 to 22 carbon atoms (-2-hydroxyethyl methacrylate, vinyl alcohol, etc.) having an ethylenically unsaturated bond and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound]. (Benzenesulfonyl isocyanate, tosyl isocyanate, phenylisocyanate, p-chlorophenylisocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl Isocyanate, 3,5-dimethylphenylisocyanate and 2,6-dipropylphenylisocyanate, etc.), aliphatic diisocyanate compounds (trymethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1, , 3-Butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentenediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, etc. Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatic diisocyanate compounds (phenylenedi isocyanate, 2,4-tolylene diisocyanate, 2,6 -Torylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalene Diisocyanate and xylylene diisocyanate, etc.)] are reacted by a known method, and alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, etc.) Heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undeci Lu alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, setanol, heptadecanol, stearyl alcohol, isostearyl alcohol, ellaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecil alcohol, hen Eikosanol, behenyl alcohol, elcil alcohol, etc.) and isocyanate with 2 to 30 carbon atoms having an ethylenically unsaturated bond [2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1 '-Methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, etc.] A monomer obtained by reacting with a known method.

Monomers having urea groups: For example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (dinormal ethylamine, dinormal propylamine, di). Normal butylamine, etc.), aniline, cycloxylamine, etc.] and 2 to 30 carbon atoms having an ethylenically unsaturated bond.
A monomer obtained by reacting with the isocyanate of the above by a known method.
Monomer having a carboxy group; for example, methacrylic acid, acrylic acid, -2-carboxyethyl (meth) acrylic acid.
Of these, it is preferable to use a monomer having a nitrile group, an amide group, a urethane group, a hydroxy group, or a urea group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a urethane group, a hydroxy group, and a urea group and an ethylenically unsaturated bond. By having these, the melting point of the polymer A tends to be high, and the heat-resistant storage stability is likely to be improved. In addition, elasticity near room temperature increases, making it easier to improve durability.

As the second polymerizable monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caproate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, pivalic acid Vinyl esters such as vinyl and vinyl octylate are also preferably used. Vinyl esters are non-conjugated monomers and have low reactivity with the first polymerizable monomer. As a result, it is considered that it becomes easy to form a state in which the monomer units derived from the first polymerizable monomer are aggregated and bonded in the polymer A, the crystallinity of the polymer A is enhanced, and the low temperature fixability is improved. It becomes easier to achieve both heat-resistant storage stability.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Moreover, it is preferable that the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4)),
Urethane group (-NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms)),
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ is an independent hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))).
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (R ¹⁵ is Independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
Is,
Preferably, R ¹ is a nitrile group (-C ≡ N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4)),
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ is an independent hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))).
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (R ¹⁵ is Independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
Is.
R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is an independent hydrogen atom or methyl group. )

The polymer A is preferably a vinyl polymer. Examples of the vinyl polymer include a polymer of a monomer containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.
The polymer A is within a range that does not impair the molar ratio of the first monomer unit derived from the first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer described above. , A third polymerizable monomer that is not included in the range of the above formula (1) or formula (2) (that is, different from the first polymerizable monomer and the second polymerizable monomer). It may contain a third monomer unit derived from.
As the third polymerizable monomer, among the monomers exemplified as the second polymerizable monomer, a monomer that does not satisfy the above formula (1) or the above formula (2) can be used. ..
In addition, the following monomers can also be used. For example, styrene such as styrene and o-methylstyrene and derivatives thereof, methyl (meth) acrylate, -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, -2-butyl (meth) acrylate. (Meta) acrylic acid esters such as ethylhexyl. When these monomers satisfy the above formula (1) or formula (2), they can be used as the second polymerizable monomer.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate.

The toner particles contain a mold release agent having a molecular weight of 1000 or more. When the molecular weight is 1000 or more, the compatibility with the polymer A is lowered and the phase is separated. As a result, the release agent easily exudes to the surface of the toner particles at the time of fixing, so that the release property is improved.
When the molecular weight of the release agent is smaller than 1000, it becomes easy to be compatible with the polymer A in the toner particles, and it becomes difficult to exude at the time of fixing, so that the releasability is lowered. Further, by being compatible with the polymer A, the crystallinity of the polymer A is lowered, and the melting point is lowered, so that the heat-resistant storage stability is likely to be lowered.
Here, the molecular weight of the release agent refers to the peak molecular weight (Mp) in the gel permeation chromatography (GPC) measurement. The measuring method will be described later.
The molecular weight of the release agent is preferably 1500 or more. The upper limit is not particularly limited, but from the viewpoint of ensuring releasability, it is preferably 10,000 or less, and more preferably 5,000 or less.

The release agent is not particularly limited as long as it has a molecular weight of 1000 or more, and examples thereof include the following.
Aliphatic hydrocarbon waxes: low molecular weight polyethylenes, low molecular weight polypropylenes, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes to which these are oxidized and acidified.
Further, an ester wax containing a fatty acid ester as a main component can also be used. From the viewpoint of molecular weight, the ester wax is preferably a trifunctional or higher functional ester wax, and more preferably a tetrafunctional or higher functional ester wax.
The trifunctional or higher functional ester wax is obtained, for example, by condensation of a trifunctional or higher functional acid and a long-chain linear saturated alcohol, or synthesis of a trifunctional or higher functional alcohol and a long-chain linear saturated fatty acid.

Examples of trifunctional or higher functional alcohols that can be used in ester wax include, but are not limited to, the following. A plurality of ester waxes can be mixed and used.
Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol. In addition, as these condensates, so-called polyglycerin such as glycerin-condensed diglycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin, trimethylolpropane condensed diglycerolpropane, trimethylolpropane and pentaerythritol Examples thereof include condensed dipentaerythritol and tricentaerythritol.
Of these, a structure having a branched structure is preferable, pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol is particularly preferable.

The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n of 5 or more and 28 or less are preferably used.
Examples include, but are not limited to: In some cases, they can be mixed and used. Examples thereof include caproic acid, caprylic acid, octyl acid, nonyl acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid and behenic acid. From the viewpoint of the melting point of the wax, myristic acid, palmitic acid, stearic acid and behenic acid are preferable.

Examples of trifunctional or higher functional acids include, but are not limited to, the following. In some cases, they can be mixed and used. Trimellitic acid, butanetetracarboxylic acid.

