JP2020132542A - Photoresponsive low-molecular weight material, adhesive, toner, and image forming method - Google Patents

Abstract

To provide a new compound that is reversibly fluidized and non-fluidized by being irradiated with light, and does not show notable coloration, and is useful as a photosensitive adhesive for toner or the like.SOLUTION: A compound represented by the following chemical formula 1. [X is NR, O or S; Zand Zare N or CH; Z≠Z; R, R, R-Rindependently represent H, a halogen atom, an alkyl group, an alkoxycarbonyl group, a hydroxy group or the like; one of Rand Ris a group represented by chemical formula 2, and the other is H, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group].SELECTED DRAWING: Figure 3

Description

The present invention relates to photoresponsive low molecular weight materials, adhesives, toners and image forming methods.

A photoresponsive liquid crystal material is known as a material whose fluidity changes with light irradiation. For example, Patent Documents 1 and 2 propose a polymer liquid crystal material using an azobenzene derivative. They undergo a cis-trans isomerization reaction of the azobenzene moiety in response to light. It is believed that this change in molecular structure induces a phase transition from the solid state to the fluid state. Further, when the wavelength is changed and re-irradiated, heated, or left in a dark place at room temperature, a reverse reaction occurs and the solidification occurs again.

Japanese Unexamined Patent Publication No. 2011-256155 Japanese Unexamined Patent Publication No. 2011-256291

However, the azobenzene derivatives described in Patent Documents 1 and 2 are all colored yellow to orange, and have a problem that a desired color cannot be reproduced when applied to industrial products such as toners and adhesives. .. Furthermore, according to the study by the present inventors, by changing the substituent of the azobenzene derivative, the coloration of yellow to orange can be adjusted to some extent, but it is basically colorless or almost colorless. It also turned out to be impossible to do.

Therefore, an object of the present invention is to provide a compound that is reversibly fluidized and immobilized by light irradiation and is not significantly colored.

Another object of the present invention is to provide an industrial product such as a toner or an adhesive using the above compound.

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

The present inventors have accumulated diligent research in view of the above problems. As a result, by using a compound having an azomethine moiety, it is reversibly fluidized and non-fluidized, and photoresponsiveness without significant coloring to the extent that it does not affect the desired color reproduction when applied to toners and adhesives. We have found that the above problems can be solved by realizing the compound, and have completed the present invention.

That is, the present invention is achieved by the photoresponsive low molecular weight materials, adhesives, toners and image forming methods shown in 1 to 16 below.

1. 1. A compound represented by the following chemical formula 1 that is reversibly fluidized and non-fluidized by light irradiation.

In the chemical formula 1,
X is NR ₁₀ , O or S,
Z ₁ and Z ₂ are independently N or CH, and Z ₁ ≠ Z ₂ , respectively.
R ₁ and R ₂ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
R ₃ and R ₄ are independently a group represented by the chemical formula 2, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group. ,
At this time, either one of R ₃ and R ₄ is a group represented by the chemical formula 2.
R ₁₀ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group or a hydroxy group.
In the chemical formula 2,
R _{5 to} R ₉ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
At this time, at least one of R _{5 to} R ₉ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is.

2. 2. At least one of R _{1 to} R ₄ in the chemical formula 1 is a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 2 to 19 carbon atoms. an acyl group or an alkoxycarbonyl group having a carbon number of 2 to 19, and / or R ₁₀ is a halogen atom, hydroxy group, the alkoxycarbonyl group of the alkyl or 2 to 19 carbon atoms having 1 to 18 carbon atoms The compound according to 1.

3. 3. 1. The above 1 or 2 wherein R ₇ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Compound.

4. Any of the above 1 to 3 in which the R ₇ is an alkyl group having 4 to 12 carbon atoms, an alkoxy group having 4 to 12 carbon atoms, an acyl group having 5 to 13 carbon atoms, or an alkoxycarbonyl group having 5 to 13 carbon atoms. The compound according to item 1.

5. At least one of the above R ₅ , R ₆ , R ₈ and R ₉ has an alkyl group having 1 to 4 carbon atoms which may have a branch, and 1 to 4 carbon atoms which may have a branch. The compound according to any one of 1 to 4 above, which is an alkoxy group or a halogen atom.

6. The compound according to any one of 1 to 5 above, wherein the wavelength of the irradiation light when the compound is fluidized by light irradiation is 280 nm or more and 480 nm or less.

7. A toner containing the compound according to any one of 1 to 6 above.

8. The toner according to 7 above, further containing a binder resin.

9. The toner according to 8 above, wherein the binder resin contains at least one selected from the group consisting of a styrene acrylic resin and a polyester resin.

10. The toner according to any one of 7 to 9 above, which further contains a colorant.

11. The toner according to any one of 7 to 10 above, further containing a release agent.

12. An image forming method including a step of forming a toner image made of the toner according to any one of 7 to 11 above on a recording medium and a step of irradiating the toner image with light to soften the toner image. ..

13. The image forming method according to 12 above, wherein the wavelength of the light when irradiating the toner image with light to soften the toner image is 280 nm or more and 480 nm or less.

14. 12. The image forming method according to 12 or 13, further comprising a step of pressurizing the toner image.

15. The image forming method according to 14 above, wherein in the pressurizing step, the toner image is further heated.

16. A photosensitive adhesive using the compound according to any one of 1 to 6 above.

According to the present invention, it is possible to provide a compound that is reversibly fluidized and immobilized by light irradiation and is not significantly colored.

Further, according to the present invention, it is possible to provide a toner containing the above-mentioned compound, which is excellent in softening rate by light irradiation and image fixability, and an image forming method using the toner.

Further, according to the present invention, it is possible to provide a photosensitive adhesive containing the above compound having excellent adhesiveness by light irradiation.

It is a schematic block diagram which shows the image forming apparatus 100 used in the image forming method by one Embodiment of this invention. It is a schematic block diagram of the irradiation part 40 in an image forming apparatus 100. In order to confirm the phase transition from the crystalline phase or the liquid crystal phase to the isotropic phase, the target compound 22 in Table 1 is enclosed in a glass sandwich cell and irradiated with light of 365 nm under a polarizing microscope observation to change the state. It is a drawing which observed. Of these, FIG. 3A is a drawing showing a photograph of a polarizing microscope in which a state before light irradiation (solid and non-fluid state before phase transition) was observed. FIG. 3B is a drawing showing a photograph of a polarizing microscope in which changes in the state after light irradiation (softening and fluidization states due to photophase transition) are observed. FIG. 3C is a drawing showing a photograph of a polarizing microscope in which changes in the state after light irradiation is stopped (resolidification due to a reverse reaction, non-fluidized state) are observed. It is the schematic of the apparatus which measures the change of adhesiveness with light irradiation of the compound synthesized in an Example and a comparative example.

The present invention is a compound represented by the following chemical formula 1 that is reversibly fluidized and non-fluidized by light irradiation.

In the chemical formula 1,
X is NR ₁₀ , O or S,
Z ₁ and Z ₂ are independently N or CH, and Z ₁ ≠ Z ₂ , respectively.
R ₁ and R ₂ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
R ₃ and R ₄ are independently a group represented by the chemical formula 2, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group. ,
At this time, either one of R ₃ and R ₄ is a group represented by the chemical formula 2.
R ₁₀ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group or a hydroxy group.
In the chemical formula 2,
R _{5 to} R ₉ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
At this time, at least one of R _{5 to} R ₉ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is.

By using such a compound having an azomethine moiety represented by the above chemical formula 1, it is reversibly fluidized and non-fluidized by light irradiation, and it affects the reproduction of a desired color when applied to a toner or an adhesive. It is possible to realize a photoresponsive compound that is not colored to the extent that it does not occur.

The details of why the compound of the present invention can obtain the above effect are unknown, but the following mechanism can be considered. The following mechanism is speculative, and the present invention is not limited to the following mechanism. In the following description, the compound represented by the above chemical formula 1 is also referred to as "a compound having an azomethine moiety".

Azobenzene compounds are known to be materials that absorb light and soften from a solid state (photophase transition), and the photophase transition is caused by the collapse of the crystal structure due to cis-trans isomerization. Conceivable. The azobenzene compounds described in Patent Documents 1 or 2 undergo a phase change upon isomerization reaction by light irradiation, but these compounds show strong absorption due to the n-π ^* transition in the long wavelength region and are orange. Since it is colored in orange, there is a problem in that a desired color cannot be reproduced when applied to an industrial product.

