JP7251193B2 - PHOTORESPONSIVE POLYMER MATERIAL, ADHESIVE, TONER AND IMAGE FORMING METHOD - Google Patents

Description

The present invention relates to a photoresponsive polymer material, a polymer that contains a structural unit derived from an azomethine derivative having a polymerizable group, and that is reversibly fluidized or non-fluidized by light irradiation, and an adhesive using the same. and toner, and an image forming method using the toner.

A photoresponsive liquid crystal material is known as a material whose fluidity is changed by light irradiation. For example, Patent Documents 1 and 2 propose polymer liquid crystal materials using azobenzene derivatives. They undergo cis-trans isomerization of azobenzene moieties in response to light. It is believed that the resulting change in molecular structure induces a phase transition from the solid state to the fluid state. Also, by re-irradiating with a different wavelength, by heating, or by leaving it in a dark place at room temperature, a reverse reaction occurs and it solidifies again.

JP 2011-256155 A JP 2011-256291 A

However, the azobenzene derivatives described in Patent Documents 1 and 2 all have yellow to orange coloring, and there is a problem that the desired color cannot be reproduced when applied to industrial products such as toners and adhesives. . Furthermore, according to the studies of the present inventors, by changing the substituents of the azobenzene derivative, even if it is possible to slightly adjust the color from yellow to orange, it is fundamentally colorless or nearly colorless. It also turned out that it is impossible to

Accordingly, an object of the present invention is to provide a polymer that is reversibly fluidized and non-fluidized by light irradiation and is free from marked coloration.

Another object of the present invention is to provide industrial products such as toners and adhesives using the polymer.

Still another object of the present invention is to provide an image forming method using the above toner.

The present inventors have made intensive studies in view of the above problems. As a result, by using a compound having an azomethine moiety, reversible fluidization and non-fluidization, and photoresponsiveness without significant coloration to the extent that it does not affect the reproduction of desired colors when applied to toners and adhesives. The inventors have found that the above problems can be solved by realizing a polymer material, and have completed the present invention.

That is, the present invention is a polymer that includes a structural unit derived from an azomethine derivative having a polymerizable group, represented by the following chemical formula (1), and that is reversibly fluidized/non-fluidized by light irradiation.

In the chemical formula (1),
X is NR ₁₀ , O or S;
R ₁ and R ₂ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or an alkyl group having 1 to 16 carbon atoms. 16 alkoxy group, acyl group having 2 to 16 carbon atoms, alkoxycarbonyl group having 2 to 16 carbon atoms, or acyloxy group having 2 to 16 carbon atoms,
Either one of R ₃ or R ₄ is a group represented by Y, and the other is a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, a carbon number an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
R ₁₀ is a group having a polymerizable group, a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 2 carbon atoms. ~16 alkoxycarbonyl group or an acyloxy group having 2 to 16 carbon atoms,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
R ₅ to R ₇ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or 1 to 1 carbon atoms. 16 alkoxy group, acyl group having 2 to 16 carbon atoms, alkoxycarbonyl group having 2 to 16 carbon atoms, or acyloxy group having 2 to 16 carbon atoms,
R ₈ and R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or a carbon number an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
At this time, at least one of R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y is a group having a polymerizable group,
When at least one of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y is a group having a polymerizable group, R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ other than the group having a polymerizable group and the group represented by Y are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, provided that R ₁₀ is a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or a carbon selected from alkoxy groups of numbers 1 to 4,
When at least one of R ₅ to R ₇ is a group having a polymerizable group, among R ₅ to R ₇ , those other than the polymerizable group, R ₈ and R ₉ are each independently a hydrogen atom, It is selected from a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

According to the present invention, it is possible to obtain a polymer that is reversibly fluidized and non-fluidized by light irradiation and that is not markedly colored.

1 is a schematic configuration diagram showing an image forming apparatus 100 used in an image forming method according to an embodiment of the invention; FIG. 2 is a schematic configuration diagram of an irradiation unit 40 in the image forming apparatus 100; FIG. 1 is a schematic diagram of an apparatus for measuring the change in adhesiveness of polymers/compounds synthesized in Examples and Comparative Examples, which was used in the photoresponsive adhesion test of Examples, and which accompanies light irradiation. FIG.

The present invention is a polymer that is reversibly fluidized/non-fluidized by light irradiation, and which contains structural units derived from an azomethine derivative having a polymerizable group, represented by the following chemical formula (1).

In the chemical formula (1),
X is NR ₁₀ , O or S;
R ₁ and R ₂ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or an alkyl group having 1 to 16 carbon atoms. 16 alkoxy group, acyl group having 2 to 16 carbon atoms, alkoxycarbonyl group having 2 to 16 carbon atoms, or acyloxy group having 2 to 16 carbon atoms,
Either one of R ₃ or R ₄ is a group represented by Y, and the other is a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, a carbon number an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
R ₁₀ is a group having a polymerizable group, a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 2 carbon atoms. ~16 alkoxycarbonyl group or an acyloxy group having 2 to 16 carbon atoms,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
R ₅ to R ₇ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or 1 to 1 carbon atoms. 16 alkoxy group, acyl group having 2 to 16 carbon atoms, alkoxycarbonyl group having 2 to 16 carbon atoms, or acyloxy group having 2 to 16 carbon atoms,
R ₈ and R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or a carbon number an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
At this time, at least one of R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y is a group having a polymerizable group,
When at least one of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y is a group having a polymerizable group, R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ other than the group having a polymerizable group and the group represented by Y are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, provided that R ₁₀ is a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or a carbon selected from alkoxy groups of numbers 1 to 4,
When at least one of R ₅ to R ₇ is a group having a polymerizable group, among R ₅ to R ₇ , those other than the polymerizable group, R ₈ and R ₉ are each independently a hydrogen atom, It is selected from a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

By using such a polymer containing a structural unit derived from the azomethine derivative represented by the above chemical formula (1), it is reversibly fluidized and non-fluidized by light irradiation, and when applied to toners and adhesives. Therefore, it is possible to realize a photoresponsive compound free from coloring to the extent that it does not affect the reproduction of desired colors.

Although the details of why the polymer of the present invention achieves the above effect are unknown, the following mechanism is conceivable. The mechanism described below is based on speculation, and the present invention is not limited to the mechanism described below. In the following description, the polymer containing the structural unit represented by the chemical formula (1) is also referred to as "polymer containing a structural unit derived from an azomethine derivative".

Azobenzene compounds with long alkyl chains at their ends are known to be materials that absorb light and soften from a solid state (optical phase transition). This is thought to be caused by structural collapse. The azobenzene compounds described in Patent Documents 1 and 2 undergo a phase change accompanying the isomerization reaction due to light irradiation, but these compounds exhibit strong absorption in the visible light region derived from n-π ^* transitions, and are colored orange. Therefore, there is a problem in that the desired color cannot be reproduced when applied to industrial products.

In the present invention, by using a polymer containing a structural unit derived from an azomethine derivative, it has been realized to provide a polymer that is reversibly fluidized and non-fluidized by light irradiation and is free from significant coloration. By introducing a structural unit derived from an azomethine derivative instead of an azobenzene compound, the strong n-π ^* absorption in the azobenzene compound can be greatly weakened, so that a polymer without significant coloration can be realized.

A polymer containing a structural unit derived from an azomethine derivative absorbs light, and the thermal energy released during the process of photoexcitation and deactivation is transmitted to the repeating unit (structural unit) to which it is attached (photothermal conversion). A reversible fluidization/non-fluidization phenomenon can be induced. In particular, when the polymer is a trans isomer, in addition to the photothermal conversion described above, photoirradiation is more likely to cause trans-cis photoisomerization, and a cis isomer having a low Tg is likely to be produced. It is thought that photoisomerization causes the ordered structure to collapse and undergo a phase transition change, which causes the ordered structure to collapse and undergo a phase transition change, thereby inducing more efficient fluidization/non-fluidization phenomena. Therefore, in order to induce the reversible mobilization/non-mobilization phenomenon, it is considered necessary to isomerize many trans isomers (E) to cis isomers (Z). However, azomethine derivatives are generally known to have a faster cis-trans isomerization rate than azobenzene derivatives, and azomethine derivatives with benzene rings attached to both ends of the C=N bond are reversible fluidized substances.・It was expected that it would be disadvantageous in inducing the non-fluidization phenomenon.

In the present invention, by introducing a heterocyclic ring on the nitrogen atom side or the carbon atom side of the C=N bond in the azomethine derivative, the amount of cis-form (Z) at the time of light irradiation increases, resulting in fluidization accompanying the photoisomerization reaction. was able to induce This is probably because the introduction of a heterocyclic ring instead of a benzene ring reduces the cis-trans isomerization rate.

Furthermore, by polymerizing the azomethine derivative, the toughness as a material can be improved. Therefore, it is considered that excellent image strength can be obtained particularly when used in toner.

For the reasons described above, it is thought that the polymer having a structural unit derived from the azomethine derivative of the present invention is colorless but can induce reversible fluidization/non-fluidization phenomena accompanying isomerization. By introducing the coalescence into the toner, it is possible to obtain a toner that can be fixed by light irradiation and has high color reproducibility.

In addition, the flow in the present invention refers to a state in which the system is deformed with no or little external force.

Preferred embodiments of the present invention are described below. In this specification, "X to Y" indicating a range means "X or more and Y or less". In this specification, unless otherwise specified, operations and measurements of physical properties are performed under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.

<Polymer Containing Structural Unit Derived from Azomethine Derivative Having Polymerizable Group>
The polymer containing a structural unit derived from an azomethine derivative having a polymerizable group of the present invention is a polymer containing a structural unit represented by the following chemical formula (1), which is reversibly fluidized/non-fluidized by light irradiation. is. In the polymer of the present invention, the cis-trans isomerization rate is reduced by introducing a heterocyclic ring represented by the following chemical formula 1 into the benzene ring of the azomethine derivative, and the amount of cis-isomer (Z) at the time of light irradiation is reduced. increased, and it is thought that fluidization accompanying the photoisomerization reaction could be induced. The polymer of the present invention is not particularly limited, but from the viewpoint of making it easier to reliably introduce an azomethine group into the molecule and efficiently inducing reversible fluidization/non-fluidization, the following chemical formula (1) It is preferably a polymer obtained by polymerizing an azomethine derivative having a polymerizable group represented as a monomer (azomethine derivative monomer).

In the chemical formula (1), X is NR ₁₀ , O or S;

R ₁ and R ₂ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or an alkyl group having 1 to 16 carbon atoms. 16 alkoxy groups, acyl groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, or acyloxy groups having 2 to 16 carbon atoms.

Either one of R ₃ or R ₄ is a group represented by Y, and the other is a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, a carbon number It is an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms.

R ₁₀ is a group having a polymerizable group, a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 2 carbon atoms. alkoxycarbonyl groups of up to 16 or acyloxy groups of 2 to 16 carbon atoms.

Z ₁ and Z ₂ are N or CH, and Z ₁ ≠Z ₂ .

R ₅ to R ₇ each independently represents a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, or 1 to 1 carbon atoms. 16 alkoxy groups, acyl groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, or acyloxy groups having 2 to 16 carbon atoms.

R ₈ and R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or a carbon number It is an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms.

At this time, at least one of R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y is a group having a polymerizable group.

When at least one of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y is a group having a polymerizable group, R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ other than the group having a polymerizable group and the group represented by Y are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, provided that R ₁₀ is a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or a carbon When at least one of R ₅ to R _{7 is a} group having a polymerizable group, R ₈ and R ₉ is independently selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

By selecting R ₁ to R ₁₀ as described above, the azomethine derivative exhibits intermolecular packing (π-π interaction) at the azomethine group portion, and exhibits high thermal motion when trans-cis isomerized. It is considered that the fluidization phenomenon is likely to be induced while increasing the strength as a material.

Here, as a substituent on the benzene ring in the case of having a polymerizable group on the hetero five-membered ring, or as a substituent on the hetero five-membered ring in the case of having a polymerizable group on the benzene ring, the above carbon number an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms, each having 1 carbon atom; It is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyloxy group having 2 to 12 carbon atoms. More preferably, each of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, or a It is an acyloxy group. With this structure, the azomethine derivative exhibits intermolecular packing (π-π interaction) at the azomethine group portion, and exhibits high thermal mobility when trans-cis isomerized, so it is strong as a material. It is considered that the fluidization phenomenon is likely to be induced while increasing the

In a more preferred embodiment of the present invention, from the viewpoint of ease of photoisomerization, at least those selected from R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y When one is a group having a polymerizable group, each of R ₅ to R ₉ is preferably independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Further, from the viewpoint of ease of photoisomerization, when _at least one of R _{5 to} R _{7 is} a group having _a polymerizable _group , Y Those not selected as groups represented by are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

In the present invention, the heteroatom of X is preferably S or N because the fixability is improved.

Halogen atoms include fluorine atom (F), chlorine atom (Cl), bromine atom (Br), iodine atom (I), and the like.

Examples of alkyl groups used for R ₁ to R ₁₀ are not particularly limited, and examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, etc. Linear alkyl group; isopropyl group, sec-butyl group, t-butyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1- methylhexyl group, t-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5 branched alkyl groups such as -trimethylhexyl group, 1-methyldecyl group and 1-hexylheptyl group.

Examples of alkoxy groups used for R ₁ to R ₁₀ include methoxy, ethoxy, n-propoxy, n-butoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n -nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, etc. A linear alkoxy group of: 1-methylpentyloxy group, 4-methyl-2-pentyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 1-methylhexyloxy group, t- octyloxy group, 1-methylheptyloxy group, 2-ethylhexyloxy group, 2-propylpentyloxy group, 2,2-dimethylheptyloxy group, 2,6-dimethyl-4-heptyloxy group, 3,5,5 branched alkoxy groups such as -trimethylhexyloxy group, 1-methyldecyloxy group and 1-hexylheptyloxy group;

Examples of acyl groups used for R ₁ to R ₁₀ are saturated or unsaturated linear or branched acyl groups such as acetyl group, propanoyl group (propionyl group), butanoyl group (butyryl group), isobutanoyl group (isobutyryl group), pentanoyl group (valeryl group), isopentanoyl group (isovaleryl group), sec-pentanoyl group (2-methylbutyryl group), t-pentanoyl group (pivaloyl group), hexanoyl group, heptanoyl group, octanoyl group, t-octanoyl group (2,2-dimethylhexanoyl group), 2-ethylhexanoyl group, nonanoyl group, isononanoyl group, decanoyl group, isodecanoyl group, undecanoyl group, lauroyl group, myristoyl group, palmitoyl group, undecylenoyl group etc.