The long-chain linear saturated alcohol is represented by C _n H _{2n + 1} OH, and those having n of 5 or more and 28 or less are preferably used.
Examples include, but are not limited to: In some cases, they can be mixed and used. Examples thereof include caprylic alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and behenyl alcohol. From the viewpoint of the melting point of the wax, myristyl alcohol, palmityl alcohol, stearyl alcohol and behenyl alcohol are preferable.

The release agent preferably contains an aliphatic hydrocarbon-based wax, and more preferably an aliphatic hydrocarbon-based wax. Since the aliphatic hydrocarbon wax has a low polarity, it easily exudes from the polymer A at the time of fixing.
The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less. When the content of the release agent in the toner particles is within the above range, the release property at the time of fixing can be easily ensured. When it is 1.0% by mass or more, the releasability of the toner becomes good. When it is 30.0% by mass or less, the release agent is not easily exposed on the surface of the toner particles, and the heat-resistant storage stability is improved.
The melting point of the release agent is preferably 60 ° C. or higher and 120 ° C. or lower. When the melting point of the release agent is in the above range, it easily melts at the time of fixing and exudes to the surface of the toner particles, so that the release property is easily exhibited. More preferably, it is 70 ° C. or higher and 100 ° C. or lower. When the melting point is 60 ° C. or higher, the release agent is less likely to be exposed on the surface of the toner particles, and the heat-resistant storage stability is improved. On the other hand, when the melting point is 120 ° C. or lower, the mold release agent is appropriately melted at the time of fixing, and the low temperature fixing property and the offset resistance are improved.

When the SP value of the polymer A is SP ₃ (J / cm ³ ) ^0.5 and the SP value of the release agent is SP _W (J / cm ³ ) ^0.5 , SP ₃ and SP _W are expressed by the following formulas ( It is preferable to satisfy 3).
(SP _3- SP _w ) ≧ 1.00 ・ ・ ・ (3)
When SP _3- SP _w satisfies the formula (3), the polymer A and the release agent are easily phase-separated in the toner. Further, the release agent has a lower polarity than the polymer A. As a result, the mold release agent effectively exudes to the surface of the toner particles at the time of fixing, and the mold release property is easily improved.
The calculation method of SP ₃ and SP _w will be described later. (SP _3- SP _w ) is preferably 1.50 or more. On the other hand, the upper limit is not particularly limited, but is preferably 10.00 or less, and more preferably 5.00 or less.

From the viewpoint of maintaining the crystallinity of the toner, the acid value of the polymer A is preferably 30.0 mgKOH / g or less, and more preferably 20.0 mgKOH / g or less.
When the acid value is 30.0 mgKOH / g or less, it is difficult to inhibit the crystallization of the polymer A, and the melting point can be easily controlled appropriately. The lower limit of the acid value is not particularly limited, but is preferably 0 mgKOH / g or more.

Further, in the polymer A, the weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component measured by GPC is preferably 10,000 or more and 200,000 or less, and 20,000 or more and 150,000 or less. Is more preferable. When Mw is within the above range, elasticity near room temperature can be easily maintained.

Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the melting point of the polymer A is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 53 ° C. or higher and 70 ° C. or lower. When the melting point of the polymer A is 50 ° C. or higher, the heat-resistant storage stability is good, and when the melting point is 80 ° C. or lower, the low-temperature fixability is good.
The melting point of the polymer A can be adjusted depending on the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like.

The content of the polymer A in the binder resin is preferably 50.0% by mass or more. When it is 50.0% by mass or more, the sharp melt property of the toner is easily maintained and the low temperature fixability is improved. It is more preferably 80.0% by mass to 100% by mass, and it is further preferable that the binder resin is the polymer A.

Examples of the resin that can be used as the binder resin other than the polymer A include vinyl-based resins, polyester resins, polyurethane resins, and epoxy resins. Of these, vinyl resins, polyester resins, and polyurethane resins are preferable from the viewpoint of electrophotographic characteristics.
The polymerizable monomer that can be used for the vinyl resin is a polymerizable single amount that can be used for the above-mentioned first polymerizable monomer, second polymerizable monomer, and third polymerizable monomer. The body etc. can be mentioned. If necessary, two or more kinds may be used in combination.

The polyester resin can be obtained by reacting a polyvalent carboxylic acid having a divalent value or higher with a polyhydric alcohol.
Examples of the polyvalent carboxylic acid include the following compounds. Dibasic acids such as amber acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid, their anhydrides or lower alkyl esters thereof, and maleic acid, fumaric acid, An aliphatic unsaturated dicarboxylic acid such as itaconic acid and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and anhydrides thereof or lower alkyl esters thereof. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include the following compounds. Alkylene glycol (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol and polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); An alkylene oxide (ethylene oxide and propylene oxide) adduct of an alicyclic diol. The alkyl moiety of the alkylene glycol and the alkylene ether glycol may be linear or branched. Further, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used alone or in combination of two or more.
For the purpose of adjusting the acid value and hydroxyl value, monovalent acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol can also be used, if necessary.
The method for producing the polyester resin is not particularly limited, and for example, a transesterification method or a direct polycondensation method can be used alone or in combination.

Next, the polyurethane resin will be described. The polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and a resin having various functionalities can be obtained by adjusting the diol and the diisocyanate.
Examples of the diisocyanate component include the following. Aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and these diisocyanates. (Urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group-containing modified product; hereinafter also referred to as "modified diisocyanate"), and these modified products. A mixture of two or more of the above.

Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylylene diisocyanate.
In addition, examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.
Further, examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate and methylcyclohexylene diisocyanate.

Among these, aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms are particularly preferable, and XDI is particularly preferable. , IPDI and HDI.
Further, in addition to the diisocyanate component, a trifunctional or higher functional isocyanate compound can also be used.
As the diol component that can be used in the polyurethane resin, the same diol component as the divalent alcohol that can be used in the polyester resin described above can be used.

The toner may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, magnetic particles and the like. In addition, a colorant conventionally used for toner may be used.
Examples of the yellow colorant include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.
Examples of the magenta colorant include the following. Condensed azo compound, diketopyrrolopyrrole compound, anthraquinone compound, quinacridone compound, base dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, perylene compound. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254 are preferably used.