In the present invention, by using a compound having an azomethine moiety, it has been realized to provide a compound that is reversibly fluidized and non-fluidized by light irradiation and has no significant coloring. By introducing an azomethine moiety instead of azobenzene, strong n-π ^* absorption in the azobenzene compound can be weakened, so that a compound without significant coloring can be realized.

In addition, the non-fluid trans form (E) of the compound that is reversibly fluidized and non-fluidized due to photoisomerization is irradiated with light and isomerized to the cis form (Z), so that the ordered structure is broken. It is considered that reversible fluidization and non-fluidization phenomena can be induced by the transitional change. Therefore, it is considered that many trans isomers (E) need to be isomerized to cis isomers (Z) in order to induce reversible fluidization and non-fluidization phenomena. However, it is generally known that azomethine compounds have a higher rate of isomerization from Z-form to E-form than azobenzene compounds, and azomethine compounds with benzene introduced at both ends are reversibly fluidized and non-reversible. It was expected to be disadvantageous for inducing a fluidization phenomenon.

In the present invention, it is considered that the introduction of the heterocycle into the azomethine compound increased the amount of the cis form (Z) during light irradiation and induced fluidization associated with the photoisomerization reaction. It is considered that this is because the rate of isomerization from Z-form to E-form decreases by introducing a heterocycle instead of benzene.

As described above, it is considered that the photophase transition of the azomethine compound is caused by the collapse of the crystal structure due to cis-trans isomerization, as in the case of the azobenzene compound. Since the π-π interaction between molecules is generally strong, the photophase transition occurs only at the very outermost surface of the crystal structure. On the other hand, in the compound having an azomethine moiety of the present invention, at least one of the substituents on the benzene ring is an alkyl group, an alkoxy group, an acyl group or an alkoxycarbonyl group. Since the alkyl group, alkoxy group, acyl group, and alkoxycarbonyl group have thermal motility, the compound having an azomethine moiety of the present invention has a periodic structure in which the π-π interaction is dominant. It forms a unique crystal structure in which isotropically disturbed structures coexist. Therefore, when the cis-trans isomerization reaction proceeds locally and the π-π interaction of the azomethine moiety is reduced, isotropic melting occurs in a chained manner throughout the system. In addition, in the compound having an azomethine moiety of the present invention, at least one of the substituents of the heterocycle is a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. It is preferably an alkoxy group, an acyl group having 2 to 19 carbon atoms or an alkoxycarbonyl group having 2 to 19 carbon atoms. With such a structure, lattice defects that favor cis-trans isomerization are generated, free volume is expressed, and π-π interaction is reduced. Therefore, it is considered that cis-trans isomerization is more likely to proceed and fluidization is more likely to occur.

For the above reasons, it is considered that the compound having an azomethine moiety of the present invention can induce a reversible fluidization and non-fluidization phenomenon with isomerization while being colorless, and the compound having an azomethine moiety is used as a toner. By introducing the toner, it is possible to obtain a toner that can be fixed by light irradiation and has high color reproducibility.

The flow in the present invention refers to a state in which the system is deformed without an external force or with a small external force.

Hereinafter, preferred embodiments of the present invention will be described. In addition, in this specification, "X to Y" indicating a range means "X or more and Y or less". Further, in the present specification, unless otherwise specified, operations and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH.

<Compound with azomethine moiety>
The compound having an azomethine moiety of the present invention is a compound represented by the following chemical formula 1 that is reversibly fluidized and non-fluidized by light irradiation. In the present invention, by introducing a heterocycle represented by the following chemical formula 1 instead of benzene into a compound having an azomethine moiety, the rate of isomerization from Z-form to E-form is reduced, and the cis form (cis form) during light irradiation ( It is considered that the amount of Z) increased and fluidization associated with the photoisomerization reaction could be induced.

In the chemical formula 1, X is NR ₁₀ , O or S.

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

R ₁ and R ₂ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.

R ₃ and R ₄ are independently a group represented by the chemical formula 2, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group. ..

At this time, either one of R ₃ and R ₄ is a group represented by the chemical formula 2.

R ₁₀ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group or a hydroxy group.

In the chemical formula 2, R _{5 to} R ₉ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group.

At this time, at least one of R _{5 to} R ₉ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is. As described above, in the compound having an azomethine moiety of the present invention, at least one of the substituents of the benzene ring of Chemical Formula 2 is an alkyl group, an alkoxy group, an acyl group or an alkoxycarbonyl group. Since the alkyl group, alkoxy group, acyl group, and alkoxycarbonyl group have thermal motility, the compound having an azomethine moiety of the present invention has a periodic structure in which the π-π interaction is dominant. It forms a unique crystal structure in which isotropically disturbed structures coexist. Therefore, if the cis-trans isomerization reaction proceeds locally and the π-π interaction at the azomethine moiety is reduced, the effect of causing isotropic melting in a chained manner in the entire system can be achieved.

In the present invention, at least one of R _{1 to} R ₄ in the chemical formula 1 is a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and carbon. It is an acyl group of number 2 to 19 or an alkoxycarbonyl group of 2 to 19 carbon atoms, and / or R ₁₀ is a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is the basis. In particular, it is preferable that at least one of R _{1 to} R ₂ and R ₁₀ not adjacent to the group represented by the chemical formula 2 is one of the substituents described above. By introducing the above-mentioned substituent of the heterocycle, the crystal is easily collapsed, the photomeltability is improved, and the fixability is improved. Specifically, the fixability of Examples 51 to 59 is improved with respect to Example 60. Among the above substituents, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms or an alkoxycarbonyl group having 2 to 19 carbon atoms are preferable. Alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, acyl groups having 2 to 13 carbon atoms or alkoxycarbonyl groups having 2 to 13 carbon atoms are more preferable, and alkyl groups having 1 to 8 carbon atoms and carbon atoms. Alkoxy groups having a number of 1 to 8, acyl groups having 2 to 9 carbon atoms or alkoxycarbonyl groups having 2 to 9 carbon atoms are more preferable. As described above, the compound having an azomethine moiety of the present invention is at least one of the substituents of the heterocyclic ring of chemical formula 1 (particularly, at least one of R _{1 to} R ₂ and R ₁₀ which is not adjacent to the group represented by the chemical formula 2). Halogen atom, cyano group, nitro group, hydroxy group, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, acyl group having 2 to 19 carbon atoms or alkoxy group having 2 to 19 carbon atoms. carbonyl group (wherein, R ₁₀ is as defined above) preferably in the range of. With such a structure, lattice defects that favor cis-trans isomerization are generated, free volume is expressed, and π-π interaction is reduced. Therefore, it is preferable in that cis-trans isomerization is more likely to proceed and fluidization is more likely to occur. Further, in the present invention, the same applies to the case where all of R _{1 to} R ₄ and R ₁₀ which are the substituents of the heterocycle of the chemical formula 1 except for the group represented by the chemical formula 2 are hydrogen atoms. It is preferable in that the fluidization of the above is easily expressed (see Compound 14 in Table 1 and Example 10 in Table 2 and Example 60 in Table 3 using the same). This is because the benzene ring (the group represented by the chemical formula 2) contains a long-chain substituent, so that even if all the substituents of the 5-membered ring (the heterocycle of the chemical formula 1) are hydrogen atoms, fluidization is possible. This is because it is easily expressed.

In the present invention, the R ₇ is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, acyl groups having 2 to 13 carbon atoms or alkoxycarbonyl groups having 2 to 13 carbon atoms are more preferable, and alkyl groups having 4 to 12 carbon atoms and carbon atoms. Alkoxy groups having a number of 4 to 12, acyl groups having 5 to 13 carbon atoms, or alkoxycarbonyl groups having 5 to 13 carbon atoms are more preferable. In this way, by introducing a long chain substituent at the para position of the benzene ring, the crystal is easily broken, the photomeltability is improved, and the fixability is improved. Specifically, the fixability of Example 65 is better than that of Example 90.