Examples of alkoxycarbonyl groups used for R ₁ to R ₁₀ are linear or branched, such as methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-hexyloxycarbonyl, n- heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n - Linear alkoxycarbonyl groups such as tetradecyloxycarbonyl group and n-pentadecyloxycarbonyl group: 1-methylpentyloxycarbonyl group, 4-methyl-2-pentyloxycarbonyl group, 3,3-dimethylbutyloxy carbonyl group, 2-ethylbutyloxycarbonyl group, 1-methylhexyloxycarbonyl group, t-octyloxycarbonyl group, 1-methylheptyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-propylpentyloxycarbonyl group, 2 , 2-dimethylheptyloxycarbonyl group, 2,6-dimethyl-4-heptyloxycarbonyl group, 3,5,5-trimethylhexyloxycarbonyl group, 1-methyldecyloxycarbonyl group, 1-hexylheptyloxycarbonyl group, etc. and branched alkoxycarbonyl groups.

Examples of acyloxy groups used for R ₁ to R ₁₀ are saturated or unsaturated linear or branched acyl groups such as acetoxy, propionyloxy, butanoyloxy and isobutanoyloxy groups. , pentanoyloxy group, isopentanoyloxy group, sec-pentanoyloxy group, t-pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, t-octanoyloxy group, 2- ethylhexanoyloxy group, nonanoyloxy group, isononanoyloxy group, decanoyloxy group, isodecanoyloxy group, undecanoyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group and the like.

The above alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, or acyloxy group may be linear or branched. is more preferable.

Further, part of the alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, or acyloxy group may be substituted with a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, carboxy groups, and the like.

The number of polymerizable groups contained in one molecule of the azomethine derivative having a polymerizable group may be one, or two or more. Among them, from the viewpoint of easily obtaining a polymer that melts easily even with a low amount of light irradiation energy, the number of polymerizable groups contained in one molecule of the azomethine derivative having a polymerizable group is one. That is, it is preferably a monofunctional polymerizable monomer.

Examples of the polymerizable group include (meth)acryloyl group, epoxy group and vinyl group, and (meth)acryloyl group and vinyl group are preferred. Anionic polymerization, cationic polymerization, and living radical polymerization are known as methods for synthesizing polymers, and a (meth)acryloyl group or a vinyl group is preferred because it is easily applicable to these polymerization methods. Among them, a (meth)acryloyl group is preferred. In addition, a (meth)acryloyl group means an acryloyl group and a methacryloyl group.

That is, the azomethine derivative having a polymerizable group preferably has a group represented by any one of the following formulas (i) to (iv) as the group having a polymerizable group. Having a group having these polymerizable groups is preferable because it is suitable for polymer synthesis. Among these, from the viewpoint of easiness of softening and melting, it is preferable to have the group represented by (ii), (iii) or (iv), and it is more preferable to have the group (iii).

In formulas (i) to (iv), A ₁ is each independently a hydrogen atom or a methyl group. Each _A2 is independently an alkylene group having 1 to 18 carbon atoms. An alkylene group having 3 to 12 carbon atoms is preferred. The alkylene group may be linear or branched, preferably linear. A part of the alkylene group may be substituted with a substituent. Examples of substituents include halogen groups, nitro groups, hydroxy groups, carboxy groups, and the like. Each _A3 is independently an alkylene group having 1 to 6 carbon atoms. An alkylene group having 1 to 4 carbon atoms is preferred. The alkylene group may be linear or branched, preferably linear. A part of the alkylene group may be substituted with a substituent. Examples of substituents include those mentioned above.

In the azomethine derivative having a polymerizable group represented by the chemical formula (1), R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y At least one of them is a group having a polymerizable group, and by facilitating photoisomerization, the polymer or the toner image formed by the toner using the polymer can be melted or softened even by light irradiation with lower energy. _{From the viewpoint of} facilitating _the More preferably, it contains a group having a group.

An azomethine derivative having a polymerizable group facilitates photoisomerization, thereby facilitating melting or softening of a polymer or a toner image formed by a toner using the polymer even when irradiated with light of lower energy. A compound represented by the chemical formula (2) is preferable.

In chemical formula (2),
X is NR ₁₀ , O or S;
R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or a carbon number an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
one of R ₃ and R ₄ is a group represented by Y, and the other is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
R ₁₀ is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
_R7 is a group having a polymerizable group.

At this time, the group having a polymerizable group is preferably a group represented by any one of the above formulas (i) to (iv), and more preferably a group represented by formula (iii). .

Furthermore, in the azomethine derivative having a polymerizable group represented by the above chemical formula (2),
(1) all of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y are hydrogen atoms, or
(2) among R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y, any one of R ₁ to R ₄ not adjacent to Y is a cyano group; a nitro group, a hydroxy group, a carboxy group, or an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a carbon number 2 to 12 acyloxy groups which are not selected as a group represented by Y among the remaining (R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ ), the above “R ₁ to R not adjacent to Y ₄ ) are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or a group having 1 to 4 carbon atoms and R ₁₀ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or
(3) R ₁₀ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms; and R ₁ , R ₂ , and R ₃ or R ₄ not selected as a group represented by Y are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms,
is preferably satisfied. Such a structure facilitates photoisomerization and facilitates melting or softening of a toner image formed by a polymer or a toner using the polymer even with lower energy light irradiation.

Among the azomethine derivatives represented by the above chemical formula (2), in a preferred embodiment, X is S, Z ₁ is CH, Z ₂ is N, and R ₁ has 1 to 12 carbon atoms. or an alkoxy group having 1 to 12 carbon atoms (especially a linear alkyl group or alkoxy group), R ₂ and R ₃ are hydrogen atoms, R ₄ is a group represented by Y, A compound in which _R7 is a group having a polymerizable group.

In another preferred embodiment of the azomethine derivative represented by the above chemical formula (2), X is NR ₁₀ , Z ₁ is CH, Z ₂ is N, and R ₁ and R ₂ are , R ₄ is a hydrogen atom, R ₃ is a group represented by Y, R ₇ is a group having a polymerizable group, R ₁₀ is a C 1-12 alkyl group or a C 1-12 is an alkoxy group (particularly a straight-chain alkyl group or alkoxy group) of

Among them, from the viewpoint of facilitating photoisomerization and thereby facilitating melting or softening of a toner image formed by a polymer or a toner using the polymer even with lower energy light irradiation, an azomethine derivative having a polymerizable group is A compound represented by the following chemical formula (3) is preferable.

In chemical formula (3),
X is NR ₁₀ , O or S;
either one of R ₃ or R ₄ is a group represented by Y,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
A ₁ is a hydrogen atom or a methyl group,
A ₂ is an alkylene group having 1 to 18 carbon atoms,
all of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y are hydrogen atoms;
or,
Among R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y, any one of R ₁ to R ₄ not adjacent to Y is a cyano group, a nitro group, hydroxy group, carboxy group, or alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, acyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms and among the remaining groups (R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y, the above "any of R ₁ to R ₄ not adjacent to Y or one”) are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms and R ₁₀ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or
R ₁₀ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyloxy group having 2 to 12 carbon atoms. and R ₁ , R ₂ , and R ₃ or R ₄ not selected as the group represented by Y are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, a carbon number It is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Examples of azomethine derivatives having a polymerizable group include derivatives 1 to 102 in which X, Y, Z ₁ , Z ₂ and R ₁ to R ₁₀ shown in Table 1 below are appropriately selected.

In the polymer of the present invention, the structural unit derived from the azomethine derivative having a polymerizable group represented by chemical formula (1) may be used alone or in combination of two or more.

<Method for preparing an azomethine derivative having a polymerizable group>
A method for preparing an azomethine derivative having a polymerizable group is not particularly limited. For example, it can be prepared by first preparing a desired azomethine derivative and introducing a polymerizable group into the obtained azomethine derivative.

For example, when preparing an azomethine derivative containing a thiophene ring, as a first step, an aniline derivative is reacted with a thiophene carboxaldehyde derivative as a compound having a thiophene ring. At this time, when either the aniline derivative or the thiophenecarboxaldehyde derivative which is the raw material has an OH group as a substituent, a polymerizable group can be easily introduced at the position of the OH group.

For example, X in the above chemical formula (1) is S, R ₁ is a methyl group, R ₂ and R ₃ are H, R ₄ is a group represented by Y, and Z ₁ is CH. , Z ₂ is N, R ₇ is a group having a polymerizable group, and R ₅ , R ₆ , R ₈ and R ₉ are H, Intermediate A can be obtained by the following reaction scheme. can be done.

Specifically, 4-hydroxyaniline and 5-methylthiophene-2-carboxaldehyde are treated in methanol (MeOH) (heated to reflux to react, the reaction solution is filtered, and the resulting powder is treated with cold ethanol. washing and recrystallization with methanol/ethanol), the desired product can be obtained.

After that, as a second step, a polymerizable group is introduced into the intermediate A described above. The method of introducing the polymerizable group is also not particularly limited. For example, when a linker moiety —C ₆ H ₁₂ — is introduced into the above intermediate A, a halogenated alcohol compound such as Cl—C ₆ H ₁₂ —OH is reacted to obtain intermediate B below.

Although the reaction conditions are not particularly limited, for example, in a solvent such as dimethylformamide (DMF), in the presence of potassium carbonate and potassium iodide, the reaction temperature is preferably within the range of 0°C to 100°C, more preferably 0°C to 60°C. It is preferable to carry out the reaction within the following range, more preferably within the range of 0° C. or higher and 40° C. or lower.

Thereafter, as the third step, the intermediate B is reacted with a compound for forming a polymerizable group, such as an acrylate or a methacrylate. Reaction conditions are not particularly limited. For example, it is preferable to carry out the reaction in a known organic solvent in the presence of tertiary amines such as triethylamine and triethanolamine. Preferably, a compound for forming a polymerizable group such as an acrylate or a methacrylate in the mixed liquid containing the intermediate B, the tertiary amines, and the solvent is maintained at 0 to 10°C. dropwise and mix. Thereafter, the mixed solution is allowed to react, for example, at room temperature for about 5 to 10 hours to obtain an azomethine derivative having a polymerizable group.

In addition, in said 1st step, the azomethine derivative which has a desired substituent can be obtained by changing the raw material to be used to another compound. For example, by reacting a benzaldehyde derivative and an aminothiophene derivative, an azomethine derivative in which Z ₁ in chemical formula (1) is N and Z ₂ is CH can be obtained. Further, by using a compound having a furan ring or a pyrrole ring instead of a compound having a thiophene ring as a raw material, an azomethine derivative in which the heteroatom of X is O or N can be obtained. Also, by changing the compounds added in the second and third stages, groups having different structures of polymerizable groups can be introduced. A person skilled in the art can synthesize an azomethine derivative having a desired polymerizable group by appropriately making the above changes and selecting appropriate reaction conditions.

Moreover, in the first step, a polymerizable group can be introduced into the intermediate A without performing the second step by appropriately selecting the raw materials to be used.

<Structural Units Other than Structural Units Derived from Azomethine Derivatives>
The polymer of the present invention may contain a structural unit (another structural unit) other than the structural unit derived from the azomethine derivative having a polymerizable group represented by the chemical formula (1).

The other structural unit is not particularly limited as long as it does not contain an azomethine group, but it is preferably a structural unit that constitutes a thermoplastic resin that softens when heated.

As the other structural unit, those having a vinyl-based polymerizable group are preferable because the synthesis of the copolymer is easy. Specifically, for example, styrene derivatives, (meth)acrylic acid derivatives, olefin derivatives, vinyl ester derivatives, vinyl ether derivatives, vinyl ketone derivatives and the like are used. Structural units are preferred.

Styrene derivatives include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene and pt-butylstyrene. , pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and the like.

(Meth)acrylic acid derivatives include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, diethylaminoethyl ( meth)acrylate, dimethylaminoethyl (meth)acrylate and the like.

Olefin derivatives include ethylene, propylene, n-butylene, isobutylene, n-pentene and the like. The olefin derivative may be linear or branched, and the number of carbon chains is not particularly limited.

Vinyl ester derivatives include vinyl propionate, vinyl acetate, vinyl benzoate and the like. Vinyl ether derivatives include vinyl methyl ether and vinyl ethyl ether. Vinyl ketone derivatives include vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone and the like.

The content of the other structural unit in the polymer is not particularly limited and may be appropriately selected, but is preferably 70% by mass or less with respect to 100% by mass of the total amount of all structural units constituting the polymer. , 40% by mass or less.

The number average molecular weight (total number average molecular weight) Mn of the polymer of the present invention is not particularly limited, but is preferably 3,500 or more, more preferably 3,500 to 100,000, still more preferably 3,500 to 70,000, and even more preferably. is 3,500 to 50,000, particularly preferably 5,000 to 50,000. If the number-average molecular weight of the polymer is 3500 or more, it is preferable because it is excellent in toughness and, when used as a toner, a toner image excellent in fixability can be obtained more easily. In addition, if the number average molecular weight is 100,000 or less, the efficiency of isomerization and softening and melting becomes high, which is preferable.

The number average molecular weight of the polymer of the present invention can be measured by gel permeation chromatography (GPC). Specifically, it can be measured by the method described in Examples below.

<Method for preparing polymer>
The method for synthesizing the polymer of the present invention is not particularly limited, and a known polymerization initiator such as anionic polymerization, cationic polymerization, and living radical polymerization is used to prepare an azomethine derivative having the above polymerizable group as a monomer. A method of polymerization can be used. A known chain transfer agent may be used as necessary.

As the polymerization initiator, for example, the following azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators are used.

Azo or diazo polymerization initiators include 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1 -carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

Peroxide polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane, tris-(t-butylperoxy)triazine and the like.