Examples of the colorant for cyan include the following. Copper phthalocyanine compound and its derivative, anthraquinone compound, basic dye lake compound. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.
The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, the content thereof is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

If necessary, a charge control agent may be contained in the toner particles. Further, the charge control agent may be externally added to the toner particles. By blending a charge control agent, it is possible to stabilize the charge characteristics and control the optimum triboelectric charge amount according to the developing system.
As the charge control agent, known ones can be used, and in particular, a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable.
Examples of the charge control agent for controlling the toner with load electrical properties include the following. Organic metal compounds and chelate compounds are effective, and examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds.
Examples of controlling the toner to be positively charged include the following. Examples thereof include niglosin, quaternary ammonium salts, metal salts of higher fatty acids, diorganosuvrates, guanidine compounds, and imidazole compounds.
The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. is there.

The toner particles may be used as they are as toner, or may be used as toner by adding an external agent such as inorganic fine particles to the toner particles.
It is preferable to add inorganic fine particles to the toner particles. Examples of the inorganic fine particles added to the toner particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, and their double oxide fine particles. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and homogenizing charge.
Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of a silicon halide, and wet silica produced from water glass. Among them, there are few silanol groups on the surface and inside the silica fine particles, and Na ₂ O and SO ₃ ^2-
Dry silica with less is preferable. Further, the dry silica may be composite fine particles of silica and other metal oxides produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

Further, by hydrophobizing the silica fine particles, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high humidity environment. Therefore, the silica fine particles that have been hydrophobized can be treated. It is more preferable to use it. The hydrophobization treatment prevents moisture absorption of silica fine particles, maintains the amount of charge of the toner, and improves developability and transferability.
Examples of the treatment agent for the hydrophobization treatment of silica fine particles include silicone oil, silane compound, silane coupling agent, other organosilicon compound, and organotitanium compound. These treatment agents may be used alone or in combination.
Among them, silica fine particles treated with silicone oil are preferable.

In the toner of the present invention, the release agent exudes to the surface of the toner particles during fixing and can prevent wrapping around the fuser. However, since the polymer A has high crystallinity in the toner, the polymer A recrystallizes after fixing. As a result, the surface of the fixed image may have minute irregularities. As a result, the gloss may decrease. Therefore, in order to maintain high gloss, it is preferable to prevent the surface of the toner particles from recrystallizing.
Silicone oil is easily compatible with polymer A and easily inhibits recrystallization. Therefore, the presence of silica fine particles treated with silicone oil on the surface of toner particles prevents recrystallization of toner on the surface of the fixed image. It hinders the formation of minute irregularities. Therefore, it becomes easy to suppress the decrease in gloss.

As the silicone oil used for treating the silica fine particles, known silicone oil can be used without particular limitation, but straight silicone is particularly preferable.
More specifically, for example, dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, methylhydrogen silicone oil and the like can be mentioned. The viscosity of the silicone oil used in the treatment is preferably 30 mm ² / s or more and 1200 mm ² / s or less, and more preferably 70 mm ² / s or more and 800 mm ² / s or less.
The method of treating the silicone oil may be, for example, directly mixing the silica fine particles and the silicone oil using a mixer such as a Henschel mixer, or a method of stirring the silica fine particles while spraying the silicone oil. Alternatively, a method may be used in which the silicone oil is dissolved or dispersed in an appropriate solvent (preferably adjusted to pH 4 with an organic acid or the like) and then mixed with silica fine particles to remove the solvent. Further, a method in which silica fine particles are placed in a reaction vessel, alcoholic water is added while stirring in a nitrogen atmosphere, a silicone oil-based treatment liquid is introduced into the reaction vessel to perform surface treatment, and the solvent is removed by heating and stirring. It may be.
The number average diameter of the primary particles of the silica fine particles is preferably 5 nm or more and 20 nm or less. Within the above range, it becomes easy to improve the fluidity of the toner.
The content of the inorganic fine particles is preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. More preferably, it is 0.2 parts by mass or more and 3.5 parts by mass or less.

It is preferable to further add silica particles having an average number of primary particles of 30 nm or more and 500 nm or less to the toner particles. More preferably, it is 50 nm or more and 300 nm or less. By adding the above silica particles, it is possible to fully exert the function as spacer particles and suppress toner deterioration at the developing nip and the regulating member nip.
The silica particles can be produced by the same production method as the above silica fine particles, but are preferably produced by the sol-gel method. The sol-gel method is a method of removing the solvent from the silica sol suspension obtained by hydrolyzing and condensing the alkoxysilane in an organic solvent in which water is present with a catalyst, drying the mixture, and forming particles. The silica particles obtained by this sol-gel method have an appropriate particle size and particle size distribution, and are monodisperse and spherical, so that they can be easily dispersed uniformly on the surface of the toner particles, and the toner has a stable spacer effect. The physical adhesion can be reduced.
The silica particles are preferably hydrophobized in the same manner as the silica fine particles.
The content of silica particles having an average number of primary particles of 30 nm or more and 500 nm or less is preferably 0.1 part by mass to 2.0 parts by mass with respect to 100 parts by mass of toner particles.

The toner particles may be produced by any conventionally known method such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and a pulverization method as long as the toner particles are within the scope of the present constitution, but the toner particles may be produced by the suspension polymerization method. It is preferably manufactured.
For example, a polymerizable monomer composition for producing a binder resin containing the polymer A is mixed with other additives such as a mold release agent and a colorant if necessary to obtain a polymerizable monomer composition. The polymerizable monomer composition is then added into a continuous phase (eg, an aqueous medium (which may optionally contain a dispersion stabilizer)). Then, the particles of the polymerizable monomer composition are formed in the continuous phase (in the aqueous medium), and the polymerizable monomer contained in the particles is polymerized. By doing so, toner particles can be obtained.