Further, from the viewpoint of efficiently inducing thermal motion, at least one of R ₁₀ on the heterocyclic (five-membered ring) side of the chemical formula 1 or R _{1 to} R ₄ not adjacent to the group represented by the chemical formula 2. R ₇ of the 6-membered ring of Chemical Formula 2 is an alkyl group having 4 to 12 carbon atoms, an alkoxy group having 4 to 12 carbon atoms, an acyl group having 5 to 13 carbon atoms, or an alkoxy group having 5 to 13 carbon atoms. It is preferably a carbonyl group.

In the present invention, at least one of R ₅ , R ₆ , R ₈ and R ₉ has the formation of lattice defects, the expression of free volume, and the intermolecular π-π interaction that favor cis-trans isomerization. It is preferable that it is an alkyl group having 1 to 4 carbon atoms which may have a branch, an alkoxy group having 1 to 4 carbon atoms which may have a branch, or a halogen atom in order to induce reduction of the above. ..

In the present invention, S or N is preferable for the heteroatom of X because the fixability is improved. Specifically, the fixability of Examples 51 to 93 and 97 to 99 of S or N is improved as compared with Examples 94 to 96 in which the heteroatom of X is O.

Examples of the alkyl group having 1 to 18 carbon atoms used in R _{1 to} R ₁₀ are not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, and the like. 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, Linear alkyl groups such as n-hexadecyl groups; isopropyl group, sec-butyl group, tert-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-trimethylhexyl group, 1-methyldecyl group, 1-hexylheptyl group and other branched alkyl groups.

Examples of the alkoxy groups having 1 to 18 carbon atoms used in R _{1 to} R ₁₀ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-hexyloxy group, n-heptyloxy group, n. -Octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n -Linear alkoxy groups such as hexadecyloxy groups: 1-methylpentyloxy group, 4-methyl-2-pentyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 1-methyl Hexyloxy 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-trimethylhexyloxy group, 1-methyldecyloxy group, 1-hexylheptyloxy group and other branched alkoxy groups.

Examples of the acyl groups having 2 to 19 carbon atoms used in R _{1 to} R ₁₀ are saturated or unsaturated linear or branched acyl groups, for example, acetyl group, propanoyl group (propionyl group), butanoyl. Group (butylyl group), isobutanoyl group (isobutyryl group), pentanoyl group (valeryl group), isopentanoyl group (isovaleryl group), sec-pentanoyl group (2-methylbutyryl group), tert-pentanoyl group (pivaloyl group), hexanoyl Group, Heptanoyl group, Octanoyl group, tert-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, stearoyl group, behenoyl group, undecylenoyl group, oleoyl group and the like.

Examples of the alkoxycarbonyl groups having 2 to 19 carbon atoms used in R _{1 to} R ₁₀ are linear or branched, and are, for example, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyl. Oxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tri Linear alkoxycarbonyl groups such as decyloxycarbonyl group, n-tetradecyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group: 1-methylpentyloxycarbonyl group, 4-methyl- 2-Pentyloxycarbonyl group, 3,3-dimethylbutyloxycarbonyl 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- Examples thereof include branched alkoxycarbonyl groups such as methyldecyloxycarbonyl group and 1-hexylheptyloxycarbonyl group.

As the compound having an azomethine moiety of the present invention, X, Z ₁ , Z ₂ , R _{1 to} R ₁₀ shown in Table 1-1, Table 1-2 and Table 1-3 below are appropriately selected from Compounds 1 to 1. 74 and the like can be mentioned.

“Group of formula 2” in R ₃ and R ₄ of Tables 1-1 to 1-3 refers to “group represented by chemical formula 2”.

As described above, the alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the acyl group having 2 to 19 carbon atoms or the alkoxycarbonyl group having 2 to 19 carbon atoms used in R _{1 to} R ₁₀ may be used. It may be linear or branched.

The wavelength of the irradiation light when the compound having the azomethine moiety is fluidized by light irradiation is preferably in the range of 280 nm or more and 480 nm or less, more preferably in the range of 300 nm or more and 420 nm or less, and further preferably in the range of 330 nm or more and 420 nm or less. Is inside. Within this range, light is absorbed well, so that the photomeltability is improved and the fixability is improved. Further, by irradiating the irradiation light of the above wavelength, fluidization can be performed without applying heat or pressure. Therefore, by introducing a compound having the azomethine moiety into the toner, fixing at the above wavelength is possible, and a toner having high color reproducibility can be obtained. The wavelength range is in the ultraviolet region, but also includes a visible light region close to ultraviolet light. This is because the compound having the azomethine moiety can be fluidized under the following irradiation conditions even with irradiation light in the visible light region close to ultraviolet rays.

The irradiation conditions of the irradiation light when the compound having a azomethine sites are fluidized, the dose is preferably 0.1 J / cm ² or more 200 J / cm ² within the range, more preferably 0.1 J / cm in the range of ² or more 100 J / cm ² or less, more preferably, in the range 0.1 J / cm ² or more 50 J / cm ² less.

On the other hand, the condition for immobilizing (resolidifying) the compound having the azomethine moiety is preferably left at room temperature (range of 25 ± 15 ° C.), that is, in a natural environment. In this case, it is better to keep it in a dark place, but it may be exposed to visible light such as natural light or a fluorescent lamp.

The method for synthesizing the compound having an azomethine moiety of the present invention is not particularly limited, and conventionally known synthetic methods can be applied. For example, for example, compound 21 in Table 1 in which the heterocycle of Chemical Formula 1 is a thiophene ring can be synthesized by the following schemes 1 to 3. The thiophene compounds of Compounds 1 to 20 and 22 to 49 in Table 1 can also be synthesized by the same method as the synthesis of Compound 21 in Table 1 shown below.

In dimethylformamide (DMF), the raw materials 4-nitrophenol and 1-iodohexane (C ₆ H ₁₃ I) are heated under reflux using potassium carbonate (K ₂ CO ₃ ) to react, and the reaction solution is washed with water. , Concentrate and purify to give 4-hexyloxynitrobenzene (see Scheme 1 below).

A mixed solvent of ethanol (EtOH) and tetrahydrofuran (THF), and stirred while sealed hydrogen gas _{(H 2)} relative to palladium on carbon (Pd / C catalyst) under 4-hexyloxy-nitrobenzene obtained in Scheme 1 4- (Hexyloxy) aniline can be obtained by reacting with the reaction solution, removing the catalyst from the reaction solution, concentrating the solution, and then recrystallizing with ethanol (see Scheme 2 below).

In ethanol (EtOH), 4- (hexyloxy) aniline obtained in Scheme 2 and 5-bromothiophene-2-carboxyaldehyde are reacted by heating and stirring, the reaction solution is filtered, and the obtained powder is cooled. By washing with ethanol and recrystallization with methanol / ethanol, the target compound 21 in Table 1 can be obtained (see Scheme 3 below). The temperature during heating and stirring of Scheme 3 is preferably in the range of 0 ° C. or higher and 100 ° C. or lower, more preferably in the range of 30 ° C. or higher and 70 ° C. or lower, and further preferably in the range of 40 ° C. or higher and 60 ° C. or lower. is there.

Further, for example, taking the compound 50 of Table 1 in which the heterocycle of Chemical Formula 1 is a thiophene ring as an example, it can be synthesized by the following schemes 4 to 5. The thiophene compound of compound 51 in Table 1 can also be synthesized by the same method as the synthesis of compound 50 in Table 1 shown below.

In dimethylformamide (DMF), the raw materials 4-hydroxy-3-methylbenzaldehyde and iodohexane (C ₆ H ₁₃ I) are heated and refluxed using potassium carbonate (K ₂ CO ₃ ) to react, and the reaction solution is prepared. 4-Hexyloxy-3-methylbenzaldehyde can be obtained by washing with water, concentrating and purifying (see Scheme 4 below).

In ethanol (EtOH), 4-hexyloxy-3-methylbenzaldehyde obtained in Scheme 4 and 5-hexylthiophen-2-amine were reacted by heating and stirring, and the reaction solution was filtered to obtain the powder. The target compound 50 can be obtained by washing with cold ethanol and recrystallization with methanol / ethanol (see Scheme 5 below). The temperature during heating and stirring of Scheme 5 is preferably in the range of 0 ° C. or higher and 100 ° C. or lower, more preferably in the range of 30 ° C. or higher and 70 ° C. or lower, and further preferably in the range of 40 ° C. or higher and 60 ° C. or lower. is there.