Chain transfer agents include, for example, benzyl dithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenylprop-2-yldithiobenzoate, 1-acetoxylethyldithiobenzoate, hexakis(thiobenzoylthiomethyl ) benzene, 1,4-bis(thiobenzoylthiomethyl)benzene, 1,2,4,5-tetrakis(thiobenzoylthiomethyl)benzene, 1,4-bis-(2-(thiobenzoylthio)prop-2 -yl)benzene, 1-(4-methoxyphenyl)ethyldithiobenzoate, benzyl dithioacetate; ethoxycarbonylmethyldithioacetate, 2-(ethoxycarbonyl)prop-2-yldithiobenzoate, 2-cyanoprop-2- yl dithiobenzoate, tert-butyl dithiobenzoate, 2,4,4-trimethylpent-2-yl dithiobenzoate, 2-(4-chlorophenyl) prop-2-yl dithiobenzoate, 3- and 4-vinyl benzyldithiobenzoate, S-benzyldiethoxyphosphinyldithioformate, t-butyltrithioperbenzoate, 2-phenylprop-2-yl 4-chlorodithiobenzoate, 2-phenylprop-2-yl 1- dithionaphthalate, 4-cyanopentanoic acid dithiobenzoate, dibenzyltetrathioterephthalate, dibenzyltrithiocarbonate, carboxymethyldithiobenzoate and the like.

The polymerization temperature is preferably 50 to 100.degree. C., more preferably 55 to 90.degree. C., depending on the types of monomers and polymerization initiators used. The polymerization time varies depending on the types of monomers and polymerization initiators used, but is preferably 2 to 60 hours, for example.

The wavelength of the irradiation light when the polymer containing the structural unit derived from the azomethine derivative is fluidized by light irradiation is preferably in the range of 280 nm or more and 480 nm or less, more preferably 300 nm or more and 420 nm or less, and still more preferably It is within the range of 330 nm or more and 420 nm or less. Within the above range, crystals are easily broken (favorable photo-meltability) and fixability is improved. In addition, by irradiating with irradiation light of the above wavelength, fluidization can be achieved without applying heat or pressure. Therefore, by introducing a polymer containing a structural unit derived from the azomethine derivative into a toner, it is possible to obtain a toner that can be fixed at the above wavelength and has high color reproducibility.

Note that the above wavelength range includes a part of visible light. Therefore, the polymer containing the structural unit derived from the azomethine derivative can only be exposed to sunlight (natural light), fluorescent light, or other illumination light. However, it is desirable to fluidize more under low-cost conditions in which the amount of irradiation and irradiation time are suppressed as much as possible. From this point of view, as irradiation conditions of the irradiation light when the polymer containing the structural unit derived from the azomethine derivative is fluidized, the irradiation dose is preferably in the range of 0.1 J/cm ² or more and 200 J/cm ² or less. more preferably 0.1 J/cm ² or more and 100 J/cm ² or less, still more preferably 0.1 J/cm ² or more and 50 J/cm ^{2 or} less.

On the other hand, the conditions for defluidizing (resolidifying) the polymer containing structural units derived from the azomethine derivative may be heating or standing at room temperature, that is, in a natural environment. It is preferable to leave it (in a natural environment) at room temperature (25±15° C. range) where it will not be exposed. In this case, it is better to put it in a dark place, but it may be exposed to visible light such as natural light or fluorescent light.

When the polymer containing a structural unit derived from the azomethine derivative is heated to be non-fluid, the heating temperature is preferably in the range of 0° C. or higher and 200° C. or lower, more preferably in the range of 20° C. or higher and 150° C. or lower. is within.

[Constitution of Toner]
One embodiment of the present invention provides a polymer that is reversibly fluidized/non-fluidized by light irradiation, and which contains a structural unit derived from an azomethine derivative having a polymerizable group, represented by the above chemical formula (1). including toner. By introducing the polymer into the toner, it is possible to obtain a toner that can be fixed by light irradiation and has high color reproducibility.

The content of the polymer containing a structural unit derived from the azomethine derivative depends on the types of the azomethine derivative and other structural units. It is preferably in the range of 5 to 90% by mass based on the total amount of the agent, release agent and polymer of the present invention.

<Binder resin>
The toner of the present invention may further contain a binder resin. The binder resin is a resin that does not have a structure derived from an azomethine derivative, and resins that are generally used as binder resins constituting toners can be used without limitation. Examples of binder resins that can be used include styrene resins, acrylic resins, styrene-acrylic resins, polyester resins, silicone resins, olefin resins, amide resins, and epoxy resins. These binder resins can be used alone or in combination of two or more.

Among these, the binder resin is at least one selected from the group consisting of styrene resins, acrylic resins, styrene-acrylic resins, and polyester resins, from the viewpoint of having low viscosity when melted and high sharp-melting properties. and more preferably at least one selected from the group consisting of styrene-acrylic resins and polyester resins.

(styrene acrylic resin)
The styrene-acrylic resin referred to in the present invention is a polymer containing at least a structural unit derived from a styrene monomer and a structural unit derived from a (meth)acrylic acid ester monomer. Here, the styrene monomer includes not only styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ but also those having a known side chain or functional group in the styrene structure.

Examples of the styrene monomer include those similar to the styrene monomer that can constitute the polymer compound described above.

A (meth)acrylic acid ester monomer has a functional group having an ester bond in its side chain. Specifically, in addition to acrylic acid ester monomers represented by CH ₂ =CHCOOR (R is an alkyl group), methacrylic acid esters represented by CH ₂ =C(CH ₃ )COOR (R is an alkyl group) Vinyl ester compounds such as monomers are included. (Meth)acrylic acid in the (meth)acrylic acid ester monomer means acrylic acid and methacrylic acid.

Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, diethylaminoethyl (meth)acrylate ) acrylate, dimethylaminoethyl (meth)acrylate, and the like.

The styrene monomer and the (meth)acrylic acid ester monomer can be used either alone or in combination of two or more.

The content of the structural unit derived from the styrene monomer and the structural unit derived from the (meth)acrylic acid ester monomer in the styrene acrylic resin is not particularly limited, and the softening point and glass transition temperature of the binder resin are controlled. It can be adjusted as appropriate from the viewpoint of Specifically, the content of structural units derived from styrene monomers is preferably 40 to 95% by mass, more preferably 50 to 80% by mass, relative to the total amount of monomers. . In addition, the content of structural units derived from (meth) acrylic acid ester monomers is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, with respect to the total amount of monomers. preferable.

The styrene-acrylic resin may further contain structural units derived from monomers other than the styrene monomer and the (meth)acrylic acid ester monomer, if necessary. Examples of other monomers include vinyl monomers. Examples of vinyl monomers that can be used in combination when forming the styrene-acrylic copolymer of the present invention are shown below, but the vinyl monomers that can be used in combination are not limited to those shown below.

(1) Olefins Ethylene, propylene, isobutylene, etc. (2) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (3) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (4) Vinyl ketones Vinyl methyl ketone, Vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc. (6) Others Vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylonitrile, methacrylo acrylic or methacrylic acid derivatives such as nitrile and acrylamide;

It is also possible to produce a crosslinked resin using a polyfunctional vinyl monomer. Furthermore, it is also possible to use vinyl monomers having ionic dissociation groups in their side chains. Specific examples of ionic dissociation groups include carboxyl groups, sulfonic acid groups, and phosphoric acid groups. Specific examples of vinyl monomers having these ionic dissociation groups are shown below.

Specific examples of vinyl monomers having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl esters, and itaconic acid monoalkyl esters. .

When forming the styrene-acrylic resin used in the present invention, the contents of the styrene monomer and the (meth)acrylic acid ester monomer are not particularly limited. It is possible to make appropriate adjustments from the viewpoint of temperature control. Specifically, the content of the styrene monomer is preferably 40 to 95% by mass, more preferably 50 to 80% by mass, based on the total monomers. Also, the content of the (meth)acrylic acid ester monomer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total amount of monomers.

The method of forming the styrene-acrylic resin is not particularly limited, and examples thereof include a method of polymerizing monomers using a known oil-soluble or water-soluble polymerization initiator. For example, a known chain transfer agent such as n-octylmercaptan may be used as required. As the oil-soluble polymerization initiator, for example, the following azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators are used.

Azo or diazo polymerization initiators include 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1 -carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

Peroxide polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane, tris-(t-butylperoxy)triazine and the like.

A water-soluble radical polymerization initiator can also be used when forming styrene-acrylic resin particles by an emulsion polymerization method. Examples of water-soluble radical polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

The polymerization temperature is preferably 50 to 100.degree. C., more preferably 55 to 90.degree. C., depending on the types of monomers and polymerization initiators used. The polymerization time varies depending on the types of monomers and polymerization initiators used, but is preferably 2 to 12 hours, for example.

The styrene-acrylic resin particles formed by the emulsion polymerization method may have a structure of two or more layers composed of resins having different compositions. In this case, the production method is to add a polymerization initiator and a polymerizable monomer to a dispersion of resin particles prepared by an emulsion polymerization treatment (first stage polymerization) according to a conventional method, and polymerize this system. A multi-stage polymerization method of processing (second-stage, third-stage polymerization) can be employed.

(polyester resin)
A polyester resin is a polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid component) and a divalent or higher alcohol (polyhydric alcohol component). Incidentally, the polyester resin may be amorphous or crystalline.

The valences of the polyhydric carboxylic acid component and the polyhydric alcohol component are preferably 2 to 3 each, more preferably 2 each. That is, the polyhydric carboxylic acid component preferably contains a dicarboxylic acid component, and the polyhydric alcohol component preferably contains a dialcohol component.

Examples of dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. (dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18 - saturated aliphatic dicarboxylic acids such as octadecanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as methylenesuccinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, dodecenylsuccinic acid; Terephthalic acid, isophthalic acid, t-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anthracenedicarboxylic acid, etc. and the like, and lower alkyl esters and acid anhydrides thereof can also be used. The dicarboxylic acid component may be used alone or in combination of two or more.

In addition, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, their anhydrides, or alkyl esters having 1 to 3 carbon atoms can also be used.

Diol components include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecane Saturated aliphatic diols such as diols, 1,18-octadecanediol, 1,20-eicosanediol, neopentyl glycol; 2-butene-1,4-diol, 3-butene-1,4-diol, 2-butyne -unsaturated aliphatic diols such as 1,4-diol, 3-butyne-1,4-diol and 9-octadecene-7,12-diol; bisphenols such as bisphenol A and bisphenol F, and ethylene oxide addition of these and aromatic diols such as alkylene oxide adducts of bisphenols such as propylene oxide adducts, and derivatives thereof can also be used. The diol component may be used alone or in combination of two or more.

The method for producing the polyester resin is not particularly limited, and the polyester resin can be produced by polycondensing (esterifying) the polyhydric carboxylic acid component and the polyhydric alcohol component using a known esterification catalyst.

Catalysts that can be used in the production of polyester resins include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; aluminum, zinc, manganese, antimony, titanium, tin, zirconium; compounds of metals such as germanium; phosphite compounds; phosphoric acid compounds; and amine compounds. Specific examples of tin compounds include dibutyltin oxide (dibutyltin oxide), tin octylate, tin dioctate, and salts thereof. Titanium compounds include titanium alkoxides such as tetra-n-butyl titanate (Ti(On-Bu) ₄ ), tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as polyhydroxytitanium stearate; Titanium chelates such as acetylacetonate, titanium lactate, titanium triethanolamine, and the like can be mentioned. Germanium dioxide etc. can be mentioned as a germanium compound. Furthermore, aluminum compounds include polyaluminum hydroxide, aluminum alkoxide, tributylaluminate, and the like. You may use these individually by 1 type or in combination of 2 or more types.

Although the polymerization temperature is not particularly limited, it is preferably 70 to 250°C. Also, the polymerization time is not particularly limited, but it is preferably 0.5 to 10 hours. During the polymerization, the pressure inside the reaction system may be reduced as necessary.

The glass transition temperature (Tg) of the toner is preferably 25 to 100.degree. C., more preferably 30 to 80.degree. The glass transition temperature (Tg) of the toner can be adjusted by the molecular weight of the polymer and, when structural units other than the azomethine derivative are included, the type and content of the structural units. When the toner contains a binder resin, it can be further adjusted by the content ratio of the polymer and the binder resin, the type of the binder resin, the molecular weight, and the like.

The toner of the present invention may be particles having a single layer structure or particles having a core-shell structure. The type of binder resin used for the core particles and the shell portion of the core-shell structure is not particularly limited.

<Colorant>
The toner of the present invention preferably further contains a colorant. Although the polymer containing the structural unit derived from the azomethine derivative is colorless, it is thought that it can induce a reversible fluidization/non-fluidization phenomenon accompanying isomerization. Therefore, by introducing a desired colorant into a toner together with a polymer containing a structural unit derived from the azomethine derivative, it is possible to obtain a toner that can be fixed by light irradiation and has high color reproducibility of the added colorant. Commonly known dyes and pigments can be used as the colorant.

Colorants for obtaining a black toner include carbon black, magnetic substances, iron-titanium composite oxide black, etc. Carbon black includes channel black, furnace black, acetylene black, thermal black, and lamp black. be Moreover, ferrite, magnetite, etc. are mentioned as a magnetic substance.

As a coloring agent for obtaining a yellow toner, C.I. I. Dyes such as Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112 and 162; I. Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 74, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 138, Pigment Yellow 155, Pigment Yellow 180 and Pigment Yellow 185.

As a colorant for obtaining a magenta toner, C.I. I. Dyes such as Solvent Red 1, 49, 52, 58, 63, 111 and 122; C.I. I. Pigment Red 5, 48:1, 53:1, 57:1, 122, 139, 144, 149, 166, 177, 178, 222.

As a colorant for obtaining a cyan toner, C.I. I. Dyes such as Solvent Blue 25, 36, 60, 70, 93 and 95; C.I. I. Pigment Blue 1, 7, 15, 15:3, 60, 62, 66, 76 and the like.

Colorants for obtaining toner of each color can be used singly or in combination of two or more for each color.

The content of the colorant is preferably 0.5 to 20% by mass, more preferably 2 to 10% by mass, in the toner particles (toner base particles) before adding the external additive.

<Release agent>
The toner according to the present invention preferably further contains a release agent. Although the polymer containing the structural unit derived from the azomethine derivative is colorless, it is thought that it can induce a reversible fluidization/non-fluidization phenomenon accompanying isomerization. Therefore, by introducing a release agent into the toner together with the polymer containing the structural unit derived from the azomethine derivative, a toner having excellent fixability and high color reproducibility can be obtained when heat fixing is performed together with light irradiation. be able to.