The calculation method and measurement method for various physical properties of toner and toner material are described below.
<Method for measuring the content ratio of monomer units derived from various polymerizable monomers in polymer A>
The content ratio of the monomer unit derived from various polymerizable monomers in the polymer A is measured by ¹ H-NMR under the following conditions.
-Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
・ Measurement frequency: 400MHz
-Pulse condition: 5.0 μs
-Frequency range: 10500Hz
・ Number of integrations: 64 times ・ Measurement temperature: 30 ° C
-Sample: 50 mg of the measurement sample is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare.
From the obtained ¹ H-NMR chart, among the peaks attributed to the components of the monomer unit derived from the first polymerizable monomer, the peaks attributed to the components of the monomer unit derived from others selects the independent peaks, calculates an integrated values S ₁ for the peak.
Similarly, from the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, a peak independent of the peaks attributed to the components of the monomer unit derived from other sources is selected. , an integrated value S ₂ is calculated for this peak.
Further, when the third polymerizable monomer is used, the component of the monomer unit derived from the peak attributable to the component of the monomer unit derived from the third polymerizable monomer is derived from the other. the peak attributable to select the independent peaks, calculates an integrated value S ₃ of the peak.
The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the above integrated values S ₁ , S ₂ and S ₃ . In addition, n ₁ , n _{2, and} n ₃ are the number of hydrogens in the component to which the peak focused on each site is assigned.
Content ratio (mol%) of monomer unit derived from the first polymerizable monomer =
{(S ₁ / n ₁ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100
Similarly, the ratio of the monomer units derived from the second polymerizable monomer and the third polymerizable monomer is determined as follows.
Content ratio (mol%) of monomer unit derived from the second polymerizable monomer =
{(S ₂ / n ₂ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} × 100
Content ratio (mol%) of monomer unit derived from the third polymerizable monomer =
{(S ₃ / n ₃ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100
When a polymerizable monomer containing no hydrogen atom is used in the constituent elements other than the vinyl group in the polymer A, the measurement nucleus is set to ¹³ C by using ¹³ C-NMR, and the single pulse mode is used. Measure in ¹ H-NMR and calculate in the same way.
Further, when the toner is produced by the suspension polymerization method, the peaks of the release agent and other resins may overlap and independent peaks may not be observed. As a result, the content ratio of the monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In that case, the polymer A'can be produced by performing the same suspension polymerization without using a release agent or other resin, and the polymer A'can be regarded as the polymer A and analyzed.

<Calculation method of SP value>
SP ₁₂ , SP ₂₂ and SP _w are obtained as follows according to the calculation method proposed by Fedors.
For each polymerizable monomer or mold release agent, for atoms or atomic groups in the molecular structure, from the table described in "polym. Eng. Sci., 14 (2), 147-154 (1974)". Evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm ³ / mol) were obtained, and (4.184 × ΣΔei / ΣΔvi) ^0.5 was set to SP value (J / cm ³ ) ^0.5 . To do.
SP ₁₁ and SP ₂₁ are calculated by the same calculation method as above for atoms or atomic groups having a molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.
SP ₃ determines the evaporation energy (Δei) and molar volume (Δvi) of the monomer unit derived from the polymerizable monomer constituting the polymer A for each monomer unit, and determines the molar amount of each monomer unit in the polymer A. The product with the ratio (j) is calculated, and the total evaporation energy of each monomer unit is divided by the total molar volume, which is calculated by the following formula (4).
SP ₃ = {4.184 × (Σj × ΣΔei) / (Σj × ΣΔvi)} ^0.5 (4)

<Measuring method of molecular weight of mold release agent>
The molecular weight (Mp) of the release agent is measured by gel permeation chromatography (GPC) as follows. Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatograph so as to have a concentration of 0.10% by mass / volume, and the mixture is dissolved at room temperature.
The release agent and o-dichlorobenzene to which the above BHT is added are placed in a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the release agent. When the release agent has melted, put it in a preheated filter unit and install it in the main body. A GPC sample that has passed through the filter unit is used. The sample solution is adjusted so that the concentration is 0.15% by mass. This sample solution is used for measurement under the following conditions.
・ Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
・ Detector: RI for high temperature
-Column: TSKgel GMHHR-HHT 2 stations (manufactured by Tosoh)
・ Temperature: 135.0 ℃
-Solvent: o-dichlorobenzene for gel chromatograph (BHT 0.10 mass / volume% added)
-Flow velocity: 1.0 ml / min
・ Injection amount: 0.4 ml
In calculating the molecular weight of the release agent, standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20," A molecular weight calibration curve prepared using F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.

<Measuring method of Mw of polymer A>
The molecular weight (Mw) of the THF-soluble component of the polymer A is measured by gel permeation chromatography (GPC) as follows.
First, the sample is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. This sample solution is used for measurement under the following conditions.
-Device: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
-Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
-Eluent: tetrahydrofuran (THF)
-Flow velocity: 1.0 ml / min
・ Oven temperature: 40.0 ℃
-Sample injection amount: 0.10 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 Corporation) is used.

<Measuring method of melting point>
The melting points of the polymer A and the release agent are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature rise rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, 5 mg of the sample is precisely weighed and placed in an aluminum pan to measure the differential scanning calorimetry. An empty silver pan is used as a reference.
The peak temperature of the maximum endothermic peak in the first temperature raising process is defined as the melting point.
The maximum endothermic peak is a peak in which the amount of heat absorption is maximum when there are a plurality of peaks.

<Measurement method of acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polymer A in the present invention is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was that 25 ml of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) Main test 2.0 g of the crushed polymer A sample is precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. .. Then, a few drops of the phenolphthalein solution are added as an indicator, and the potassium hydroxide solution is used for titration. The end point of the titration is when the light red color of the indicator continues for 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Solution factor, S: mass (g) of sample.

<Measuring method of the number average diameter of silica fine particles and primary particles of silica particles>
The number average diameter of the silica fine particles and the primary particles of the silica particles was observed using a scanning electron microscope S4700 (manufactured by Hitachi, Ltd.), the major axis of 100 particles was measured, and the average value was averaged by the number of primary particles. The diameter was set.

Hereinafter, the present invention will be specifically described with reference to Examples, but these are not intended to limit the present invention in any way. In the following formulations, parts are based on mass unless otherwise specified.

<Preparation of monomer having urethane group>
50.0 parts of methanol was charged into the reaction vessel. Then, under stirring, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40 ° C. After completion of the dropping, stirring was performed for 2 hours while maintaining 40 ° C. Then, the unreacted methanol was removed by an evaporator to prepare a monomer having a urethane group.

<Preparation of monomer having urea group>
50.0 parts of dibutylamine was charged into the reaction vessel. Then, under stirring, 5.0 parts of Calends MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature. After completion of the dropping, stirring was performed for 2 hours. Then, the unreacted dibutylamine was removed by an evaporator to prepare a monomer having a urea group.