Further, for example, taking the compound 55 of Table 1 in which the heterocycle of Chemical Formula 1 is a furan ring as an example, it can be synthesized by the following schemes 6 to 8. The furan compounds of compounds 52 to 54 and 56 to 58 in Table 1 can also be synthesized by the same method as the synthesis of compound 55 in Table 1 shown below. Further, for example, the furan rings in which Z ₁ and Z ₂ of compounds 52 to 58 in Table 1 are exchanged are not exemplified in Table 1, but are synthesized with reference to the above schemes 4 to 5 and the following schemes 6 to 8. it can.

In dimethylformamide (DMF), the raw materials 2-methyl-4-nitrophenol and 1-iodohexane (C ₆ H ₁₃ I) are heated and refluxed using potassium carbonate (K ₂ CO ₃ ) to react and react. The solution is washed with water, concentrated and purified to obtain 3-methyl-4-hexyloxynitrobenzene (see Scheme 6 below).

Hydrogen gas (H ₂ ) with respect to 3-methyl-4- (hexyloxy) nitrobenzene obtained in the above scheme 6 under palladium carbon (Pd / C catalyst) in a mixed solvent of ethanol (EtOH) and tetrahydrofuran (THF). ) Is sealed and reacted, the catalyst is removed from the reaction solution, the solution is concentrated, and then recrystallized with ethanol to obtain 3-methyl-4- (hexyloxy) aniline (below). See scheme 7).

In ethanol (EtOH), 3-methyl-4- (hexyloxy) aniline obtained in Scheme 7 and 5-bromo-2-flualdehyde were reacted by heating and stirring, and the reaction solution was filtered to obtain the obtained solution. If the powder is washed with cold ethanol and recrystallized from methanol / ethanol, the target compound 55 can be obtained (see Scheme 8 below). The temperature during heating and stirring of Scheme 8 is preferably in the range of 0 ° C. or higher and 100 ° C. or lower, more preferably in the range of 30 ° C. or higher and 70 ° C. or lower, and further preferably in the range of 40 ° C. or higher and 60 ° C. or lower. is there.

Further, for example, taking the compound 70 of Table 1 in which the heterocycle of Chemical Formula 1 is a pyrrole ring as an example, it can be synthesized by the following schemes 9 to 11. The pyrrole compounds of compounds 59 to 69 and 71 to 74 in Table 1 can also be synthesized by the same method as the synthesis of compound 70 in Table 1 shown below. Further, for example, the pyrrole rings in which Z ₁ and Z ₂ of compounds 59 to 74 in Table 1 are exchanged are not exemplified in Table 1, but are synthesized with reference to the above schemes 4 to 5 and the following schemes 9 to 11. it can.

In dimethylformamide (DMF), the raw materials 2-methyl-4-nitrophenol and (C ₆ H ₁₃ I) are heated and refluxed using potassium carbonate (K ₂ CO ₃ ) to react, and the reaction solution is washed with water. , Concentrate and purify to give 4-hexyloxy-3-methylnitrobenzene (see Scheme 9 below).

Hydrogen gas (H ₂ ) was added to 4-hexyloxy-3-methylnitrobenzene obtained in Scheme 9 under palladium carbon (Pd / C catalyst) in a mixed solvent of ethanol (EtOH) and tetrahydrofuran (THF). 3-Methyl-4- (hexyloxy) aniline can be obtained by stirring and reacting while encapsulating, removing the catalyst from the reaction solution, concentrating the solution, and then recrystallizing with ethanol (scheme 10 below). reference).

In ethanol (EtOH), 3-methyl-4- (hexyloxy) aniline obtained in Scheme 10 and pyrrole-2-carboxyaldehyde are reacted by heating and stirring, and the reaction solution is filtered to obtain a powder. The desired compound 70 can be obtained by washing with cold ethanol and recrystallizing with methanol / ethanol (see Scheme 11 below). The temperature during heating and stirring of Scheme 11 is preferably in the range of 0 ° C. or higher and 100 ° C. or lower, more preferably in the range of 30 ° C. or higher and 70 ° C. or lower, and further preferably in the range of 40 ° C. or higher and 60 ° C. or lower. is there.

The compound having an azomethine moiety of the present invention can be used alone or in combination of two or more.

[Toner configuration]
The toner of the present invention contains the compound having the azomethine moiety that is reversibly fluidized and non-fluidized by the above-mentioned light irradiation. By introducing the compound having an azomethine moiety 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 compound having the azomethine moiety depends on the compound type and the resin type, but from the viewpoint of fixability and color reproducibility, the compound having the azomethine moiety: binder resin = 5:95 to 95: 5 is preferable. The range may be in the range of (mass ratio), but the range of 10:90 to 90:10 (mass ratio) is more preferable, and the range of 10:90 to 80:20 (mass ratio) is further preferable. The range of 70:30 (mass ratio) is particularly preferable, and the range of 10:90 to 60:40 (mass ratio) is particularly preferable.

<Bundling resin>
The toner of the present invention preferably further contains a binder resin in addition to the compound having an azomethine moiety. It is generally known that toner particles having a substantially uniform particle size and shape can be produced by using the emulsion aggregation method described later as a method for producing toner. Toners can be produced by adding the compound having the azomethine moiety alone or other additives such as a colorant and a mold release agent without using a binder resin (see Example 104 in Table 3). By using the compound having an azomethine moiety and the binder resin in combination, toner particles having a substantially uniform particle size and shape can be produced by using salting out in the emulsion aggregation method. Therefore, the toner containing the compound having the azomethine moiety and the binder resin can be easily applied by the toner for electrophotographic.

As such a binder resin, a resin generally used as a binder resin constituting a toner can be used without limitation. Specific examples thereof include styrene resin, acrylic resin, styrene acrylic resin, polyester resin, silicone resin, olefin resin, amide resin, and epoxy resin. These binder resins can be used alone or in combination of two or more.

Among these, at least one binder resin is selected from the group consisting of styrene resin, acrylic resin, styrene acrylic resin, and polyester resin from the viewpoint of having low viscosity when melted and having high sharp melt property. It is preferable to contain at least one selected from the group consisting of styrene acrylic resin and polyester resin.

Hereinafter, styrene acrylic resin and polyester resin, which are preferable binder resins, will be described.

(Styrene acrylic resin)
The styrene acrylic resin referred to in the present invention is formed by polymerizing at least a styrene monomer and 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 a structure having a known side chain or functional group in the styrene structure.

Further, the (meth) acrylic acid ester monomer has a functional group having an ester bond in the side chain. _{Specifically,} CH 2 = CHCOOR (R is an alkyl group) other acrylic acid ester monomer represented _by, methacrylic acid ester represented by _{CH 2 = C (CH 3)} COOR (R is an alkyl group) Contains vinyl ester compounds such as monomers.

Specific examples of the styrene monomer and the (meth) acrylic acid ester monomer capable of forming the styrene acrylic resin are shown below, but the present invention is not limited to those shown below.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and p-. Examples thereof include t-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene.

The (meth) acrylic acid ester monomer is typically the acrylic acid ester monomer and the methacrylate ester monomer shown below, and examples of the acrylic acid ester monomer include methyl acrylate and the like. Examples thereof include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate and phenyl acrylate phenyl. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. , Lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

These styrene monomer, acrylic acid ester monomer, or methacrylic acid ester monomer can be used alone or in combination of two or more.

In addition to the above-mentioned copolymers formed only of the styrene monomer and the (meth) acrylic acid ester monomer, the styrene-acrylic copolymer also includes these styrene monomer and the (meth) acrylic acid ester. In addition to the monomer, some are formed by using a general vinyl monomer in combination. Hereinafter, vinyl monomers that can be used in combination when forming the styrene-acrylic copolymer referred to in the present invention will be illustrated, 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, etc. Vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc. (6) Other vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylonitrile, methacrylo Acrylic acid such as nitrile and acrylamide, or methacrylic acid derivative.

It is also possible to prepare a resin having a crosslinked structure by using a polyfunctional vinyl monomer. Furthermore, it is also possible to use a vinyl monomer having an ionic dissociation group in the side chain. Specific examples of the ionic dissociating group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specific examples of vinyl monomers having these ionic dissociative groups are shown below.

Specific examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, silicic acid, fumaric acid, maleic acid monoalkyl ester, and itaconic acid monoalkyl ester. ..