The release agent used is not particularly limited, and various known waxes can be used. Examples of waxes include low-molecular-weight polypropylene, polyethylene, polyolefins such as oxidized low-molecular-weight polypropylene and polyethylene, paraffin wax, synthetic ester wax, and the like. Among them, paraffin wax is preferably used from the viewpoint of improving the storage stability of the toner.

The content of the release agent is preferably 1 to 30% by mass, more preferably 3 to 15% by mass, based on the toner base particles.

<Charge control agent>
The toner according to the present invention may contain a charge control agent. The charge control agent to be used is not particularly limited as long as it is a substance capable of imparting positive or negative charge by triboelectrification and is colorless. An electrostatic charge control agent can be used.

The content of the charge control agent is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, in the toner particles (toner base particles) before adding the external additive.

<External Additives>
In order to improve the fluidity, chargeability, cleanability, etc. of the toner, the toner according to the present invention is produced by adding an external additive such as a fluidizing agent, which is a so-called post-treatment agent, or a cleaning aid, to the toner base particles. may be configured.

Examples of external additives include inorganic oxide particles such as silica particles, alumina particles and titanium oxide particles, inorganic stearate compound particles such as aluminum stearate particles and zinc stearate particles, strontium titanate particles and zinc titanate particles. Inorganic particles such as inorganic titanate compound particles such as If necessary, these inorganic particles may be hydrophobized. These can be used alone or in combination of two or more.

Among these, the external additive is preferably, for example, sol-gel silica particles, surface-hydrophobicized silica particles (hydrophobic silica particles) or titanium oxide particles (hydrophobic titanium oxide particles). More preferably, more than one external additive is used.

The number average primary particle size of the external additive is preferably in the range of 1 to 200 nm, more preferably 10 to 180 nm. At this time, it is particularly preferable that at least one of the external additives has a thickness of 30 nm or more and 180 nm or less.

The amount of these external additives added is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass in the toner.

<Average Particle Diameter of Toner>
The average particle diameter of the toner is preferably 4 to 20 μm, more preferably 5 to 15 μm, as a volume-based median diameter (D50). When the volume-based median diameter (D50) is within the above range, the transfer efficiency is high, the image quality of halftones is improved, and the image quality of fine lines and dots is improved.

The volume-based median diameter (D50) of the toner is obtained by a computer system (manufactured by Beckman Coulter, Inc.) equipped with "Software V3.51" for data processing in "Coulter Counter 3" (manufactured by Beckman Coulter, Inc.). can be measured and calculated using a measuring device connected to

Specifically, 0.02 g of the measurement sample (toner) was mixed with 20 mL of a surfactant solution (for example, a surfactant obtained by diluting a neutral detergent containing a surfactant component with pure water 10 times for the purpose of dispersing the toner particles). solution) and allowed to acclimatize, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is pipetted into a beaker containing "ISOTON II" (manufactured by Beckman Coulter, Inc.) in a sample stand until the concentration indicated by the measuring device reaches 8%.

Here, by setting the display density within the above range, reproducible measured values can be obtained. Then, in the measuring device, the measured particle count number is 25000, the aperture diameter is 50 μm, and the measurement range of 1 to 30 μm is divided into 256 to calculate the frequency value. The particle diameter of is defined as the volume-based median diameter (D50).

[Toner manufacturing method]
The method for producing the toner of the present invention is not particularly limited. For example, in the case of making a toner only from a polymer containing a structural unit derived from the above azomethine derivative, the above polymer is pulverized using an apparatus such as a hammer mill, feather mill, counter jet mill, and the like, and then spin air is applied. A manufacturing method comprising classifying to a desired particle size using a dry classifier such as a sieve, a classifier, or a micron classifier is preferred.

In the case of producing a toner containing a polymer containing a structural unit derived from the above azomethine derivative and a coloring agent but not containing a binder resin, a solvent in which both the above polymer and the coloring agent are dissolved is used to dissolve the above polymer. A manufacturing method is preferred which comprises combining and dissolving a coloring agent to form a solution, removing the solvent, and then pulverizing and classifying in the same manner as described above.

When producing a toner containing a polymer containing a structural unit derived from the above azomethine derivative, a binder resin, and optionally a colorant, a production method using an emulsion aggregation method that facilitates control of the particle size and shape. is preferably

Such a manufacturing method is
(1A) Binder resin particle dispersion preparing step for preparing a binder resin particle dispersion (1B) Polymer compound particle dispersion for preparing a dispersion of polymer compound particles represented by general formula (1) Preparation step (1C) If necessary, a colorant particle dispersion preparation step of preparing a colorant particle dispersion (2) Binder resin particles, polymer compound particles, and optionally colorant particles are present. (3) Toner particles are formed by controlling the shape of the associated particles by adding an aggregating agent to the water-based medium in which the salting out is progressed and at the same time performing aggregation and fusion to form associated particles. (4) Filtration and washing process for filtering toner particles from an aqueous medium and removing surfactants from the toner particles (5) Drying process for drying the washed toner particles (6) Drying process It is preferable to include each step of an external additive adding step of adding an external additive to the formed toner particles.

The steps (1A) to (1C) will be described below.

(1A) Binder Resin Particle Dispersion Preparation Step In this step, resin particles are formed by conventionally known emulsion polymerization or the like, and the resin particles are aggregated and fused to form binder resin particles. As an example, a polymerizable monomer constituting the binder resin is put into an aqueous medium and dispersed, and the polymerizable monomer is polymerized with a polymerization initiator to prepare a dispersion liquid of binder resin particles. .

As a method for obtaining a binder resin particle dispersion, in addition to the method of polymerizing a polymerizable monomer in an aqueous medium using a polymerization initiator, for example, dispersion treatment in an aqueous medium without using a solvent is performed. Alternatively, a method of dissolving the crystalline resin in a solvent such as ethyl acetate to form a solution, emulsifying and dispersing the solution in an aqueous medium using a dispersing machine, and then removing the solvent.

At this time, if necessary, the binder resin may contain a release agent in advance. In addition, for dispersion, polymerize in the presence of an appropriately known surfactant (e.g., anionic surfactants such as polyoxyethylene (2) sodium dodecyl ether sulfate, sodium dodecyl sulfate, dodecylbenzenesulfonic acid). is also preferred.

The volume-based median diameter of the binder resin particles in the dispersion is preferably 50 to 300 nm. The volume-based median diameter of the binder resin particles in the dispersion can be measured by a dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

(1B) Polymer compound particle dispersion preparation step In this polymer compound particle dispersion preparation step, the polymer containing the structural unit derived from the above azomethine derivative is dispersed in an aqueous medium in the form of fine particles to obtain the above polymer. This is a step of preparing a dispersion of polymer particles containing a structural unit derived from an azomethine derivative.

In preparing a dispersion of polymer particles containing structural units derived from the azomethine derivative, first, an emulsion of the polymer is prepared. The emulsified solution of the polymer can be prepared by, for example, dissolving the polymer in an organic solvent and then emulsifying the resulting solution in an aqueous medium.

The method of dissolving the polymer in the organic solvent is not particularly limited, and examples thereof include a method of adding the polymer to the organic solvent and stirring and mixing so that the polymer is dissolved. The amount of the polymer added is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the organic solvent.

Next, the resulting polymer solution and an aqueous medium are mixed and stirred using a known dispersing machine such as a homogenizer. As a result, the polymer forms droplets and is emulsified in the aqueous medium to prepare an emulsion of the polymer.

The amount of the polymer solution to be added is preferably 10 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the aqueous medium.

When the polymer solution and the aqueous medium are mixed, the temperatures of the polymer solution and the aqueous medium are in a temperature range below the boiling point of the organic solvent, preferably 20° C. or higher and 80° C. or lower, and more. The temperature is preferably 30°C or higher and 75°C or lower. When the polymer solution and the aqueous medium are mixed, the temperature of the polymer solution and the temperature of the aqueous medium may be the same or different, preferably the same.

As for the stirring conditions of the disperser, for example, when the volume of the stirring vessel is 1 to 3 L, the rotation speed is preferably 7000 rpm or more and 20000 rpm or less, and the stirring time is preferably 10 minutes or more and 30 minutes or less.

A dispersion of the polymer particles is prepared by removing the organic solvent from the polymer emulsion. Examples of the method for removing the organic solvent from the polymer emulsion include known methods such as air blowing, heating, pressure reduction, or a combination thereof.

As an example, the emulsion of the polymer is preferably 25° C. or higher and 90° C. or lower, more preferably 30° C. or higher and 80° C. or lower, under an inert gas atmosphere such as nitrogen, for example, at an initial organic solvent amount of The organic solvent is removed by heating until about 80% to 95% by weight is removed. As a result, the organic solvent is removed from the aqueous medium, and a dispersion of the polymer particles in which the polymer particles are dispersed in the aqueous medium is prepared.

The mass average particle size of the polymer particles in the polymer particle dispersion is preferably 90 nm or more and 1200 nm or less. The mass average particle diameter is determined by the viscosity when the polymer compound is blended in the organic solvent, the blending ratio of the polymer solution and the aqueous medium, and the stirring speed of the disperser when preparing the polymer emulsion. It can be set within the above range by appropriately adjusting the above. The mass average particle size of the polymer compound particles in the polymer particle dispersion can be measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).

<Organic solvent>
The organic solvent used in this step is not particularly limited as long as it can dissolve a polymer containing a structural unit derived from an azomethine derivative having a polymerizable group represented by chemical formula (1). Specifically, esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; saturated hydrocarbons such as hexane and heptane; Examples include halogenated hydrocarbons such as chlorocarbons.

Such organic solvents can be used alone or in combination of two or more. Among these organic solvents, ketones and halogenated hydrocarbons are preferred, and methyl ethyl ketone and dichloromethane are more preferred.

<Aqueous medium>
Examples of the aqueous medium used in this step include water, or an aqueous medium containing water as a main component and water-soluble solvents such as alcohols and glycols, and optional ingredients such as surfactants and dispersants. be done. A mixture of water and a surfactant is preferably used as the aqueous medium.

Examples of surfactants include cationic surfactants, anionic surfactants, and nonionic surfactants. Examples of cationic surfactants include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, hexadecyltrimethylammonium bromide and the like. Examples of anionic surfactants include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecylbenzenesulfonate, and sodium dodecylsulfate. Examples of nonionic surfactants include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl Sucrose etc. are mentioned.

Such surfactants can be used alone or in combination of two or more. Among surfactants, anionic surfactants, more preferably sodium dodecylbenzenesulfonate, are preferably used.

The amount of the surfactant added is preferably 0.01 to 10 parts by mass, more preferably 0.04 to 1 part by mass with respect to 100 parts by mass of the aqueous medium.

(1C) Colorant Particle Dispersion Preparation Step This colorant particle dispersion preparation step is a step of dispersing the colorant in the form of fine particles in an aqueous medium to prepare a colorant particle dispersion.

Dispersion of the colorant can be performed using mechanical energy. The number-based median diameter of the colorant particles in the dispersion is preferably 10 to 300 nm, more preferably 50 to 200 nm. The number-based median diameter of the colorant particles can be measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).

The steps from (2) association step to (6) external additive addition step can be carried out according to various conventionally known methods.

Although the flocculant used in the (2) association step is not particularly limited, one selected from metal salts is preferably used. Examples of metal salts include monovalent metal salts such as salts of alkali metals such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; trivalent metal salts such as iron and aluminum. etc. Specific metal salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, etc., of which less It is particularly preferred to use a divalent metal salt because it can promote These can be used alone or in combination of two or more.

[Developer]
For example, the toner according to the present invention may be used as a one-component magnetic toner containing a magnetic material, mixed with a so-called carrier and used as a two-component developer, or used as a non-magnetic toner alone. and any of them can be suitably used.

As the magnetic material, for example, magnetite, γ-hematite, or various ferrites can be used.

The carrier contained in the two-component developer includes magnetic particles made of conventionally known materials such as metals such as iron, steel, nickel, cobalt, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead. can be used.

The carrier may be a coated carrier in which the surfaces of magnetic particles are coated with a coating agent such as a resin, or a resin-dispersed carrier in which magnetic powder is dispersed in a binder resin. The coating resin is not particularly limited, but for example, olefin resin, acrylic resin, styrene resin, styrene-acrylic resin, silicone resin, polyester resin, fluorine resin, or the like is used. Moreover, the resin for constituting the resin-dispersed carrier particles is not particularly limited, and known resins can be used. can do.

The volume-based median diameter of the carrier is preferably 20 to 100 μm, more preferably 25 to 80 μm. The volume-based median diameter of the carrier can typically be measured by a laser diffraction particle size distribution analyzer "HELOS" (manufactured by SYMPATEC) equipped with a wet disperser.

The mixing amount of the toner with the carrier is preferably 2 to 10% by weight, with the total weight of the toner and the carrier being 100% by weight.

[Image forming method]
The toner of the present invention can be used in various known electrophotographic image forming methods. For example, it can be used for a monochrome image forming method and a full-color image forming method. In the full-color image forming method, there is a four-cycle image forming method configured by four types of color developing devices for yellow, magenta, cyan, and black, respectively, and one photoreceptor, and a color developing method for each color. The present invention can be applied to any image forming method such as a tandem image forming method in which an image forming unit having a device and a photoreceptor is mounted for each color.

That is, the image forming method according to one embodiment of the present invention includes the steps of: 1) forming a toner image made of the toner of the present invention on a recording medium; and 2) irradiating the toner image with light to form the toner image. and softening.

Step 1) In this step, a toner image made of the toner of the present invention is formed on a recording medium.

(recoding media)
A recording medium is a member for holding a toner image. Examples of recording media include coated printing paper such as plain paper, fine paper, art paper, and coated paper, commercially available Japanese paper and postcard paper, OHP or packaging resin film, and cloth. .

The recording medium may be in the form of a sheet (leaf) having a predetermined size, or may be in the form of a long sheet that is wound into a roll after the toner image is fixed.

The formation of the toner image can be carried out, for example, by transferring the toner image on the photosensitive member onto the recording medium, as will be described later.