<Preparation of polymer A0>
The following materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube under a nitrogen atmosphere.
100.0 parts of toluene ・ 100.0 parts of monomer composition (The monomer composition shall be a mixture of behenyl acrylate, methacrylonitrile, and styrene in the following proportions).
Behenyl acrylate (first polymerizable monomer) 67.0 parts (28.9 mol%)
-Methacrylonitrile (second polymerizable monomer) 22.0 parts (53.8 mol%)
11.0 parts (17.3 mol%) of styrene (third polymerizable monomer)
-Polymerization initiator t-butyl peroxypivalate (manufactured by Nichiyu Co., Ltd .: perbutyl PV) 0.5 part While stirring the inside of the above reaction vessel at 200 rpm, heat to 70 ° C. to carry out a polymerization reaction for 12 hours, and carry out a single amount A solution in which the polymer of the body composition was dissolved in toluene was obtained. Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the insoluble methanol. The obtained methanol-insoluble matter was filtered off, washed with methanol, and vacuum dried at 40 ° C. for 24 hours to obtain polymer A0. The weight average molecular weight (Mw) of the polymer A0 was 68,400, the acid value was 0.0 mgKOH / g, and the melting point was 62 ° C.
When the above polymer A0 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 28.9 mol%, the monomer unit derived from methacrylnitrile was 53.8 mol%, and the monomer unit derived from styrene was 17.3 mol%. Was included.

<Preparation of amorphous resin>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
30.0 parts ・ Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
33.0 parts, terephthalic acid 21.0 parts, dodecenyl succinic acid 15.0 parts, dibutyltin oxide 0.1 parts After the system was replaced with nitrogen by a reduced pressure operation, stirring was performed at 215 ° C. for 5 hours. Then, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and the temperature was maintained for another 2 hours. An amorphous resin, which is an amorphous polyester, was synthesized by air-cooling when it became a viscous state and stopping the reaction. The amorphous resin had Mn of 5,200, Mw of 23,000, and Tg of 55 ° C.

<Preparation of silica fine particles>
10.0 parts of polydimethylsiloxane (viscosity = 100 mm ² ) for 100 parts of fumed silica (trade name AEROSIL380S, specific surface area of 380 m ² / g by BET method, average number of primary particles 7 nm, manufactured by Nippon Aerosil Co., Ltd.) / S) was sprayed and stirring was continued for 30 minutes. Then, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours to prepare silica fine particles 1.
The silica fine particles not subjected to the polydimethylsiloxane treatment were designated as silica fine particles 2.

<Preparation of silica particles>
542.7 parts of methanol, 42.0 parts of pure water and 47.1 parts of 28% by mass aqueous ammonia were placed in a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer and mixed. The obtained solution was adjusted to 35 ° C., and 1100.0 parts of tetramethoxysilane and 395.2 parts of 5.4 mass% aqueous ammonia were started to be added simultaneously with stirring. Tetramethoxysilane was added dropwise over 7 hours, and aqueous ammonia was added dropwise over 6 hours.
After the dropping was completed, the mixture was further stirred for 0.2 hours and hydrolyzed to obtain a methanol-aqueous dispersion of spherical sol-gel silica fine particles. Then, this dispersion was sufficiently dried under reduced pressure at 80 ° C. to obtain untreated silica particles. The number average diameter of the primary particles of the silica particles before the treatment was 120 nm.
Subsequently, 100.0 parts of the untreated silica particles were placed in a reaction vessel, and 5.0 parts of polydimethylsiloxane (viscosity = 100 mm ² / s) was added to 5.0 parts of normal hexane while stirring under a nitrogen atmosphere. The diluted solution was sprayed. Then, the mixture was stirred at 300 ° C. for 60 minutes by nitrogen airflow, dried, and cooled to obtain silica particles. The number average diameter of the primary particles of the silica particles was 120 nm.

<Example 1>
[Manufacturing of toner by suspension polymerization method]
(Manufacturing of toner particles 1)
100.0 parts of monomer composition (The monomer composition shall be a mixture of the following behenyl acrylate, methacrylonitrile, and styrene in the proportions shown below).
Behenyl acrylate (first polymerizable monomer) 67.0 parts (28.9 mol%)
-Methacrylonitrile (second polymerizable monomer) 22.0 parts (53.8 mol%)
11.0 parts (17.3 mol%) of styrene (third polymerizable monomer)
・ Pigment Blue 15: 3 6.5 parts ・ G-t-Aluminum salicylate 1.0 parts ・ Release agent 1 10.0 parts (Release agent 1: Exellex 30050B, molecular weight (Mp) 2700, melting point 91 ° C, Mitsui Chemicals Co., Ltd.)
A mixture consisting of 100.0 parts of toluene was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having a diameter of 5 mm to obtain a raw material dispersion.
On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and the mixture was stirred at 12000 rpm. However, the temperature was raised to 60 ° C. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining 60 ° C. The pH was adjusted to 6.0 by adding 10% hydrochloric acid to obtain an aqueous medium containing a dispersion stabilizer.
Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60 ° C. while stirring at 100 rpm. To this, 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) was added as a polymerization initiator, and the mixture was stirred at 100 rpm for 5 minutes while maintaining 60 ° C. It was put into an aqueous medium that was stirred at 12000 rpm. Stirring was continued at 12000 rpm for 20 minutes with the above high-speed stirring device while maintaining 60 ° C. to obtain a granulated liquid.
The granulated solution was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 70 ° C. while stirring at 150 rpm in a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 10 hours while maintaining 70 ° C. Then, the reflux condenser was removed from the reaction vessel, the temperature of the reaction solution was raised to 95 ° C., and toluene was removed by stirring at 150 rpm for 5 hours while maintaining 95 ° C. to obtain a toner particle dispersion.
The obtained toner particle dispersion was cooled to 20 ° C. while stirring at 150 rpm, and then dilute hydrochloric acid was added until the pH became 1.5 while maintaining the stirring to dissolve the dispersion stabilizer. The solid content was filtered off, thoroughly washed with ion-exchanged water, and then vacuum dried at 40 ° C. for 24 hours to obtain toner particles 1 containing the polymer A1 of the monomer composition.
Further, in the method for producing the toner particles 1, the polymer A1'was obtained in the same manner except that Pigment Blue 15: 3, G-t-Aluminum salicylate, and Release Agent 1 were not used. The weight average molecular weight (Mw) of the polymer A1'was 56,000, the acid value was 0.0 mgKOH / g, and the melting point was 62 ° C. When the polymer A1 was analyzed by NMR, 28.9 mol% of the monomer unit derived from behenyl acrylate, 53.8 mol% of the monomer unit derived from methacrylonitrile, and 17.3 mol% of the monomer unit derived from styrene were contained. It was. Since the polymer A1 and the polymer A1'are produced in the same manner, it was judged that they have the same physical properties.