The method for forming the styrene acrylic resin is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. If necessary, a known chain transfer agent such as n-octyl mercaptan may be used.

When the styrene acrylic resin used in the present invention is formed, the contents of the styrene monomer and the acrylic acid ester monomer are not particularly limited, and the softening temperature and the glass transition temperature of the binder resin are controlled. It is possible to make appropriate adjustments from the viewpoint. Specifically, the content of the styrene monomer is preferably 40 to 95% by mass, more preferably 50 to 80% by mass, based on the entire monomer. The content of the acrylic acid ester monomer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the entire monomer.

The method for forming the styrene acrylic resin is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include the following azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators.

Examples of the azo or diazo polymerization initiator include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1). -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

Examples of the peroxide-based polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, Examples thereof include 4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,5-t-butylperoxycyclohexyl) propane, and tris- (t-butylperoxy) triazine.

Further, when styrene acrylic resin particles are formed by the emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

The polymerization temperature varies depending on the type of monomer and polymerization initiator used, but is preferably 50 to 100 ° C, more preferably 55 to 90 ° C. The polymerization time varies depending on the type of monomer and polymerization initiator used, but is preferably 2 to 12 hours, for example.

The styrene acrylic resin particles formed by the emulsification polymerization method may have two or more layers made of resins having different compositions. In this case, as a production method, a polymerization initiator and a polymerizable monomer are added to a dispersion of resin particles prepared by an emulsion polymerization treatment (first-stage polymerization) according to a conventional method, and this system is polymerized. A multi-stage polymerization method for processing (second-stage polymerization) can be adopted.

(Polyester resin)
The polyester resin is a known 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). The polyester resin may be amorphous or crystalline.

The valences of the polyvalent carboxylic acid component and the polyhydric alcohol component are preferably 2 to 3 respectively, and particularly preferably 2 each. Therefore, as a particularly preferable form, the valences are 2 each (that is, dicarboxylic acid). Acid component, diol component) will be described.

Examples of the dicarboxylic acid component include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, and 1,10-decandicarboxylic acid. (Dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanediocarboxylic acid, 1,18 -Saturated aliphatic dicarboxylic acids such as octadecanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as methylenesuccinic acid, fumaric acid, maleic acid, 3-hexendioic acid, 3-octendioic acid, dodecenylsuccinic acid; phthalic acid, Telephthalic acid, isophthalic acid, t-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylene diacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anthracendicarboxylic acid, etc. The unsaturated aromatic dicarboxylic acid of the above; and the like, and these lower alkyl esters and acid anhydrides can also be used. The dicarboxylic acid component may be used alone or in combination of two or more.

In addition, trimellitic acid, pyromellitic acid and other trivalent or higher valent carboxylic acids, anhydrides of the above carboxylic acid compounds, alkyl esters having 1 to 3 carbon atoms and the like can also be used.

Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 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-octadecanediols, 1,20-eicosanediols, neopentyl glycols; 2-butene-1,4-diols, 3-butene-1,4-diols, 2-butins. Unsaturated aliphatic diols such as -1,4-diol, 3-butin-1,4-diol, 9-octadecene-7,12-diol; bisphenols such as bisphenol A and bisphenol F, and addition of ethylene oxide thereof. Examples thereof include 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 polyvalent carboxylic acid component and the polyhydric alcohol component using a known esterification catalyst.

As catalysts that can be used in the production of polyester resins, 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, Examples thereof include metal compounds such as germanium; phosphite compounds; phosphoric acid compounds; and amine compounds. Specifically, examples of the tin compound include dibutyltin oxide (dibutyltin oxide), tin octylate, tin dioctylate, and salts thereof. Titanium compounds include titanium alkoxides such as tetranormal butyl titanate (Ti (On-Bu) ₄ ), tetraisopropyl titanate, tetramethyl titanate, tetrastearyl titanate; titanium acylate such as polyhydroxytitanium stearate; titanium tetra. Examples thereof include titanium chelates such as acetylacetonate, titanium lactate, and titanium triethanolaminate. Examples of the germanium compound include germanium dioxide and the like. Further, examples of the aluminum compound include polyaluminum hydroxide, aluminum alkoxide, tributylaluminate and the like. These may be used alone or in combination of two or more.

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

When the toner of the present invention contains a binder resin, the content ratio may be in the range of the compound having an azomethine moiety: binder resin = 5:95 to 95: 5 (mass ratio), but from 10:90 to The range of 90:10 (mass ratio) is preferable, the range of 10:90 to 80:20 (mass ratio) is more preferable, and the range of 10:90 to 70:30 (mass ratio) is even more preferable. A range of 60:40 (mass ratio) is particularly preferred. Within this range, the photophase transition of the compound having the azomethine moiety is likely to occur, and the softening rate due to the light irradiation of the toner becomes sufficient.

The toner containing the compound having the azomethine moiety and the binder resin may have a single-layer structure or a core-shell structure. The type of the binder resin used for the core particles of the core-shell structure and the shell portion is not particularly limited.

<Colorant>
The toner of the present invention preferably further contains a colorant. It is considered that the compound having an azomethine moiety can induce reversible fluidization and non-fluidization phenomena with isomerization while being colorless. Therefore, by introducing a desired colorant into the toner together with the compound having the azomethine moiety, it is possible to obtain a toner that can be fixed by light irradiation and has high color reproducibility of the added colorant. As the colorant, generally known dyes and pigments can be used.

Examples of colorants for obtaining black toner include carbon black, magnetic material, and iron / titanium composite oxide black, and carbon black includes channel black, furnace black, acetylene black, thermal black, lamp black, and the like. Can be mentioned. Further, examples of the magnetic material include ferrite and magnetite.

Examples of the colorant for obtaining the yellow toner include C.I. I. Dyes such as Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162; C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185 and the like.

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

Examples of the colorant for obtaining cyan toner include C.I. I. Dyes such as Solvent Blue 25, 36, 60, 70, 93, 95; C.I. I. Pigment Blue 1, 7, 15, 60, 62, 66, 76 and other pigments can be mentioned.

As the colorant for obtaining the toner of each color, one kind or a combination of two or more kinds can be used for each color.

The content ratio of the colorant is preferably 0.5 to 20% by mass, and more preferably 2 to 10% by mass in the toner.

<Release agent>
The toner according to the present invention preferably further contains a mold release agent. By introducing a release agent into the toner together with the compound having an azomethine moiety, a toner having more excellent fixability can be obtained.

The release agent used is not particularly limited, and various known waxes can be used. Examples of the wax include low molecular weight polypropylene, polyethylene, oxidized low molecular weight polypropylene, polyolefin such as polyethylene, paraffin, synthetic ester wax, etc. In particular, synthetic ester wax is used because of its low melting point and low viscosity. It is particularly preferable to use behenyl behenate, glycerin tribehenate, pentaerythritol tetrabehenate and the like as the synthetic ester wax.

The content ratio of the release agent is preferably in the range of 1 to 30% by mass in the toner, and more preferably in the range of 3 to 15% by mass.

<Charge control agent>
The toner according to the present invention may further contain a charge control agent. The charge control agent used is not particularly limited as long as it is a substance capable of giving positive or negative charge by triboelectric charge and is colorless, and various known positive charge control agents and negative charge control agents and negative charges are used. A chargeable charge control agent can be used.

The content ratio of the charge control agent is preferably in the range of 0.01 to 30% by mass, and more preferably in the range of 0.1 to 10% by mass in the toner.

<External agent>
In order to improve the fluidity, chargeability, cleaning property, etc. of the toner, the toner of the present invention is composed by adding an external agent such as a fluidizing agent and a cleaning aid, which are so-called post-treatment agents, to the toner particles. You may.

Examples of the external additive include inorganic oxide particles such as silica particles, alumina particles, and titanium oxide particles, inorganic stearic acid compound particles such as aluminum stearate particles and zinc stearate particles, strontium titanate particles, and zinc titanate particles. Inorganic particles such as inorganic titanic compound particles such as. These can be used alone or in combination of two or more.

These inorganic particles may be surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat resistance and storage stability and environmental stability.