Step 2) In this step, the formed toner image is irradiated with light to soften the toner image. As a result, the toner image can be adhered onto the recording medium.

The wavelength of the light to be irradiated is not particularly limited as long as the toner image can be sufficiently softened by photothermal conversion by the polymer in the toner. Within the above range, the toner image can be softened more efficiently. From the same point of view, the irradiation amount of light is preferably 0.1 to 200 J/cm ² , more preferably 0.1 to 100 J/cm ² , still more preferably 0.1 to 50 J/cm ² .

Light irradiation can be performed using a light source such as a light emitting diode (LED) or a laser light source, as described later.

After step 2), step 3) of pressing the softened toner image may be further carried out, if necessary.

Step 3) In this step, the softened toner image is pressed.

The pressure when pressing the toner image on the recording medium is not particularly limited, but is preferably 0.01 to 5.0 MPa, more preferably 0.05 to 1.0 MPa. By setting the pressure to 0.01 MPa or more, the amount of deformation of the toner image can be increased, so the contact area between the toner image and the recording paper S increases, and the fixability of the image can be further improved. Also, by setting the pressure to 5.0 MPa or less, shock noise during pressurization can be suppressed.

The pressing step may be performed before or at the same time as the step of applying light to soften the toner image (step 2) above). It is preferable because it can be pressed, and as a result, the fixability of the image is further improved.

Further, in the pressing step, the softened toner image may be further heated. That is, the pressing process may be performed while heating the toner image.

The heating temperature of the toner image (the surface temperature of the toner image during heating) is preferably (Tg+20) to (Tg+100)°C, where Tg is the glass transition temperature of the toner, and is (Tg+25) to (Tg+80)°C. is more preferable. When the surface temperature of the toner image is (Tg+20)° C. or higher, the toner image is easily deformed by pressure, and when it is (Tg+100)° C. or lower, hot offset is easily suppressed. Note that hot offset refers to a phenomenon in which a part of the toner is transferred to a pressure member such as a roller in the fixing process, and the toner layer is divided.

In addition, before the step 2), the step 4) of heating the toner image in advance may be further performed if necessary. As described above, the sensitivity of the polymer compound of the present invention to light can be further increased by further performing the step 4) of heating the toner image in advance before the step of 2). As a result, even if it is a polymer, the sensitivity to light is less likely to be impaired, and the melting or softening of the toner image by light irradiation is facilitated.

The image forming method of the present invention can be performed by using, for example, the following image forming apparatus.

FIG. 1 is a schematic configuration diagram showing an image forming apparatus 100 used in an image forming method according to an embodiment of the invention. However, the image forming apparatus used in the present invention is not limited to the following forms and illustrated examples. Although FIG. 1 shows an example of a monochrome image forming apparatus 100, the present invention can also be applied to a color image forming apparatus.

The image forming apparatus 100 is an apparatus for forming an image on a recording sheet S as a recording medium,
Equipped with an image reading device 71 and an automatic document feeder 72 , the image forming section 10 , the irradiation section 40 and the pressing section 9 form an image on the recording paper S transported by the paper transport system 7 .

Further, although the image forming apparatus 100 uses the recording paper S as a recording medium, the medium on which the image is formed may be other than the paper.

The document d placed on the document table of the automatic document feeder 72 is scanned and exposed by the optical system of the scanning exposure device of the image reading device 71 and read into the image sensor CCD. An analog signal photoelectrically converted by the image sensor CCD is subjected to analog processing, A/D conversion, shading correction, image compression processing, etc. in the image processing section 20, and then input to the exposure device 3 of the image forming section 10. be.

The paper transport system 7 includes a plurality of trays 16, a plurality of paper feed units 11, transport rollers 12, a transport belt 13, and the like. Each tray 16 accommodates recording paper S of a predetermined size, and the paper feeding unit 11 of the tray 16 determined according to an instruction from the control unit 90 is operated to supply the recording paper S. FIG. The transport roller 12 transports the recording paper S sent out from the tray 16 by the paper feeding unit 11 or the recording paper S carried in from the manual paper feeding unit 15 to the image forming unit 10 .

The image forming unit 10 includes a charger 2 , an exposure unit 3 , a developing unit 4 , a transfer unit 5 and a cleaning unit 8 arranged in this order around the photoreceptor 1 along the rotational direction of the photoreceptor 1 . It is

A photoreceptor 1, which is an image carrier, is an image carrier having a photoconductive layer formed on its surface, and is configured to be rotatable in the direction of the arrow in FIG. 1 by a driving device (not shown). A thermo-hygrometer 17 for detecting temperature and humidity in the image forming apparatus 100 is provided near the photoreceptor 1 .

The charger 2 uniformly charges the surface of the photoreceptor 1 to uniformly charge the surface of the photoreceptor 1 . The exposure unit 3 has a beam light source such as a laser diode, and irradiates the charged surface of the photoreceptor 1 with a beam light to eliminate the electric charge on the irradiated portion, thereby forming a static image on the photoreceptor 1 according to the image data. Forms an electrostatic latent image. The developing unit 4 supplies toner contained therein to the photoreceptor 1 to form a toner image based on an electrostatic latent image on the surface of the photoreceptor 1 .

The transfer unit 5 faces the photoreceptor 1 with the recording paper S interposed therebetween, and transfers the toner image onto the recording paper S. As shown in FIG. The cleaning section 8 has a blade 85 . The blade 85 cleans the surface of the photoreceptor 1 to remove the developer remaining on the surface of the photoreceptor 1 .

The recording paper S onto which the toner image has been transferred is conveyed to the pressure bonding section 9 by the conveying belt 13 . The pressure-bonding unit 9 is optionally installed, and applies pressure alone or heat and pressure to the recording paper S to which the toner image has been transferred by the pressure members 91 and 92, thereby performing a fixing process, thereby recording. The image is fixed on the paper S. The recording paper S on which the image has been fixed is transported to the paper discharge section 14 by the transport roller, and is discharged from the paper discharge section 14 to the outside of the apparatus.

In addition, the image forming apparatus 100 includes a paper reversing unit 24, and the recording paper S subjected to the heat fixing process is conveyed to the paper reversing unit 24 before the paper discharging unit 14, and then reversed and discharged. Alternatively, the recording paper S whose front and back sides have been reversed is conveyed to the image forming section 10 again, and images can be formed on both sides of the recording paper S. FIG.

<Irradiation unit>
FIG. 2 is a schematic configuration diagram of the irradiation unit 40 in the image forming apparatus 100. As shown in FIG.

An image forming apparatus 100 according to one embodiment of the present invention includes an irradiation section 40 . The irradiation unit 40 irradiates the toner image formed on the recording paper S with light. Examples of devices that constitute the irradiation unit 40 include light emitting diodes (LEDs) and laser light sources.

The irradiation unit 40 irradiates light toward the first surface of the recording paper S holding the toner image on the photosensitive member side. It is arranged on the photoreceptor side with respect to the

The irradiation unit 40 is arranged downstream of the nip position between the photoreceptor 1 and the transfer unit 5 in the sheet conveying direction and upstream of the pressing unit 9 in the sheet conveying direction.

According to the image forming method according to one embodiment of the present invention, after charging the photoreceptor 1 by applying a uniform potential to the photoreceptor 1 by the charger 2, the photoreceptor 1 is exposed with a light beam irradiated by the exposure device 3 based on the original image data. It scans over the body 1 and forms an electrostatic latent image. Next, the developer containing the toner of the present invention is supplied onto the photosensitive member 1 by the developing section 4 .

When the toner image carried on the surface of the photoreceptor 1 reaches the position of the transfer unit 5 due to the rotation of the photoreceptor 1 , the recording paper S is conveyed from the tray 16 to the image forming unit 10 , and transferred to the transfer unit 5 . The toner image on the photoreceptor 1 is transferred onto the recording paper S nipped between the transfer portion 5 and the photoreceptor 1 by the applied transfer bias.

The transfer unit 5 also serves as a pressure member, and can transfer the toner image from the photoreceptor 1 to the recording paper S while ensuring that the polymer compound contained in the toner image adheres firmly to the recording paper S. can be made

After the toner image is transferred onto the recording paper S, the blade 85 of the cleaning section 8 removes the developer remaining on the surface of the photoreceptor 1 .

While the recording paper S having the toner image transferred thereon is conveyed to the pressing unit 9 by the conveying belt 13 , the irradiation unit 40 irradiates the toner image transferred onto the recording paper S with light. By irradiating the toner image on the first surface of the recording paper S with light from the irradiation unit 40, the toner image can be melted more reliably, and the fixability of the toner image to the recording paper S can be improved. can be done.

When the recording sheet S carrying the toner image reaches the pressing section 9 by the conveying belt 13 , the pressing members 91 and 92 press the toner image onto the first surface of the recording sheet S. As shown in FIG. Since the toner image is softened by light irradiation from the irradiating unit 40 before the fixing process is performed by the pressing unit 9, energy saving for pressing the image onto the recording sheet S can be achieved.

The pressure when pressing the toner image is as described above. The pressing step may be performed before, at the same time as, or after the step of softening the toner image by irradiating light. From the viewpoint of being able to apply pressure to the toner image that has been softened in advance and to easily increase the image strength, it is preferable that the application of pressure is performed after the light irradiation.

Further, the pressure member 91 can heat the toner image on the recording paper S when the recording paper S passes between the pressure members 91 and 92 . The toner image softened by the light irradiation is further softened by this heating, and as a result, the fixability of the toner image to the recording paper S is further improved.

The heating temperature of the toner image is as described above. The heating temperature of the toner image (the surface temperature of the toner image) can be measured with a non-contact temperature sensor. Specifically, for example, a non-contact temperature sensor may be installed at a position where the recording medium is discharged from the pressure member to measure the surface temperature of the toner image on the recording medium.

The toner image pressed by the pressing members 91 and 92 is solidified and fixed on the recording sheet S. As shown in FIG.

(Photosensitive adhesive)
Since the polymer of the present invention is reversibly fluidized and non-fluidized by light irradiation, the compound of the present invention can be used to prepare a photosensitive adhesive that can be used repeatedly. For example, it can be applied to various adhesion techniques as a photosensitive adhesive that can be repetitively photodetachable in response to changes in viscosity (coefficient of friction). Thus, one embodiment of the invention is a photosensitive adhesive comprising the polymer of the invention.

The photosensitive adhesive of the present invention can be used for temporary fixing that can be used repeatedly, and is also suitable for recycling, but is not limited to these.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.

[Example 1]
<Synthesis of azomethine derivative monomer 1>

4-Aminophenol (5 g, 0.046 mol), 5-methylthiophene-2-carboxaldehyde (5.8 g, 0.046 mol), and 100 ml of ethanol were charged into a 100 ml four-headed flask and heated with stirring. The reaction solution was subjected to suction filtration, and the resulting powder was washed with cold ethanol. Further, recrystallization was performed with methanol/ethanol to obtain the desired product 1.

Next, in a 200 ml four-necked flask, the target product 1 (5 g, 0.023 mol) obtained above was dissolved in 25 ml of dimethylformamide (DMF). To this, 4.88 g (0.035 mol) of potassium carbonate was added and stirred while maintaining the temperature at 30°C. To this, 10.2 mg (0.06 mmol) of potassium iodide and 6-chloro-1-hexanol (3.54 g, 0.026 mol) were added and reacted at 110°C. It was cooled to room temperature, added to 650 g of ice and filtered. The crystals were dispersed in 400 ml of water, washed with stirring overnight, filtered and dried. Further, recrystallization was performed with ethanol to obtain the target substance 2.

Next, a 100 ml four-headed flask was charged with the target product 2 (3 g, 0.001 mol) obtained above, 1.34 ml (0.001 mol) of triethylamine, and 30 ml of dichloromethane. At this time, the raw material was in a dispersed state. While maintaining the internal temperature at 0°C, a solution of 1.04 g (0.011 mol) of acrylic acid chloride dissolved in 10 ml of dichloromethane was added dropwise while maintaining the internal temperature at 0 to 5°C. As it was dripped, the raw material dissolved.

After completion of dropping, the reaction solution was returned to room temperature and stirred. After completion of the reaction, dichloromethane was removed by concentration, dissolved in ethyl acetate, washed with dilute hydrochloric acid, aqueous sodium hydrogencarbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate and then concentrated. The resulting orange crystals were purified with a silica gel column (ethyl acetate/heptane=1/5) to obtain azomethine derivative monomer 1.

<Synthesis of Polymer 1>
In a 100 ml four-necked flask, 1.5 g (4.096 mmol) of the azomethine derivative monomer 1 obtained above, 5 mg (0.023 mmol) of 4-cyanopentanoic acid dithiobenzoate and 1 mg (0.006 mmol) of AIBN were added. was dissolved in 4 ml of anisole. Then, after creating an argon gas atmosphere by freezing and degassing, the temperature was raised to 75° C., and polymerization was performed by stirring. After 40 ml of methanol was gradually added dropwise to the obtained polymer solution, unreacted azomethine derivative monomer 1 was removed by adding THF. The collected polymer solution was dried in a vacuum drying oven at 40° C. for 24 hours to obtain Polymer 1. The number average molecular weight Mn of the obtained polymer 1 was 12,000 when measured by the GPC method.

<Preparation of Polymer Particle Dispersion Liquid 1>
80 parts by mass of dichloromethane and 20 parts by mass of polymer 1 obtained above were mixed and stirred while heating at 50° C. to obtain a solution containing polymer 1 . A mixture of 99.5 parts by mass of distilled water warmed to 50° C. and 0.5 parts by mass of a 20% by mass sodium dodecylbenzenesulfonate aqueous solution was added to 100 parts by mass of the obtained solution. Thereafter, the mixture was emulsified by stirring at 16,000 rpm for 20 minutes using a homogenizer (manufactured by Heidolf) equipped with a shaft generator 18F, and an emulsion of polymer 1 was obtained.

The resulting emulsified liquid was put into a separable flask, and the organic solvent was removed by heating and stirring at 40° C. for 90 minutes while supplying nitrogen into the gas phase to obtain a polymer particle dispersion liquid 1. When the particle size of the polymer particles in the polymer particle dispersion 1 was measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), the mass average particle size was 193 nm. .