(Preparation of toner 1)
The toner particles 1 were externally added. Toner 1 was obtained by dry-mixing 1.8 parts of silica fine particles 1 and 0.3 parts of silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes with respect to 100.0 parts of toner particles 1. The physical properties of the obtained toner 1 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Examples 2-26, 35, 36>
In Example 1, toner particles 2-26, 35, and 36 were obtained in the same manner except that the types and amounts of the monomer compositions and mold release agents used were changed as shown in Table 1. The types of mold release agents are shown in Table 4.
Further, the same external addition as in Example 1 was performed to obtain toners 2-26, 35, 36. The physical properties are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Example 27>
Toner 27 was obtained by dry-mixing 1.8 parts of silica fine particles 2 and 0.3 parts of silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes with respect to 100.0 parts of toner particles 27. The physical properties of the obtained toner 27 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Example 28>
Toner 28 was obtained by dry mixing 1.8 parts of silica fine particles 1 with 100.0 parts of toner particles 28 using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes. The physical properties of the obtained toner 28 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Example 35>
Toner 35 was obtained by dry-mixing 1.8 parts of silica fine particles 1 and 0.3 parts of silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes with respect to 100.0 parts of the toner particles 35. The physical properties of the obtained toner 35 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Example 29>
[Preparation of toner by emulsification and agglutination method]
(Preparation of polymer dispersion)
-Toluene 300.0 parts-Polymer A0 100.0 parts The above materials were weighed and mixed and dissolved at 90 ° C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700.0 parts of ion-exchanged water and dissolved by heating at 90 ° C. Next, the above-mentioned toluene solution and the aqueous solution were mixed, and the ultra-high-speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix Corporation). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact disperser nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Then, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain a polymer dispersion having a concentration of 20% of the polymer fine particles.
The 50% particle size (D50) based on the volume distribution of the polymer fine particles was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.
(Preparation of release agent dispersion 1)
・ Release agent 1 100.0 parts ・ Anionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 5.0 parts ・ Ion-exchanged water 395.0 parts Weighed the above materials and put them in a mixing container equipped with a stirrer. After that, the mixture was heated to 90 ° C. and circulated to Clairemix W Motion (manufactured by M-Technique) for 60 minutes for dispersion treatment. The conditions for distributed processing were as follows.
・ Rotor outer diameter 3 cm
・ Clearance 0.3mm
・ Rotor rotation speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the mold release agent fine particles 1 are released at a concentration of 20% by cooling to 40 ° C. under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C./min. Agent dispersion 1 was obtained.
The 50% particle size (D50) of the release agent fine particle 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.
(Preparation of colorant dispersion 1)
・ Colorant 50.0 parts (Cyan pigment Dainichiseika: Pigment Blue 15: 3)
・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.5 parts ・ Ion-exchanged water 442.5 parts Weigh, mix and dissolve the above materials, and use a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo) The mixture was dispersed for 1 hour to obtain a colorant dispersion 1 having a concentration of 10% of the colorant fine particles 1 in which the colorant was dispersed.
The 50% particle size (D50) of the colorant fine particles 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.
(Manufacturing of toner 29)
・ Polymer dispersion 500.0 parts ・ Release agent dispersion 1 50.0 parts ・ Colorant dispersion 1 80.0 parts ・ Ion exchange water 160.0 parts Put each of the above materials into a round stainless steel flask. , Mixed. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultratarax T50 (manufactured by IKA). After adding a 1.0% aqueous nitric acid solution and adjusting the pH to 3.0, use a stirring blade in a water bath for heating while appropriately adjusting the rotation speed so that the mixed solution is stirred at 58 ° C. Heated to. The volume average particle diameter of the formed aggregated particles was appropriately confirmed using Coulter Multisizer III, and when the aggregated particles having a weight average particle diameter (D4) of 6.0 μm were formed, a 5% aqueous sodium hydroxide solution was formed. The pH was adjusted to 9.0 using. Then, while continuing stirring, it was heated to 75 ° C. Then, the agglomerated particles were fused by holding at 75 ° C. for 1 hour.
Then, the polymer was cooled to 50 ° C. and held for 3 hours to promote crystallization of the polymer.
Then, the mixture was cooled to 25 ° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After the washing was completed, the toner particles 29 having a weight average particle diameter (D4) of 6.07 μm were obtained by drying using a vacuum dryer.
The toner particles 29 were externally added in the same manner as in Example 1 to obtain the toner 29. The physical properties of the toner 29 are shown in Tables 2-1 and 2-2, and the evaluation results are shown in Table 7.