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 size of toner>
The average particle size of the toner is preferably 4 to 10 μm, more preferably 6 to 9 μm in terms of volume-based median diameter (D50). When the volume-based median diameter (D50) is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

In the present invention, the toner volume-based median diameter (D50) is a computer system (Beckman Coulter) in which data processing software "Software V3.51" is mounted on "Coulter Counter 3" (manufactured by Beckman Coulter Co., Ltd.). It is measured and calculated using a measuring device connected to (manufactured by Co., Ltd.).

Specifically, 0.02 g of the measurement sample (toner) is 20 mL of a surfactant solution (for the purpose of dispersing toner particles, for example, a neutral detergent containing a surfactant component diluted 10-fold with pure water). After adding to the solution) and acclimatizing, ultrasonic dispersion was performed for 1 minute to prepare a toner dispersion, and this toner dispersion contained "ISOTONII" (manufactured by Beckman Coulter, Inc.) in the sample stand. Pipette into the beaker until the indicated concentration on the measuring device is 8%.

Here, by setting this concentration range, a reproducible measured value can be obtained. Then, in the measuring device, the number of measured particles is 25,000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integration fraction is 50 from the largest. The particle size 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, when only the compound having the azomethine moiety is used as the toner, the additive other than the binder resin obtained by the above synthesis method is pulverized using an apparatus such as a hammer mill, a feather mill, or a counter jet mill. After that, a production method including classifying to a desired particle size using a dry classifier such as spin air sheave, classy seal, or micron classifier is preferable.

In the case of producing a toner containing the compound having an azomethine moiety and an additive such as a colorant and not containing a binder resin, a solvent in which both the compound having an azomethine moiety and the additive such as a colorant are dissolved is used. A production method including dissolving a compound having an azomethine moiety and an additive such as a colorant to prepare a solution, removing the solvent, and then pulverizing and classifying by the same method as described above is preferable.

When producing a toner containing an additive such as a compound having an azomethine moiety, a binder resin and a colorant, it is preferable to use a production method using an emulsion aggregation method in which the particle size and shape can be easily controlled.

Such a manufacturing method
(1A) Binder resin particle dispersion preparation step for preparing a dispersion of binder resin particles (1B) Colorant particle dispersion preparation step for preparing a dispersion of colorant particles (1C) Compound particles having an azomethine moiety Compound particle dispersion preparation step of preparing a dispersion liquid having an azomethine moiety (2) A flocculant is added to an aqueous medium in which binder resin particles, colorant particles and compound particles having an azomethine moiety are present, and a salt is added. Assembling step of forming aggregated particles by aggregating and fusing at the same time as proceeding with analysis (3) Aging step of forming toner particles by controlling the shape of the associated particles (4) Filtering the toner particles from the aqueous medium Filtration and cleaning steps to remove surfactants and the like from the toner particles (5) Drying step to dry the washed toner particles (6) Addition of an external additive to the dried toner particles It is preferable to include each step of the addition step. Hereinafter, the steps (1A) to (1C) will be described.

(1A) Bundling Resin Particle Dispersion Liquid 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 binding resin particles. As an example, a dispersion liquid of the binder resin particles is prepared by putting the polymerizable monomers constituting the binder resin into an aqueous medium and dispersing them, and polymerizing these polymerizable monomers with a polymerization initiator. ..

Further, as a method for obtaining a binder resin particle dispersion solution, in addition to the method of polymerizing a polymerizable monomer with a polymerization initiator in the above-mentioned aqueous medium, for example, a dispersion treatment in an aqueous medium without using a solvent is performed. Or a binder resin (crystalline resin, etc.) is dissolved in a solvent such as ethyl acetate to prepare a solution, and the solution is emulsified and dispersed in an aqueous medium using a disperser, and then desolvated. The method etc. can be mentioned.

At this time, if necessary, the binding resin may contain a release agent (wax) in advance. Further, for dispersion, polymerization is appropriately carried out in the presence of a known surfactant (for example, anionic surfactant such as polyoxyethylene (2) sodium dodecyl ether sulfate, sodium dodecyl sulfate, dodecylbenzene sulfonic acid). Is also preferable. In addition to the binder resin particle dispersion, a release agent particle dispersion is prepared in the same manner as in the colorant particle dispersion preparation step, and is present in the aqueous medium of the association step of (2) above. May be good.

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 "Microtrack UPA-150" (manufactured by Nikkiso Co., Ltd.).

(1B) Colorant Particle Dispersion Solution Preparation Step This colorant particle dispersion preparation step is a step of preparing a dispersion of colorant particles by dispersing the colorant in fine particles in an aqueous medium.

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

(1C) Compound particle dispersion preparation step having an azomethine moiety In this azobenzene derivative particle dispersion preparation step, a compound having an azomethine moiety is dispersed in an aqueous medium in the form of fine particles to prepare a dispersion of compound particles having an azomethine moiety. It is a process to do. In preparing a compound particle dispersion having an azomethine moiety, first, an emulsion of a compound having an azomethine moiety is prepared. As a method for preparing an emulsion of a compound having an azomethine moiety, for example, after obtaining a compound solution having an azomethine moiety in which a compound having an azomethine moiety is dissolved in an organic solvent, the compound solution having the azomethine moiety is placed in an aqueous medium. There is a method of emulsifying with.

The method of dissolving the compound having an azomethine moiety in an organic solvent is not particularly limited, and for example, there is a method of adding a compound having an azomethine moiety to an organic solvent and stirring and mixing so that the compound having an azomethine moiety is dissolved. .. The addition ratio of the compound having an azomethine moiety is preferably 5 parts by mass or more and 100 parts by mass or less, and 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 compound solution having an azomethine moiety and an aqueous medium are mixed and stirred using a known disperser such as a homogenizer. As a result, the compound having an azomethine moiety becomes droplets and is emulsified in an aqueous medium to prepare an emulsified solution of the compound having an azomethine moiety.

The addition ratio of the compound solution having an azomethine moiety is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the aqueous medium.

Further, when the compound solution having an azomethine moiety and the aqueous medium are mixed, the temperatures of the compound solution having the azomethine moiety and the aqueous medium are in a temperature range lower than the boiling point of the organic solvent, preferably 20 ° C. or higher. It is 80 ° C. or lower, more preferably 30 ° C. or higher and 75 ° C. or lower. When the compound solution having an azomethine moiety and the aqueous medium are mixed, the temperature of the compound solution having the azomethine moiety and the temperature of the aqueous medium may be the same or different from each other, and are preferably the same as each other.

As for the stirring conditions of the disperser, for example, when the capacity is 1 to 3 L, the rotation speed is preferably 7,000 rpm or more and 20,000 rpm or less, and the stirring time is preferably 10 minutes or more and 30 minutes or less.

A compound particle dispersion having an azomethine moiety is prepared by removing an organic solvent from an emulsion of a compound having an azomethine moiety. Examples of the method for removing the organic solvent from the emulsion of the compound having an azomethine moiety include known methods such as blowing air, heating, depressurizing, or a combination thereof.

As an example, the emulsion of the compound having an azomethine moiety is preferably 25 ° C. or higher and 90 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower, and the initial amount of organic solvent in an atmosphere of an inert gas such as nitrogen. The organic solvent is removed by heating until about 80% by mass or more and 95% by mass or less of the above is removed. As a result, the organic solvent is removed from the aqueous medium, and a compound particle dispersion having an azomethine moiety is prepared in which the compound particles having an azomethine moiety are dispersed in the aqueous medium.

The mass average particle size of the compound particles having an azomethine moiety in the compound particle dispersion liquid having an azomethine moiety is preferably 90 nm or more and 1200 nm or less. The mass average particle size of the compound particles having the azomethine moiety is the viscosity when the compound having the azomethine moiety is blended in the organic solvent, the blending ratio of the compound solution having the azomethine moiety and water, and the emulsion of the compound having the azomethine moiety. It can be set within the above range by appropriately adjusting the stirring speed of the disperser at the time of preparation. The mass average particle size of the compound particles having an azomethine moiety in the compound particle dispersion having an azomethine moiety 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 the compound having the azomethine moiety of the present invention. 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, dichloromethane, dichloroethane, and tetra. Examples thereof include halogenated hydrocarbons such as carbon chloride.

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

<Aqueous medium>
Examples of the aqueous medium used in this step include water or an aqueous medium containing water as a main component, a water-soluble solvent such as alcohols and glycols, and an optional component such as a surfactant and a dispersant. Be done. As the aqueous medium, a mixture of water and a surfactant is preferably used.

Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant and the like. Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate and the like. Examples of the nonionic surfactant include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, and monodecanoyl. Examples include sucrose.

Such surfactants can be used alone or in combination of two or more. Among the surfactants, an anionic surfactant is preferably used, and more preferably sodium dodecylbenzenesulfonate is used.

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

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

The coagulant used in (2) the associating step is not particularly limited, but one selected from metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum. And so on. Specific examples of the metal salt include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, etc., among which agglomerates in a smaller amount. It is particularly preferable to use a divalent metal salt because the above can be promoted. These can be used alone or in combination of two or more.

[Developer]
For example, the toner of the present invention may contain a magnetic substance and be used as a one-component magnetic toner, may be mixed with a so-called carrier and used as a two-component developer, or a non-magnetic toner may be used alone. , Any of which can be preferably used.

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

As the carrier constituting the two-component developer, magnetic particles made of metals such as iron, steel, nickel, cobalt, ferrite and magnetite, and magnetic particles made of conventionally known materials such as alloys of these metals with metals such as aluminum and lead are used. Can be used.

As the carrier, it is preferable to use a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, or a so-called resin dispersion type carrier in which magnetic powder is dispersed in a binder resin. The resin for coating is not particularly limited, and for example, an olefin resin, a styrene resin, a styrene acrylic resin, a silicone resin, a polyester resin, a fluororesin, or the like is used. Further, the resin for forming the resin-dispersed carrier is not particularly limited, and known ones can be used. For example, acrylic resin, styrene acrylic resin, polyester resin, fluororesin, phenol resin and the like can be used. Can be done.

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

The amount of the toner mixed with the carrier is preferably 2 to 10% by mass, with the total mass of the toner and the carrier as 100% by mass.

[Image formation 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 or a full-color image forming method. In the full-color image forming method, a four-cycle image forming method composed of four types of color developing devices for each of yellow, magenta, cyan, and black and one photoconductor, and color developing for each color. It can be applied to any image forming method such as a tandem image forming method in which an image forming unit having an apparatus and a photoconductor is mounted for each color. In the image forming method according to the embodiment of the present invention, a step of forming a toner image composed of a toner containing a compound having an azomethine moiety on a recording medium and a step of irradiating the toner image with light to soften the toner image. It is preferable to include a step of causing. Further, from the viewpoint of sufficiently fluidizing the compound having an azomethine moiety in the toner and quickly softening the toner image, the wavelength of light when irradiating the toner image with light is preferably 280 nm or more and 480 nm or less. Further, from the viewpoint of obtaining better fixability, it is preferable to further include a step of pressurizing the toner image. Further, from the viewpoint of obtaining better fixability, it is preferable to further heat the toner image in the pressurizing step.

FIG. 1 is a schematic configuration diagram showing an image forming apparatus 100 used in the image forming method according to the embodiment of the present 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 a device that forms an image on the recording paper S as a recording medium, includes an image reading device 71 and an automatic document feeder 72, and has an image on the recording paper S conveyed by the paper conveying system 7. An image is formed by the forming portion 10, the irradiation portion 40, and the crimping portion 9.

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

The document d placed on the platen 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. The analog signal photoelectrically converted by the image sensor CCD is input to the exposure device 3 of the image forming unit 10 after analog processing, A / D conversion, shading correction, image compression processing, etc. are performed in the image processing unit 20. To.

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

The image forming unit 10 surrounds the photoconductor 1 along the rotation direction of the photoconductor 1, and includes a charger 2, an exposure device 3, a developing unit 4, a transfer unit 5, a static elimination unit (not shown), and a cleaning unit 8. Are arranged and configured in this order.

The photoconductor 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 an arrow in FIG. 1 by a driving device (not shown). A thermohygrometer 17 for detecting the temperature and humidity inside the image forming apparatus 100 is provided in the vicinity of the photoconductor 1.

The charger 2 uniformly charges the surface of the photoconductor 1, and uniformly charges the surface of the photoconductor 1. The exposure device 3 is provided with a beam emitting source such as a laser diode, and by irradiating the surface of the charged photoconductor 1 with the beam light, the charge of the irradiated portion is eliminated, and the photoconductor 1 is statically charged according to the image data. Form an electro-latent image. The developing unit 4 supplies the toner contained therein to the photoconductor 1, and creates a toner image based on the electrostatic latent image on the surface of the photoconductor 1.

The transfer unit 5 faces the photoconductor 1 via the recording paper S and transfers the toner image to the recording paper S. The static elimination unit performs static elimination on the photoconductor 1 after transferring the toner image. The cleaning unit 8 includes a blade 85. The surface of the photoconductor 1 is cleaned by the blade 85 to remove the developer remaining on the surface of the photoconductor 1.

The recording paper S on which the toner image is transferred is conveyed to the crimping portion 9 by the conveying belt 13. The crimping portion 9 is arbitrarily installed, and the recording paper S on which the toner image is transferred is subjected to a fixing process by applying pressure only or heat and pressure by the pressure members 91 and 92, thereby recording. The image is fixed on the paper S. The recording paper S on which the image is fixed is conveyed to the paper ejection unit 14 by the conveying roller, and is ejected from the paper ejection unit 14 to the outside of the machine.

Further, the image forming apparatus 100 includes a paper reversing unit 24, and the recording paper S that has been heat-fixed is conveyed to the paper reversing unit 24 in front of the paper ejection unit 14, and the front and back sides are inverted and ejected. Alternatively, the recording paper S whose front and back sides are reversed can be conveyed to the image forming unit 10 again to form an image on both sides of the recording paper S.

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

The image forming apparatus 100 according to the embodiment of the present invention includes an irradiation unit 40. Examples of the device constituting the irradiation unit 40 include a light emitting diode (LED), a laser light source, and the like.

The irradiation unit 40 melts and fluidizes a compound (a compound having an azomethine moiety of the present invention) that undergoes a phase transition due to light absorption contained in the toner of a developing agent. The wavelength of the light to be irradiated may be such that it can be sufficiently fluidized, preferably in the range of 280 nm or more and 480 nm or less, more preferably in the range of 300 nm or more and 420 nm or less, and further preferably in the range of 330 nm or more and 420 nm or less. Irradiate light with a wavelength. The irradiation amount of light in the irradiation unit 40 may be such that it can be sufficiently fluidized, preferably within the range of 0.1 to 200 J / cm ² , and more preferably within the range of 0.1 to 100 J / cm ² . , More preferably in the range of 0.1 to 50 J / cm ² .

When a compound having an azomethine moiety is mobilized (resolidified), it may be solubilized by leaving it as it is at room temperature (range of 25 ± 15 ° C.).

That is, the image forming method according to the embodiment of the present invention includes a step of forming a toner image made of the toner of the present invention on a recording medium and irradiating the toner image with light having a wavelength of 280 nm or more and 480 nm or less. A step of softening the toner image and a step of solidifying the toner image and fixing it on a recording medium by leaving the softened toner image at room temperature (range of 25 ± 15 ° C.). Including. It is preferable that the fixing step further includes a step of pressurizing the softened toner image. In the pressurizing step, it is preferable to further heat the softened toner image. This is because it can be softened more by heating.

The heating temperature for further heating in the pressurizing step is preferably 30 ° C. or higher and 100 ° C. or lower, and more preferably 40 ° C. or higher and 100 ° C. or lower.

The irradiation unit 40 irradiates light toward the first surface of the recording paper S that holds the toner image on the photoconductor side, and the recording paper S surface nipped into the photoconductor 1 and the transfer roller 5 that is the transfer unit. It is arranged on the photoconductor side. Further, the irradiation unit 40 is arranged along the transport direction (paper transport direction) of the recording paper S.

The irradiation unit 40 is arranged on the downstream side in the paper transport direction with respect to the nip position of the photoconductor 1 and the transfer roller 5, and on the upstream side in the paper transport direction with respect to the crimping portion 9.

According to the image forming method according to the embodiment of the present invention, the photoconductor 1 is charged with a uniform potential by the charger 2, and then exposed to light flux irradiated by the exposure device 3 based on the original image data. Scan on the body 1 to form an electrostatic latent image. Next, the developing unit 4 supplies a developer having a toner containing a compound (a compound having an azomethine moiety) that undergoes a phase transition by light absorption onto the photoconductor 1.