<Preparation of styrene acrylic resin particle dispersion>
(First stage polymerization)
A reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device was charged with a solution of 8 parts by mass of sodium dodecyl sulfate dissolved in 3000 parts by mass of ion-exchanged water, and stirred at a stirring speed of 230 rpm under a nitrogen stream. while increasing the internal temperature to 80°C. After raising the temperature, a solution obtained by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added, and the liquid temperature was raised to 80° C. again. 0 parts by weight of n-octyl-3-mercaptopropionate and 16.0 parts by weight of n-octyl-3-mercaptopropionate was added dropwise over 1 hour, followed by heating and stirring at 80°C for 2 hours for polymerization. to prepare a styrene-acrylic resin particle dispersion (1A) containing the styrene-acrylic resin particles (1a).

(Second-stage polymerization)
A reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device was charged with a solution of 7 parts by mass of polyoxyethylene (2) sodium dodecyl ether sulfate dissolved in 800 parts by mass of ion-exchanged water, and heated to 98°C. 260 parts by mass of the styrene acrylic resin particle dispersion (1A) obtained above, 245 parts by mass of styrene, 120 parts by mass of n-butyl acrylate, and 1.5 parts by mass of n-octyl-3-mercaptopropionate. is added at 90 ° C. and mixed and dispersed for 1 hour with a mechanical disperser "CREARMIX (registered trademark)" (manufactured by M Technic Co., Ltd.) having a circulation path, emulsified particles A dispersion containing (oil droplets) was prepared. Next, an initiator solution prepared by dissolving 6 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water is added to the dispersion, and the system is heated and stirred at 82° C. for 1 hour to carry out polymerization. A styrene-acrylic resin particle dispersion (1B) containing styrene-acrylic resin particles (1b) was prepared.

(Third stage polymerization)
A solution of 11 parts by mass of potassium persulfate dissolved in 400 parts by mass of ion-exchanged water was added to the resulting styrene-acrylic resin particle dispersion (1B), and then 435 parts by mass of styrene was added at a temperature of 82°C. , 130 parts by mass of n-butyl acrylate, 33 parts by mass of methacrylic acid and 8 parts by mass of n-octyl-3-mercaptopropionate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated and stirred for 2 hours for polymerization, and then cooled to 28° C. to obtain a styrene-acrylic resin particle dispersion liquid 1 containing styrene-acrylic resin 1. Moreover, when the glass transition temperature (Tg) of the styrene acrylic resin 1 was measured, it was 45°C.

(Preparation of Cyan Colorant Particle Dispersion (Cy-1))
90 parts by mass of sodium n-dodecylsulfate was added to 1600 parts by mass of deionized water. While stirring this solution, 420 parts by mass of copper phthalocyanine (C.I. Pigment Blue 15:3) was gradually added to the solution, and then using a stirring device "CLEARMIX" (manufactured by M Technic Co., Ltd.). A cyan colorant particle dispersion liquid (Cy-1) was prepared by performing a dispersion treatment with the

The volume-based median diameter of the colorant particles in the cyan colorant particle dispersion (Cy-1) was 110 nm.

<Preparation of Release Agent Dispersion 1>
80 parts by mass of dichloromethane and 20 parts by mass of paraffin wax “HNP-11” (manufactured by Nippon Seiro Co., Ltd.), which is a release agent, are mixed and stirred while being heated at 50° C. to obtain a solution containing the release agent. Obtained. A mixture of 99.5 parts by mass of distilled water warmed to 50° C. and 0.5 parts by mass of a 20% by mass sodium dodecylbenzenesulfonate aqueous solution was added to 100 parts by mass of the resulting solution. Thereafter, the mixture was emulsified by stirring at 16000 rpm for 20 minutes using a homogenizer (manufactured by Heidolf) equipped with a shaft generator 18F to obtain an emulsion of a release agent.

The resulting emulsified liquid was put into a separable flask, and the organic solvent was removed by heating and stirring at 40° C. for 90 minutes while supplying nitrogen into the gas phase, to obtain Release Agent Dispersion 1. The particle size of the release agent particles in Release Agent Dispersion 1 was measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), and the mass average particle size was 125 nm. there were.

<Preparation of Toner 1>
456 parts by mass of polymer particle dispersion liquid 1 prepared above in terms of solid content, 114 parts by mass of styrene acrylic resin particle dispersion liquid 1 in terms of solid content, and cyan colorant particle dispersion liquid (Cy-1) in terms of solid content 52 parts by mass of the release agent dispersion liquid 1 in terms of solid content, and 900 parts by mass of ion-exchanged water were charged into a reactor equipped with a stirrer, a temperature sensor, and a cooling pipe. The temperature inside the container was kept at 30° C., and the pH was adjusted to 10 by adding a 5 mol/liter sodium hydroxide aqueous solution.

Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added dropwise over 10 minutes while stirring. C., and the particle growth reaction was continued while maintaining the temperature at 70.degree. In this state, the particle size of the associated particles was measured using "Multisizer 3" (manufactured by Beckman Coulter, Inc.). was dissolved in 760 parts by mass of ion-exchanged water to stop grain growth. After stirring at 70° C. for 1 hour, the temperature was further increased and the mixture was heated and stirred at 75° C. to promote fusion of the particles. Thereafter, by cooling to 30° C., a dispersion liquid of toner base particles was obtained.

The dispersion liquid of the obtained toner base particles was subjected to solid-liquid separation with a centrifuge to form a wet cake of the toner base particles. The wet cake is washed with ion-exchanged water at 35°C in a centrifuge until the electric conductivity of the filtrate reaches 5 μS/cm, and then transferred to a “flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.)”, and the water content is It was dried to 0.5% by mass to prepare toner base particles.

1% by mass of hydrophobic silica (number-average primary particle size: 12 nm) and 0.3% by mass of hydrophobic titania (number-average primary particle size: 20 nm) were added to the obtained toner base particles, and a Henschel mixer (registered Toner 1 was obtained by blending with a trademark).

[Example 2]
Polymer 2 was obtained in the same manner as in Example 1 <Synthesis of Azomethine Derivative Monomer 1> except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde. Toner 2 was obtained in the same manner as in Example 1 except that Polymer 2 was used instead of Polymer 1.

[Example 3]
Polymer 3 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-octylthiophene-2-carboxaldehyde. Toner 3 was obtained in the same manner as in Example 1, except that Polymer 3 was used instead of Polymer 1.

[Example 4]
Polymer 4 was obtained in the same manner as in Example 1 <Synthesis of Azomethine Derivative Monomer 1>, except that 5-t-butylthiophene-2-carboxaldehyde was used instead of 5-methylthiophene-2-carboxaldehyde. Toner 4 was obtained in the same manner as in Example 1, except that Polymer 4 was used instead of Polymer 1.

[Example 5]
Polymer 5 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methoxythiophene-2-carboxaldehyde. Toner 5 was obtained in the same manner as in Example 1, except that Polymer 5 was used instead of Polymer 1.

[Example 6]
Polymer 6 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexyloxythiophene-2-carboxaldehyde. Toner 6 was obtained in the same manner as in Example 1, except that Polymer 6 was used instead of Polymer 1.

[Example 7]
Polymer 7 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-carboxylate methylthiophene-2-carboxaldehyde. Toner 7 was obtained in the same manner as in Example 1, except that Polymer 7 was used instead of Polymer 1.

[Example 8]
Polymer 8 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> of Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 5-carboxylic acid hexylthiophene-2-carboxaldehyde. . Toner 8 was obtained in the same manner as in Example 1, except that Polymer 8 was used instead of Polymer 1.

[Example 9]
Polymer 9 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-acetylthiophene-2-carboxaldehyde.

[Example 10]
Polymer 10 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexanoylthiophene-2-carboxaldehyde. Toner 10 was obtained in the same manner as in Example 1, except that Polymer 10 was used instead of Polymer 1.

[Example 11]
Polymer 11 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 2-thiophenecarboxaldehyde. Toner 11 was obtained in the same manner as in Example 1, except that Polymer 11 was used instead of Polymer 1.

[Example 12]
Polymer 12 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 5-bromothiophene-2-carboxaldehyde. Toner 12 was obtained in the same manner as in Example 1, except that Polymer 12 was used instead of Polymer 1.

[Example 13]
Polymer 13 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-cyanothiophene-2-carboxaldehyde. Toner 13 was obtained in the same manner as in Example 1, except that Polymer 13 was used instead of Polymer 1.

[Example 14]
Polymer 14 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-nitrothiophene-2-carboxaldehyde. Toner 14 was obtained in the same manner as in Example 1 except that Polymer 14 was used instead of Polymer 1.

[Example 15]
Polymer 15 was prepared in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 4-methyl-5-hexylthiophene-2-carboxaldehyde. Obtained. Toner 15 was obtained in the same manner as in Example 1 except that Polymer 15 was used instead of Polymer 1.

[Example 16]
Polymer 16 was prepared in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 3-methyl-5-hexylthiophene-2-carboxaldehyde. Obtained. Toner 16 was obtained in the same manner as in Example 1 except that Polymer 16 was used instead of Polymer 1.

[Example 17]
In <Synthesis of azomethine derivative monomer 1> of Example 1, 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde, and 4-aminophenol was changed to 4-amino-m-cresol. Polymer 17 was obtained in the same manner except for the changes. Toner 17 was obtained in the same manner as in Example 1 except that Polymer 17 was used instead of Polymer 1.

[Example 18]
In <Synthesis of azomethine derivative monomer 1> of Example 1, 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde, and 4-aminophenol was changed to 4-amino-o-cresol. Polymer 18 was obtained in the same manner except for the changes. Toner 18 was obtained in the same manner as in Example 1, except that Polymer 18 was used instead of Polymer 1.

[Example 19]
Polymer 19 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 4-hexylthiophene-2-carboxaldehyde was used instead of 5-methylthiophene-2-carboxaldehyde. Toner 19 was obtained in the same manner as in Example 1, except that Polymer 19 was used instead of Polymer 1.

[Example 20]
Polymer 20 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methylthiophene-3-carboxaldehyde. Toner 20 was obtained in the same manner as in Example 1, except that Polymer 20 was used instead of Polymer 1.

[Example 21]
Polymer 21 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-3-carboxaldehyde. Toner 21 was obtained in the same manner as in Example 1, except that Polymer 21 was used instead of Polymer 1.

[Example 22]
The same method as in <Synthesis of azomethine derivative monomer 1> in Example 1 except that 4-hydroxybenzaldehyde was used in place of 4-aminophenol and 2-amino-5-hexylthiophene was used in place of 5-methylthiophene-2-carboxaldehyde. to give polymer 22. Toner 22 was obtained in the same manner as in Example 1, except that Polymer 22 was used instead of Polymer 1.

[Example 23]
In <Synthesis of azomethine derivative monomer 1> of Example 1, 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde, and 6-chloro-1-hexanol was replaced with 8-chloro-1. -Polymer 23 was obtained in the same manner, except that octanol was used. Toner 23 was obtained in the same manner as in Example 1, except that Polymer 23 was used instead of Polymer 1.

[Example 24]
In <Synthesis of azomethine derivative monomer 1> of Example 1, 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde, and 4-aminophenol was changed to 4-(hydroxyhexyl)aniline. A polymer 24 was obtained in the same manner except that the step of obtaining the objective product 2 was omitted. Toner 24 was obtained in the same manner as in Example 1, except that Polymer 24 was used instead of Polymer 1.

[Example 25]
Same as Example 1 <Synthesis of Azomethine Derivative Monomer 1> except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylthiophene-2-carboxaldehyde and acrylic acid chloride was changed to methacrylic acid chloride. Polymer 25 was obtained in a similar manner. Toner 25 was obtained in the same manner as in Example 1, except that Polymer 25 was used instead of Polymer 1.

[Example 26]
Polymer 26 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 4-aminophenol was changed to 3-aminophenol. Toner 26 was obtained in the same manner as in Example 1, except that Polymer 26 was used instead of Polymer 1.

[Example 27]
Polymer 27 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1 except that 4-aminophenol was changed to 2-aminophenol. Toner 27 was obtained in the same manner as in Example 1, except that Polymer 27 was used instead of Polymer 1.

[Example 28]
Same as Example 1 <Synthesis of azomethine derivative monomer 1> except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hydroxythiophene-2-carboxaldehyde and 4-aminophenol was changed to p-toluidine. Polymer 28 was obtained in a similar manner. Toner 28 was obtained in the same manner as in Example 1, except that Polymer 28 was used instead of Polymer 1.

[Example 29]
Polymer 29 was obtained in the same manner as in Example 28 except that p-toluidine was changed to 4-hexylaniline. Toner 29 was obtained in the same manner except that Polymer 29 was used instead of Polymer 28.

[Example 30]
Polymer 30 was obtained in the same manner as in Example 28 except that p-toluidine was changed to 4-hexyloxyaniline. Toner 30 was obtained in the same manner except that Polymer 30 was used instead of Polymer 28.

[Example 31]
Polymer 31 was obtained in the same manner as in Example 28 except that p-toluidine was changed to aniline. Toner 31 was obtained in the same manner except that Polymer 31 was used instead of Polymer 28.

[Example 32]
Polymer 32 was obtained in the same manner as in Example 28 except that p-toluidine was changed to 3-methyl-4-hexylaniline. Toner 32 was obtained in the same manner except that Polymer 32 was used instead of Polymer 28.

[Example 33]
Polymer 33 was obtained in the same manner as in Example 28, except that 5-hydroxythiophene-2-carboxaldehyde was changed to 5-hydroxythiophene-3-carboxaldehyde. Toner 33 was obtained in the same manner except that Polymer 33 was used instead of Polymer 28.

[Example 34]
Polymer 34 was obtained in the same manner as in Example 28 except that 5-hydroxythiophene-2-carboxaldehyde was changed to 5-hydroxymethylthiophene-2-carboxaldehyde. Toner 34 was obtained in the same manner except that Polymer 34 was used instead of Polymer 28.

[Example 35]
Polymer 35 was obtained in the same manner as in Example 31 except that 5-hydroxythiophene-2-carboxaldehyde was changed to 4-hydroxythiophene-2-carboxaldehyde. Toner 35 was obtained in the same manner except that Polymer 35 was used instead of Polymer 31.