<Example 30>
[Preparation of toner by dissolution suspension method]
(Preparation of fine particle dispersion 1)
In a reaction vessel with a stirring rod and a thermometer set, 683.0 parts of water, 11.0 parts of sodium salt of ethylene methacrylate (EO) adduct sulfate (eleminol RS-30, manufactured by Sanyo Kasei Kogyo Co., Ltd.), 130 parts of styrene. When 0.0 part, 138.0 parts of methacrylic acid, 184.0 parts of -n-butyl acrylate and 1.0 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white suspension was obtained. It was. The mixture was heated to a temperature inside the system of 75 ° C. and reacted for 5 hours.
Further, 30.0 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to obtain a fine particle dispersion 1 of a vinyl polymer. The 50% particle size (D50) of the fine particle dispersion 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.
(Preparation of colorant dispersion 2)
・ C. I. Pigment Blue 15: 3 100.0 parts, ethyl acetate 150.0 parts, glass beads (1 mm) 200.0 parts Put the above materials in a heat-resistant glass container, disperse with a paint shaker for 5 hours, and nylon mesh. The glass beads were removed in the above method to obtain a colorant dispersion liquid 2. The 50% particle size (D50) based on the volume distribution of the colorant dispersion was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.
(Preparation of release agent dispersion 2)
-Release agent 1 20.0 parts, ethyl acetate 80.0 parts The above was put into a reaction vessel that can be sealed, and heated and stirred at 80 ° C. Then, the inside of the system was cooled to 25 ° C. over 3 hours while gently stirring at 50 rpm to obtain a milky white liquid.
This solution is put into a heat-resistant container together with 30.0 parts by mass of glass beads having a diameter of 1 mm, dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), the glass beads are removed with a nylon mesh, and a release agent dispersion liquid is used. I got 2. The 50% particle size (D50) of the release agent dispersion 2 based on the volume distribution was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.23 μm.
(Preparation of oil phase)
-Polymer A0 100.0 parts, ethyl acetate 85.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 1 minute using a disper (manufactured by Tokushu Kika).
・ Release agent dispersion 2 (solid content 20%) 50.0 parts ・ Colorant dispersion 2 (solid content 40%) 12.5 parts ・ Ethyl acetate 5.0 parts Further put the above material in a beaker and disperse An oil phase was prepared by stirring at 6000 rpm for 3 minutes using (manufactured by Tokushu Kagaku Co., Ltd.).
(Preparation of aqueous phase)
・ Fine particle dispersion 1 15.0 parts ・ Aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON7, manufactured by Sanyo Chemical Industries, Ltd.) 30.0 parts ・ Ion-exchanged water 955.0 parts Put the above materials in a beaker and disperse (special machine) The aqueous phase was prepared by stirring at 3000 rpm for 3 minutes.
(Manufacturing of toner 30)
The oil phase was added to the aqueous phase, and the mixture was dispersed for 10 minutes at a rotation speed of 10,000 rpm with a TK homomixer (manufactured by Tokushu Kika). Then, the solvent was removed for 30 minutes at 30 ° C. under a reduced pressure of 50 mmHg. Next, filtration was performed, and the operations of filtration and redispersion in ion-exchanged water were repeated until the conductivity of the slurry became 100 μS to remove the surfactant, and a filtered cake was obtained.
Toner particles 30 were obtained by vacuum-drying the filtered cake and then performing wind power classification.
The toner particles 30 were externally added in the same manner as in Example 1 to obtain the toner 30. The physical properties of the toner 30 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Example 31>
[Making toner by crushing method]
・ Polymer A0 100.0 parts ・ C.I. I. Pigment Blue 15: 3 6.5 parts, mold release agent 1 2.0 parts, charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2.0 parts FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) After pre-mixing with, the mixture was melt-kneaded by a twin-screw kneading extruder (PCM-30 type manufactured by Ikegai Iron Works Co., Ltd.).
The obtained kneaded product is cooled, roughly crushed with a hammer mill, and then crushed with a mechanical crusher (T-250 manufactured by Turbo Industries, Ltd.), and the obtained finely crushed powder is often used for the Coanda effect. Classification was performed using a division classifier to obtain toner particles 31 having a weight average particle size (D4) of 7.0 μm.
The toner particles 31 were externally added in the same manner as in Example 1 to obtain the toner 31. The physical properties of the toner 31 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Examples 32 to 34>
(Preparation of amorphous resin dispersion)
-Toluene 300.0 parts-Amorphous resin 100.0 parts The above materials were weighed and mixed and dissolved at 90 ° C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700.0 parts of ion-exchanged water and dissolved by heating at 90 ° C. Next, the above-mentioned toluene solution and the aqueous solution were mixed, and the ultra-high-speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix Corporation). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact disperser nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Then, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an amorphous resin dispersion having a concentration of 20% of amorphous resin fine particles.
The 50% particle size (D50) of the amorphous resin fine particles based on the volume distribution was measured using a dynamic light scattering type particle size distribution meter Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.38 μm.

(Manufacturing of toners 32 to 34)
Toner particles 32 to 34 were obtained in the same manner except that the amount of the dispersion liquid used in the production example of the toner 29 was changed as shown in Table 6.
Further, the toner particles 32 to 34 were externally added in the same manner as in the production example of the toner 29 to obtain toners 32 to 34. The physical properties are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Comparative Examples 1 to 6>
Comparative toner particles 1 to 6 were obtained in the same manner in Example 1 except that the types and amounts of the monomer compositions and mold release agents used were changed as shown in Table 1.
Further, in Example 1, comparative toners 1 to 6 were obtained in the same manner except that the type and amount of the external additive used were changed as shown in Table 5.
The physical properties of the comparative toners 1 to 6 are shown in Tables 2-1 and 2, and the evaluation results are shown in Table 7.

<Toner evaluation method>
<1> Low-temperature fixability A process cartridge filled with toner was left for 48 hours in a room temperature and humidity (N / N) environment (23 ° C., 60% RH). Using the LBP-7700C modified so that it can operate even when the fuser is removed, an unfixed image of an image pattern in which 9 points of 10 mm × 10 mm square images are evenly arranged on the entire transfer paper is output. The toner loading amount on the transfer paper was 0.80 mg / cm ² , and the fixing start temperature was evaluated. As the transfer paper, Fox River Bond (90 g / m ² ) was used.
As the fuser, an external fuser was used in which the fuser of the LBP-7700C was removed to the outside so that the fuser could operate outside the laser beam printer. In the external fixing device, the fixing temperature was raised from 100 ° C. to 10 ° C. in increments of 10 ° C., and fixing was performed under the condition of process speed: 240 mm / sec.
The fixed image was rubbed with Sylbon paper [Lens Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)] under a load of 50 g / cm ² . Then, the low temperature fixability was evaluated according to the following criteria, with the temperature at which the concentration decrease rate before and after rubbing was 20% or less as the fixing start temperature. The evaluation results are shown in Table 7.
[Evaluation criteria]
A: Fixing start temperature is 100 ° C
B: Fixing start temperature is 110 ° C
C: Fixing start temperature is 120 ° C
D: Fixing start temperature is 130 ° C
E: Fixing start temperature is 140 ° C or higher