[Example 36]
Polymer 36 was obtained in the same manner as in Example 31, except that 5-hydroxythiophene-2-carboxaldehyde was changed to 4-hydroxythiophene-3-carboxaldehyde. Toner 36 was obtained in the same manner except that Polymer 36 was used instead of Polymer 31.

[Example 37]
Polymer 37 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methylfuran-2-carboxaldehyde. Toner 37 was obtained in the same manner as in Example 1, except that Polymer 37 was used instead of Polymer 1.

[Example 38]
Polymer 38 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexylfuran-2-carboxaldehyde. Toner 38 was obtained in the same manner as in Example 1, except that Polymer 38 was used instead of Polymer 1.

[Example 39]
Polymer 39 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 2-furancarboxaldehyde. Toner 39 was obtained in the same manner as in Example 1 except that Polymer 39 was used instead of Polymer 1.

[Example 40]
Polymer 40 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methylfuran-3-carboxaldehyde. Toner 40 was obtained in the same manner as in Example 1, except that Polymer 40 was used instead of Polymer 1.

[Example 41]
Polymer 41 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to pyrrole-3-carboxaldehyde. Toner 41 was obtained in the same manner as in Example 1, except that Polymer 41 was used instead of Polymer 1.

[Example 42]
Polymer 42 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 3-formyl-1-methylpyrrole. Toner 42 was obtained in the same manner as in Example 1 except that Polymer 42 was used instead of Polymer 1.

[Example 43]
Polymer 43 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 3-formyl-1-hexylpyrrole. Toner 43 was obtained in the same manner as in Example 1, except that Polymer 43 was used instead of Polymer 1.

[Example 44]
Polymer 44 was obtained in the same manner as in Example 1 <Synthesis of Azomethine Derivative Monomer 1>, except that 3-formyl-1-octylpyrrole was used instead of 5-methylthiophene-2-carboxaldehyde. Toner 44 was obtained in the same manner as in Example 1 except that Polymer 44 was used instead of Polymer 1.

[Example 45]
Polymer 45 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 3-formyl-1-acetoxypyrrole. Toner 45 was obtained in the same manner as in Example 1, except that Polymer 45 was used instead of Polymer 1.

[Example 46]
Polymer 46 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methyl-1H-pyrrole-3-carbaldehyde. . Toner 46 was obtained in the same manner as in Example 1, except that Polymer 46 was used instead of Polymer 1.

[Example 47]
Polymer 47 was obtained in the same manner except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexyl-1H-pyrrole-3-carbaldehyde in <Synthesis of azomethine derivative monomer 1> in Example 1. rice field. Toner 47 was obtained in the same manner as in Example 1 except that Polymer 47 was used instead of Polymer 1.

[Example 48]
Polymer 48 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-octyl-1H-pyrrole-3-carbaldehyde. . Toner 48 was obtained in the same manner as in Example 1, except that Polymer 48 was used instead of Polymer 1.

[Example 49]
Polymer 49 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-methyl-3-formyl-1-methylpyrrole. . Toner 49 was obtained in the same manner as in Example 1, except that Polymer 49 was used instead of Polymer 1.

[Example 50]
Polymer 50 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-hexyl-3-formyl-1-methylpyrrole. . Toner 50 was obtained in the same manner as in Example 1, except that Polymer 50 was used instead of Polymer 1.

[Example 51]
Polymer 51 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> in Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 5-octyl-3-formyl-1-methylpyrrole. . Toner 51 was obtained in the same manner as in Example 1, except that Polymer 51 was used instead of Polymer 1.

[Example 52]
Polymer 52 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 2-formyl-5-methylpyrrole. Toner 52 was obtained in the same manner as in Example 1, except that Polymer 52 was used instead of Polymer 1.

[Example 53]
Polymer 53 was obtained in the same manner as in <Synthesis of azomethine derivative monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 2-formyl-5-hexylpyrrole. Toner 53 was obtained in the same manner as in Example 1, except that Polymer 53 was used instead of Polymer 1.

[Example 54]
Polymer 54 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1, except that 5-methylthiophene-2-carboxaldehyde was changed to 2-formyl-4-methylpyrrole. Toner 54 was obtained in the same manner as in Example 1, except that Polymer 54 was used instead of Polymer 1.

[Example 55]
Polymer 55 was obtained in the same manner as in <Synthesis of Azomethine Derivative Monomer 1> of Example 1 except that 5-methylthiophene-2-carboxaldehyde was changed to 2-formyl-1-methylpyrrole. Toner 55 was obtained in the same manner as in Example 1, except that Polymer 55 was used instead of Polymer 1.

[Example 56]
Polymer 56 was obtained in the same manner as in Example 28, except that 5-hydroxythiophene-2-carboxaldehyde was changed to 2-hydroxy-4-formyl-1-methylpyrrole. Toner 56 was obtained in the same manner except that Polymer 56 was used instead of Polymer 28.

[Example 57]
Polymer 57 was obtained in the same manner as in Example 28 except that 5-hydroxythiophene-2-carboxaldehyde was changed to 3-hydroxy-5-formyl-1-methylpyrrole. Toner 57 was obtained in the same manner except that polymer 57 was used instead of polymer 28.

[Example 58]
Same as Example 1 <Synthesis of Azomethine Derivative Monomer 1> except that 5-methylthiophene-2-carboxaldehyde was changed to 1-hydroxypyrrole-3-carbaldehyde and 4-aminophenol was changed to p-toluidine. Polymer 58 was obtained in a similar manner. Toner 58 was obtained in the same manner as in Example 1, except that Polymer 55 was used instead of Polymer 1.

[Example 59]
Polymer 59 was obtained in the same manner as in Example 58, except that p-toluidine was changed to 4-hexylaniline. Toner 59 was obtained in the same manner except that Polymer 59 was used instead of Polymer 58.

[Example 60]
Polymer 60 was obtained in the same manner as in Example 58 except that p-toluidine was changed to 4-hexyloxyaniline. Toner 60 was obtained in the same manner except that Polymer 60 was used instead of Polymer 58.

[Example 61]
Polymer 61 was obtained in the same manner as in Example 58 except that p-toluidine was changed to aniline. Toner 61 was obtained in the same manner except that Polymer 61 was used instead of Polymer 58.

[Example 62]
Polymer 62 was obtained in the same manner as in Example 58, except that 1-hydroxypyrrole-3-carbaldehyde was changed to 1-hydroxypyrrole-2-carbaldehyde. Toner 62 was obtained in the same manner except that Polymer 62 was used instead of Polymer 58.

[Example 63]
Polymer 63 was prepared in the same manner as in <Synthesis of Polymer 1> in Example 1 except that the amount of azomethine derivative monomer 1 was changed from 1.5 g to 1.2 g and 0.3 g of n-hexyl acrylate was added. Obtained. Toner 63 was obtained in the same manner as in Example 1, except that Polymer 63 was used instead of Polymer 1.

[Example 64]
Polymer 64 was obtained in the same manner as in Example 63 except that n-hexyl acrylate was changed to n-butyl methacrylate. Toner 64 was obtained in the same manner except that Polymer 64 was used instead of Polymer 63.

[Example 65]
Polymer 65 was obtained in the same manner as in Example 63, except that n-hexyl acrylate was changed to styrene. Toner 65 was obtained in the same manner except that Polymer 65 was used instead of Polymer 63.

[Example 66]
Polymer 66 was obtained in the same manner as in Example 63, except that n-hexyl acrylate was changed to 1-hexene. Toner 66 was obtained in the same manner except that Polymer 66 was used instead of Polymer 63.

[Example 67]
Polymer 67 was obtained in the same manner as in Example 63, except that 0.3 g of n-hexyl acrylate was changed to 0.15 g and 0.15 g of styrene was added. Toner 67 was obtained in the same manner except that Polymer 67 was used instead of Polymer 63.

[Example 68]
The procedure was the same as in <Preparation of Toner 1> of Example 1, except that the amount of polymer particle dispersion 1 added was changed from 523 parts by mass to 607 parts by mass in terms of solid content, and styrene-acrylic resin particle dispersion 1 was omitted. Toner 68 was obtained by the method.

[Example 69]
In <Preparation of Toner 1> of Example 1, the amount of polymer particle dispersion liquid 1 added was changed from 523 parts by mass to 303 parts by mass in terms of solid content, and the amount of styrene-acrylic resin particle dispersion liquid 1 added was changed in terms of solid content. Toner 69 was obtained in the same manner except that the content was changed from 79 parts by mass to 303 parts by mass.

[Example 70]
In <Preparation of Toner 1> of Example 1, the amount of polymer particle dispersion liquid 1 added was changed from 523 parts by mass to 79 parts by mass in terms of solid content, and the amount of styrene acrylic resin resin dispersion liquid 1 added was changed in terms of solid content. Toner 70 was obtained in the same manner except that the content was changed from 79 parts by mass to 523 parts by mass.

[Example 71]
(Preparation of polyester resin particle dispersion liquid 1 containing polyester resin 1)
A 10-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with 524 parts by mass of bisphenol A propylene oxide 2 mol adduct, 105 parts by mass of terephthalic acid, 69 parts by mass of fumaric acid, and 2 parts by mass of tin octylate (esterification catalyst) were added, and a polycondensation reaction was carried out at a temperature of 230° C. for 8 hours. Furthermore, after continuing the polycondensation reaction at 8 kPa for 1 hour, the mixture was cooled to 160° C. to obtain a polyester resin 1. 100 parts by mass of polyester resin 1 was pulverized with "Randell Mill type: RM" (manufactured by Tokuju Kosakusho Co., Ltd.), mixed with 638 parts by mass of a 0.26% by mass sodium lauryl sulfate aqueous solution prepared in advance, and superimposed while stirring. Ultrasonic dispersion was performed for 30 minutes at V-LEVEL and 300 μA using a sonic homogenizer “US-150T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a polyester resin particle dispersion liquid 2. When the particle size of the polyester resin particles in the polyester resin particle dispersion 2 was measured by dynamic light scattering using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.), the volume-based median diameter was 135 nm. there were. Moreover, when the glass transition temperature (Tg) of this polyester resin 1 was measured, it was 42°C.

<Production of Toner 71>
Toner 71 was obtained in the same manner as in <Preparation of Toner 1> of Example 1, except that the styrene-acrylic resin particle dispersion 1 was changed to the polyester resin dispersion 1 prepared above.

[Comparative Example 1]
<Comparative compound>
The following comparative compound 1 (number average molecular weight Mn: 2870) was obtained by the method described in paragraphs 0217 to 0227 of JP-A-2014-191078.

<Preparation of Comparative Compound Dispersion>
A comparative compound dispersion was obtained in the same manner as in <Preparation of Polymer Particle Dispersion 1> of Example 1, except that Polymer 1 was changed to Comparative Compound 1.

<Production of Toner 72>
Toner 72 was obtained in the same manner except that polymer particle dispersion 1 of Example 1 was changed to the comparative compound dispersion prepared above.

(Number average molecular weight Mn)
The number average molecular weights Mn of Polymers 1 to 67 and Comparative Compound 1 were measured by the GPC method. Specifically, using an apparatus "HLC-8120GPC" (manufactured by Tosoh Corporation) and a column "TSKguardcolumn + TSKgelSuperHZ-M triplet" (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) as a carrier solvent ) was flowed at a flow rate of 0.2 mL/min. The measurement sample was dissolved in tetrahydrofuran to a concentration of 1 mg/ml. The solution was prepared by processing at room temperature for 5 minutes using an ultrasonic disperser. Then, it was treated with a membrane filter having a pore size of 0.2 μm to obtain a sample solution, and 10 μL of this sample solution was injected into the apparatus together with the above carrier solvent and detected using a refractive index detector (RI detector). The molecular weight distribution of the measurement sample was calculated based on a calibration curve prepared using monodisperse polystyrene standard particles. Ten points of polystyrene were used for the calibration curve measurement.

(Glass transition temperature (Tg))
The glass transition temperature (Tg) of the binder resin was measured with DSC7000X manufactured by Hitachi High-Tech Science. Specifically, about 3 mg of the binder resin was accurately weighed to two decimal places, sealed in an aluminum pan, and set. An empty aluminum pan was used as a reference. A first heating process in which the temperature is raised from 0 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min; a cooling process in which the temperature is lowered from 200 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min; and a temperature increase rate of 10 ° C./min. A second heating process in which the temperature is raised from 0° C. to 200° C. per minute was set as the measurement condition in this order. Then, an analysis was performed based on the data in the second heating process. The glass transition temperature was defined as the intersection point between the extension of the baseline before the rise of the first endothermic peak and the tangential line indicating the maximum slope from the rise of the first endothermic peak to the apex of the peak. The glass transition temperatures of the polymers and toners produced in Examples and Comparative Examples can also be measured in the same manner.

[Production of developer]
For Toners 1 to 72 prepared above, ferrite carrier particles having a volume average particle diameter of 30 μm coated with a copolymer resin of cyclohexane methacrylate and methyl methacrylate (monomer mass ratio 1:1) were added to toner particles at a toner particle concentration of 6 mass. % to obtain developers 1-72. Mixing was performed for 30 minutes using a V-blender.

[Evaluation: Photoresponsive adhesion test of polymer]
Polymers 1 to 67 prepared in Examples 1 to 67, and the change in adhesiveness due to light irradiation of Comparative Compound 1 of Comparative Example were evaluated by the following photoresponsive adhesion test using the apparatus shown in FIG. As shown in FIG. 3, 2 mg of a polymer is placed on a 18 mm square cover glass 1 within a radius of 6 mm from the center of the glass, and a cover glass 2 of the same size is shifted about 4 mm in a parallel direction to the cover glass 1. , the polymer was all overlaid. This was heated, the sample was melted, and the cover glass 1 and the cover glass 2 were adhered. Each obtained sample was subjected to the following non-fluidity→fluidity test, and then subjected to the following fluidity→non-fluidity (return) test.

<Non-fluidity → fluidity test>
The part (A) shown in FIG. 3 was fixed to the table with cellophane tape, and the part (C) was fixed with cellophane tape with a vinyl cord having a length of 30 cm to which a weight of 100 g was attached. The portion (B) was irradiated with light of 365 nm at an irradiation dose of 25 J/cm ² to confirm whether the cover glass 2 was peeled off from the cover glass 1, and judged according to the following evaluation criteria. Both Polymers 1 to 67 prepared in Examples 1 to 67 and Comparative Compound 1 in Comparative Example were ◯ (cover glass 2 was completely peeled off from cover glass 1).