<2> Heat-resistant storage property The heat-resistant storage property was evaluated in order to evaluate the stability during storage. After putting 6 g of toner in a 100 ml resin cup and leaving it in an environment of temperature 50 ° C. and humidity 20% for 10 days, the degree of toner cohesion was measured as follows and evaluated according to the following criteria. ..
As the measuring device, a digital display type vibrometer "Digivibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side surface of the shaking table of the "powder tester" (manufactured by Hosokawa Micron Co., Ltd.). Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were stacked and set on the shaking table of the powder tester in this order from the bottom. The measurement was carried out in an environment of 23 ° C. and 60% RH as follows.
(1) The vibration width of the shaking table was adjusted in advance so that the displacement value of the digital display type vibrometer was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above is left in advance in an environment of 23 ° C. and 60% RH for 24 hours, of which 5 g of toner is precisely weighed and gently placed on a sieve having an opening of 150 μm on the uppermost stage. It was.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of cohesion was calculated based on the following formula. The evaluation results are shown in Table 7.
Cohesion (%) = {(sample mass (g) on a sieve with an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass (g) on a sieve with an opening of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve with an opening of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: Cohesion is less than 20% B: Cohesion is 20% or more and less than 25% C: Cohesion is 25% or more and less than 30% D: Cohesion is 30% or more and less than 35% E: Cohesion is 35% or more

<3> The printer was used as the releasability evaluation machine, and GF-500 (A4, basis weight 64.0 g / m ² , sold by Canon Marketing Japan Inc.) was used as the evaluation paper. The paper passing direction was vertical. An unfixed image having a width of 100 mm at a distance of 1 mm from the tip of the evaluation paper in the paper passing direction and a width of 200 mm in the direction orthogonal to the paper passing direction was prepared. The toner loading amount of the unfixed image was 1.2 mg / cm ² .
Then, using the fixing device, the fixing start temperature in the evaluation of the low temperature fixing property was raised in increments of 10 ° C., and it was measured whether or not the fixing image was wound around the fixing roller. The temperature range in which wrapping does not occur was evaluated according to the following criteria.
The evaluation results are shown in Table 7.
[Evaluation criteria]
A: Temperature range where wrapping does not occur is 40 ° C or higher B: Temperature range where wrapping does not occur is 30 ° C
C: The temperature range where wrapping does not occur is 20 ° C.
D: The temperature range where wrapping does not occur is 10 ° C.
E: Wrapping occurs in all areas

<4> Durability A commercially available Canon printer LBP9200C was used to evaluate the durability. The LBP9200C employs one-component contact development, and the amount of toner on the developing carrier is regulated by a toner regulating member. As the evaluation cartridge, the toner contained in the commercially available cartridge was extracted, the inside was cleaned by an air blow, and then 260 g of the toner to be evaluated was filled. The evaluation was carried out by mounting the above cartridge on the cyan station and mounting a dummy cartridge on the others.
An image having a printing rate of 1% was continuously output using a Fox River Bond (90 g / m ² ) at 23 ° C. and a 60% RH environment. A solid image and a halftone image were output every time 1,000 sheets were output, and the presence or absence of vertical streaks, so-called development streaks, caused by toner fusion to the regulating member was visually confirmed. Finally, 20,000 images were output. The evaluation results are shown in Table 7.
[Evaluation criteria]
A: No occurrence even with 20,000 sheets B: Occurs with 20,000 sheets C: Occurs with 18,000 or 19,000 sheets D: Occurs with 17,000 sheets or less

<5> Gloss At a temperature 20 ° C higher than the fixing start temperature evaluated in the above evaluation <1>, in the same image as the above evaluation <1>, the handy gloss meter gloss meter PG-3D (Nippon Denshoku Kogyo) The gloss value was measured at three arbitrary points on the image under the condition of an incident angle of light of 75 °, and the average value was taken as the gloss value. The evaluation results are shown in Table 7.
[Evaluation criteria]
A: Gross value is 25 or more and B: Gross value is 20 or more and less than 25 C: Gross value is 15 or more and less than 20 D: Gross value is less than 15

Claims (15)

A toner having toner particles containing a binder resin and a mold release agent.
The binding resin
A polymer having a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Contains A,
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the polymer A.
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfy (1)
A toner characterized by having a molecular weight of the release agent of 1000 or more.
3.00 ≤ (SP _21- SP ₁₁ ) ≤ 25.00 ... (1) A toner having toner particles containing a binder resin and a mold release agent.
The binding resin
It contains polymer A, which is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer.
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. Yes,
The SP value of the first polymerizable monomer is SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is SP ₂₂ (J / cm ³ ) ^0.5. When, the following formula (2) is satisfied,
A toner characterized by having a molecular weight of the release agent of 1000 or more.
0.60 ≤ (SP _22- SP ₁₂ ) ≤ 15.00 ... (2) Claim 1 in which the content ratio of the second monomer unit in the polymer A is 40.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the polymer A. Toner described in. The content ratio of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. The toner according to claim 2. The toner according to any one of claims 1 to 4, wherein the content of the polymer A in the binder resin is 50.0% by mass or more. Any one of claims 1 to 5, wherein the first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms. The toner described in item 1. The toner according to any one of claims 1 to 6, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
Urethane group (-NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms)),
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ is an independent hydrogen atom or an alkyl group having 1 to 6 carbon atoms)),
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (R ¹⁵ is Independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ is a hydrogen atom or a methyl group. )
(In the formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The toner according to claim 7, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ is an independent hydrogen atom or an alkyl group having 1 to 6 carbon atoms)),
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (R ¹⁵ is Independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ is a hydrogen atom or a methyl group. )
(In the formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The polymer A has a first polymerizable monomer and a third monomer unit derived from a third polymerizable monomer different from the second polymerizable monomer.
The toner according to any one of claims 1 to 8, wherein the third polymerizable monomer is at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate. The toner according to any one of claims 1 to 9, wherein the release agent has a melting point of 60 ° C. or higher and 120 ° C. or lower. When the SP value of the polymer A is SP ₃ (J / cm ³ ) ^0.5 and the SP value of the release agent is SP _W (J / cm ³ ) ^0.5 , SP ₃ and SP _W are as follows. The toner according to any one of claims 1 to 10, which satisfies the formula (3).
(SP _3- SP _w ) ≧ 1.00 ・ ・ ・ (3) The toner according to any one of claims 1 to 11, wherein the release agent contains an aliphatic hydrocarbon wax. The toner has an external additive and
The toner according to any one of claims 1 to 12, wherein the external additive contains silica fine particles treated with silicone oil. The toner has an external additive and
The toner according to any one of claims 1 to 13, wherein the external additive contains silica particles having an average number of primary particles of 30 nm or more and 500 nm or less. The toner according to any one of claims 1 to 14, wherein the polymer A is a vinyl polymer.