－Evaluation criteria for non-fluidity → fluidity test－
◯: The cover glass 2 was completely separated from the cover glass 1 Δ: The cover glass 2 was displaced ×: The cover glass 2 did not move.

<Test of fluidity → non-fluidity (return)>
Non-fluidity → After 1 hour of fluidity test execution (1 hour was left in a natural environment, that is, at room temperature), cover the sample part ((B) part) of the cover glass 1 used in the above test so as to cover it. A glass 3 (same size as the cover glasses 1 and 2) was placed, and it was confirmed whether or not the cover glasses 1 and 3 adhered to each other, and judgment was made according to the following evaluation criteria. All of the polymers 1 to 67 prepared in Examples 1 to 67 were ◯: not adhered (non-fluidized), and it was confirmed that they reversibly fluidized and non-fluidized. Comparative compound 1 was x: adhered (fluidized state was maintained).

-Evaluation criteria for fluidity → non-fluidity (return) test-
〇: Not adhered (non-fluidized)
△: Partially adhered (partially fluidized state was maintained)
x: Adhered (fluidized state was maintained).

In addition, for the polymers 1 to 67 prepared in Examples 1 to 67, which were evaluated as ○ in the above fluidity → non-fluidity (return) test, all of them were reprocessed after conducting the non-fluidity → fluidity test. It was confirmed that it was solidified.

[Evaluation: fixability test]
The fixability test was conducted using the developers 1 to 72 obtained above under normal temperature and normal humidity environment (temperature 20° C., humidity 50% RH). Between a pair of parallel plate (aluminum) electrodes, one side of which is a developer and the other side is a plain paper (basis weight: 64 g/m ² ) as a recording medium, the developer is placed between the electrodes while being slid by a magnetic force. The gap is 0.5 mm, the DC bias and the AC bias are developed under the condition that the toner adhesion amount is 5 g/m ² , the toner layer is formed on the surface of the plain paper, fixed by each fixing device, and printed. (imaging). A 1 cm square toner image of this printed matter was rubbed 10 times with JK Wiper (registered trademark) (manufactured by Nippon Paper Crecia Co., Ltd.) under a pressure of 40 kPa to evaluate the fixation rate of the image. A fixation rate of 60% or more was regarded as acceptable. The image fixation rate is defined by measuring the reflection density of the image after printing and the image after rubbing with a fluorescence spectrodensitometer "FD-7" (manufactured by Konica Minolta, Inc.), and the solid image after rubbing. is a value obtained by dividing the reflection density of the printed solid image by the reflection density of the solid image after printing and expressed as a percentage.

As the fixing device, the following three types of fixing devices configured by appropriately modifying the device shown in FIG. 2 were used.

No. 1: Without the crimping part 9 in FIG. 2, the wavelength of the ultraviolet light emitted from the irradiation part 40 is 365 nm (light source: LED light source with an emission wavelength of 365 nm ± 10 nm), and the irradiation amount is 13 J / cm ² ;
No. 2: There is the crimping part 9 of FIG. The light source and irradiation amount of the irradiation unit 40 are No. is similar to 1;
No. 3: There is the crimping portion 9 of FIG. 2, the temperature of the pressing member 91 is 80° C., and the pressure during pressing is 0.2 MPa. The light source and irradiation amount of the irradiation unit 40 are No. Same as 1.

[Evaluation of color reproducibility]
The images of Examples and Comparative Examples obtained above were evaluated for color reproducibility by visual evaluation by 10 monitors according to the following evaluation criteria. Specifically, as a sample for evaluation comparison, a toner was produced by changing all the polymer 1 in the toner 1 of Example 1 to a styrene-acrylic resin. Using this, a developer was prepared in the same manner as described above, and developed in the same manner as in the image formation in the fixability test described above. 4, fixing was performed.

Fixing device No. 4: There is the crimping part 9 of FIG. do not.

Ten monitors were shown the sample for evaluation comparison and the images obtained in the above Examples and Comparative Examples in order, and were asked whether the colors of the two images were clearly different. Table 3 below shows the evaluation results based on the following color reproducibility evaluation criteria.

-Evaluation Criteria for Color Reproducibility-
◎: 2 or less people answered that they were clearly different ○: 3 to 4 people answered that they were clearly different △: 5 to 7 people answered that they were clearly different ×: 8 or more people answered that they were clearly different .

The composition of each toner, the type of fixing device, and the evaluation results are shown in Tables 2 to 4 below.

As is clear from Table 3, it was confirmed that the polymer containing a structural unit derived from an azomethine derivative prepared in each example was reversibly fluidized/non-fluidized by irradiation with light. In contrast, with Comparative Compound 1 in Comparative Example 1, reversible fluidization/non-fluidization was not confirmed.

Further, as shown in Table 4, the toners produced in each example exhibited high fixability and excellent color reproducibility. On the other hand, it was found that the toner of the comparative example had good fixability but low color reproducibility. Since the ultraviolet light source and the ultraviolet irradiation conditions used in the fixability test were constant throughout Examples 51 to 109 and Comparative Example 110, the toners of Examples compared to the toners of Comparative Examples were reversible by light irradiation. It can be said that the effect of the polymer, which is substantially fluidized/non-fluidized and is not markedly colored, is sufficiently exhibited.

Comparing the fixing devices, No. 1 uses the same toner 1, irradiates ultraviolet rays under the same conditions, and does not use a pressure member. No. 1 fixing device pressurized by the pressure member than No. 1 fixing device. No. 2 fixing device and No. 2 fixing device heated and pressurized by a pressure member. It was found that the use of the fixing device No. 3 provides higher fixability (comparison of Examples 1, 72, and 73).

As shown in each example, any polymer containing a structure derived from a specific azomethine derivative can be reversibly fluidized or non-fluidized by light irradiation, has little coloration, and can be used with a toner using it. It can be seen that an excellent fixation rate of 60% or more is exhibited in the fixability test of the toner image.

As the polymerizable group, good results were obtained when any of the polymerizable groups (ii), (iii), and (iv) were introduced. is further improved (comparison between Examples 2 and 24, and Examples 31 and 34).

When the polymerizable group is introduced at any position of R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , R ₃ or R ₄ in the chemical formula (1) which is not selected as a group represented by Y However, when R ₇ , R ₁₀ or any one of R ₁ to R ₄ not adjacent to the group represented by Y is introduced into one position, the fixation rate of the toner image is further improved. (comparison of Examples 1, 26 and 27, comparison of Examples 11, 35 and 36).

Among them, the toners of Examples 1 to 3, 5, 6, and 42 to 44 were particularly good in fixing rate of images.

A good fixation rate can be similarly obtained by combining not only the structural unit derived from the azomethine derivative but also other structural units.

In addition to the polymer, the toner may further contain a binder resin. It was confirmed that a good fixing rate was similarly obtained when a binder resin was further used. By using the above polymer, a good fixing rate can be obtained even if the content of the binder resin is small.

1 photoreceptor,
2 charger,
3 exposure device,
4 developing section,
5 transfer unit,
7 paper transport system,
8 cleaning section,
9 crimping part,
10 image forming unit,
11 paper feeding unit,
12 transport rollers,
13 conveyor belts,
14 paper ejection section,
15 manual feed unit,
16 trays,
17 thermo-hygrometer,
20 image processing unit,
24 paper reversing section,
40 irradiation unit,
71 image reader,
72 automatic document feeder,
85 blades,
90 control unit,
91, 92 pressure member,
100 image forming apparatus,
d manuscript,
S Recording paper.

Claims (17)

A polymer represented by the following chemical formula (1), containing a structural unit derived from an azomethine derivative having a polymerizable group, and fluidized by light irradiation and reversibly non-fluidized:

In the chemical formula (1),
X is NR ₁₀ , O or S;
R ₁ is a group having a polymerizable group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 2 carbon atoms. ~16 acyl group, an alkoxycarbonyl group having 2 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms,
R ₂ is a group having a polymerizable group, a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an alkoxy group having 1 to 16 carbon atoms,
Either one of R ₃ or R ₄ is a group represented by Y, and the other is a group having a polymerizable group, a hydrogen atom , an alkyl group having 1 to 16 carbon atoms, or an alkoxy having 1 to 16 carbon atoms. is the basis ,
R ₁₀ is a group having a polymerizable group, a hydrogen atom , an alkyl group having 1 to 16 carbon atoms , or an acyloxy group having 2 to 16 carbon atoms,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
R ₅ to R ₇ are each independently a group having a polymerizable group, a hydrogen atom , an alkyl group having 1 to 16 carbon atoms, or an alkoxy group having 1 to 16 carbon atoms,
R ₈ and R ₉ are each independently a hydrogen atom , an alkyl group having 1 to 16 carbon atoms, or an alkoxy group having 1 to 16 carbon atoms;
At this time, at least one of R ₁ , R ₂ , R ₅ to R ₇ , R ₁₀ , and R ₃ or R ₄ not selected as the group represented by Y is a group having a polymerizable group,
When at least one of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y is a group having a polymerizable group, R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ other than the group having a polymerizable group and the group represented by Y are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, provided that R ₁₀ is selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
When at least one of R ₅ to R ₇ is a group having a polymerizable group, among R ₅ to R ₇ , those other than the group having a polymerizable group, R ₈ and R ₉ are each independently selected from a hydrogen atom , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms ,
At this time, the group having the polymerizable group is a group represented by any one of the following formulas (i) to (iv),

In formulas (i) to (iv), A ₁ is a hydrogen atom or a methyl group, A ₂ is an alkylene group having 1 to 18 carbon atoms, and A ₃ is an alkylene group having 1 to 6 carbon atoms. be:
The polymer is a polymer containing only structural units derived from an azomethine derivative having a polymerizable group represented by the chemical formula (1), or a polymerizable polymer represented by the chemical formula (1) The total amount of all structural units constituting the polymer, including structural units derived from an azomethine derivative having a group and structural units derived from a styrene derivative, a (meth)acrylic acid derivative, or an olefin derivative, is 100% by mass. is a copolymer containing 30% by mass or more of structural units derived from an azomethine derivative having a polymerizable group represented by the chemical formula (1),
The polymer has a number average molecular weight Mn of 3,500 or more. wherein the azomethine derivative has a group having the polymerizable group in any one of R ₁ to R ₄ not adjacent to R ₇ , R ₁₀ or the group represented by Y in the chemical formula (1); 1. The polymer according to 1 . The polymer according to claim 2 , wherein the azomethine derivative is represented by the following chemical formula (2):

In chemical formula (2),
X is NR ₁₀ , O or S;
R ₁ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, carbon an alkoxycarbonyl group having 2 to 16 carbon atoms or an acyloxy group having 2 to 16 carbon atoms,
R ₂ is a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an alkoxy group having 1 to 16 carbon atoms,
one of R ₃ and R ₄ is a group represented by Y, the other is a hydrogen atom , an alkyl group having 1 to 16 carbon atoms, or an alkoxy group having 1 to 16 carbon atoms;
R ₁₀ is a hydrogen atom , an alkyl group having 1 to 16 carbon atoms , or an acyloxy group having 2 to 16 carbon atoms,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
_R7 is a group having a polymerizable group. In the azomethine derivative represented by the chemical formula (2),
All of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y are hydrogen atoms, or
Among R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y, any one of R ₁ to R ₄ not adjacent to Y is a cyano group, a nitro group, hydroxy group, carboxy group, or alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, acyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms and the rest are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₁₀ is , a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or
R ₁₀ is an alkyl group having 1 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms, and is not selected as a group represented by Y among R ₁ , R ₂ , and R ₃ or R ₄ are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. . The polymer according to claim 4 , wherein the azomethine derivative is represented by the following chemical formula (3):

In chemical formula (3),
X is NR ₁₀ , O or S;
either one of R ₃ or R ₄ is a group represented by Y,
Z ₁ and Z ₂ are N or CH and Z ₁ ≠Z ₂ ,
A ₁ is a hydrogen atom or a methyl group,
A ₂ is an alkylene group having 1 to 18 carbon atoms,
all of R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y are hydrogen atoms;
or,
Among R ₁ , R ₂ , R ₁₀ , and R ₃ or R ₄ not selected as a group represented by Y, any one of R ₁ to R ₄ not adjacent to Y is a cyano group, a nitro group, hydroxy group, carboxy group, or alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, acyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms and the rest are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₁₀ is , a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or
R ₁₀ is an alkyl group having 1 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms, and is not selected as a group represented by Y among R ₁ , R ₂ , and R ₃ or R ₄ are each independently a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The polymer according to any one of claims 1 to 5 , wherein the wavelength of the irradiation light is 280 nm or more and 480 nm or less. A toner comprising the polymer according to any one of claims 1-6 . 8. The toner according to claim 7 , further comprising a binder resin. 9. The toner according to claim 8 , wherein the binder resin contains at least one selected from the group consisting of styrene acrylic resins and polyester resins. The toner of any one of claims 7-9 , further comprising a colorant. The toner according to any one of claims 7 to 10 , further comprising a release agent. An image comprising the steps of: forming a toner image made of the toner according to any one of claims 7 to 11 on a recording medium; and irradiating the toner image with light to soften the toner image. Forming method. 13. The image forming method according to claim 12 , wherein the light has a wavelength of 280 nm or more and 480 nm or less. 14. The image forming method according to claim 12 , further comprising pressing the softened toner image. 15. The image forming method according to claim 14 , wherein the softened toner image is further heated in the pressing step. A photosensitive adhesive comprising the polymer according to any one of claims 1-6 . The polymer is a polymer containing only structural units derived from an azomethine derivative having a polymerizable group represented by the chemical formula (1), or a polymerizable polymer represented by the chemical formula (1) The total amount of all structural units constituting the polymer, including structural units derived from an azomethine derivative having a group and structural units derived from a styrene derivative, a (meth)acrylic acid derivative, or an olefin derivative, is 100% by mass. 2. The polymer according to claim 1, which is a copolymer containing 80% by mass or more of structural units derived from the azomethine derivative having a polymerizable group represented by the chemical formula (1).

Images