When the toner image carried on the surface of the photoconductor 1 reaches the position of the transfer roller 5 which is the transfer unit by the rotation of the photoconductor 1, the recording paper S is conveyed from the tray 16 to the image forming unit 10. Due to the transfer bias applied to the transfer roller 5, the toner image on the photoconductor 1 is transferred onto the recording paper S nipped into the transfer roller 5 and the photoconductor 1.

Further, the transfer member 5 also serves as a pressurizing member, and while the toner image can be transferred from the photoconductor 1 to the recording paper S, the compound having an azomethine moiety contained in the toner image is surely transferred to the recording paper S. Can be brought into close contact.

After the toner image is transferred to the recording paper S, the blade 85 of the cleaning unit 8 removes the developer remaining on the surface of the photoconductor 1.

In the process in which the recording paper S on which the toner image is transferred is conveyed to the crimping portion 9 by the conveying belt 13, the irradiation unit 40 transmits a wavelength of 280 nm or more and 480 nm or less with respect to the toner image transferred on the recording paper S. Irradiate the light you have. By irradiating the toner image on the first surface of the recording paper S with ultraviolet light by the irradiation unit 40, the toner image can be more reliably melted, and the fixability of the toner image to the recording paper S is improved. be able to.

When the recording paper S on which the toner image is held reaches the crimping portion 9 by the transport belt 13, the pressurizing members 91 and 92 crimp the toner image to the first surface of the recording paper S. Since the toner image is softened by the irradiation of ultraviolet light by the irradiation unit 40 before the fixing process is performed by the pressure-bonding portion 9, energy saving of image crimping on the recording paper S can be achieved. In the image forming method of the present invention, in the step of solidifying the toner image and fixing it on a recording medium, the step of pressurizing the toner image with the pressurizing members 91 and 92 while leaving the toner image at room temperature (range of 25 ± 15 ° C.) is performed. It is preferable to further include it. By applying pressure by the pressure members 91 and 92, the fixability of the toner image on the recording paper S is further improved.

The pressure at which the toner image on the recording medium is pressed 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 that the contact area between the toner image and the recording paper S increases, and it is easy to further improve the fixability of the image. Further, by setting the pressure to 5.0 MPa or less, shock noise during pressurization can be suppressed.

Further, in the pressurizing step, it is preferable to further heat the toner image. By applying pressure and heat by the pressure members 91 and 92, the fixability of the toner image on the recording paper S is further improved. Specifically, in the pressurizing member 91, when the recording paper S passes between the pressurizing members 91 and 92, the toner image softened by light irradiation is pressed in a state of being further softened by heating. As a result, the fixability of the toner image on the recording paper S is further improved.

Then, the toner image on the recording paper S is solidified in a natural environment (leaving at room temperature). Specifically, the recording paper S that has passed between the pressurizing members 91 and 92 is left in a natural environment (a state of being left at room temperature) up to the paper ejection portion 14, so that the toner image on the recording paper S is displayed. It can be solidified more reliably, and the fixability of the toner image to the recording paper S can be further improved.

When an image is formed on both sides of the recording paper S, the crimped recording paper S is conveyed to the paper reversing section 24 in front of the paper ejection section 14 and ejected by inverting the front and back sides, or the front and back surfaces are inverted. The recording paper S is conveyed to the image forming unit 10 again.

(Photosensitive adhesive)
Since the compound of the present invention is reversibly fluidized and non-fluidized by light irradiation, it is possible to prepare a photosensitive adhesive that can be repeatedly used by using the compound of the present invention. For example, it can be applied to various adhesive technologies as a photosensitive adhesive that can be repeatedly photoattached and detached in response to a change in viscosity (coefficient of friction).

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 thereto.

The effect of the present invention will be described with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.

The compound having an azomethine moiety in which the heterocycle of Chemical Formula 1 used in Examples 1-41 is a thiophene ring was synthesized by the same method as the synthesis of Compound 21 in Table 1 used in Example 16 shown below. The synthetic method of Example 16 is shown as a representative.

[Synthesis of compounds with azomethine moiety]
<Example 16: Synthesis of compound 21 in Table 1>

Scheme 1
4-Nitrophenol (4.2 g, 30.2 mmol), 1-iodohexane (19.2 g, 90.6 mmol), potassium carbonate (19.2 g, 90.6 mmol) in a 100 ml 4-head flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. 10.4 g, 75.5 mmol) and 50 ml of dimethylformamide were added and refluxed by heating. The reaction mixture was washed with water, concentrated, and purified by column chromatography (ethyl acetate: heptane = 1: 9 (volume ratio)) to obtain 5.8 g (yield 86%) of 4- (hexyloxy) nitrobenzene. ..

Scheme 2
In a 500 ml Erlenmeyer flask, put 4- (hexyloxy) nitrobenzene (5.8 g, 26.1 mmol) and palladium carbon (0.12 g, 258 mmol), put 60 ml each of ethanol and tetrahydrofuran, and add hydrogen (H ₂ ). Stirred while encapsulating. Palladium on carbon was removed from the reaction solution, the obtained solution was concentrated, and then recrystallized from ethanol to obtain 3.8 g (yield 75%) of 4- (hexyloxy) aniline.

Scheme 3
4- (Hexyloxy) aniline (1.1 g, 5.7 mmol) and 5-bromothiophene-2-carboxyaldehyde (1.1 g,) in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. 5.7 mmol) and 20 ml of ethanol were added, and the mixture was heated and stirred at 50 ° C. The reaction solution was suction filtered, and the obtained powder was washed with cooling ethanol. Further, recrystallization was carried out with methanol / ethanol to obtain 0.85 g (yield 41%) of the target compound 21.

¹ The formation of compound 21 was confirmed by ¹ H NMR. ¹ H NMR (400 MHz, CDCl ₃ ); 8.35 ppm (s, 1H, CH = N), 7.71 ppm (d, 2H, aryl), 6.95 ppm (d, 2H, aryl), 6,89 ppm (d). , 2H, thiophene), 4.08 ppm (t, 2H, methylene), 1.81 ppm (m, 2H, methylene), 1.45 ppm (m, 2H, methylene), 1.38 ppm (m, 4H, methylene), 0.85 ppm (t, 3H, methylene).

In addition, a polarizing microscope observation was performed to confirm the phase transition from the crystalline phase or the liquid crystal phase to the isotropic phase. The target compound 21 was encapsulated in a glass sandwich cell, irradiated with light of 365 nm under a polarizing microscope observation, and a change in state was observed. FIG. 3 shows photographs of a polarizing microscope (a) before light irradiation, (b) after light irradiation, and (c) after light irradiation is stopped. By light irradiation, isomerization and reversible phase change of crystal phase-isotropic phase were confirmed.

The other compounds were also synthesized by the same method using the corresponding raw materials to obtain compounds having an azomethine moiety in which the heterocycle of Chemical Formula 1 of Examples 1-41 is a thiophene ring (see Table 2).

<Examples 1 to 12: Synthesis of a compound having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
In each case, 4-nitrophenol (30 mmol) was changed to 2-methyl-4-nitrophenol (30 mmol),
5-Bromothiophene-2-carboxyaldehyde (5.7 mmol),
In Compound 1 of Example 1, 5-hexylthiophene-2-carboxyaldehyde (5.0 mmol),
In Compound 4 of Example 2, 5-propylthiophene-2-carboxyaldehyde (5.8 mmol),
In Compound 5 of Example 3, 5-methylthiophene-2-carboxyaldehyde (5.2 mmol),
In Compound 6 of Example 4, 5-hexyloxythiophene-2-carboxyaldehyde (5.1 mmol),
In Compound 8 of Example 5, 5-hexylcarbonylthiophene-2-carboxyaldehyde (5.6 mmol),
In Compound 9 of Example 6, 5-bromothiophene-2-carboxyaldehyde (5.8 mmol),
In Compound 10 of Example 7, 5-cyanothiophene-2-carboxyaldehyde (5-formylthiophene-2-carbonitrile) (5.1 mmol),
In Compound 12 of Example 8, 5-methoxythiophene-2-carboxyaldehyde (5.0 mmol),
In compound 13 of Example 9, 5-hydroxythiophene-2-carboxyaldehyde (5.3 mmol),
In compound 14 of Example 10, 2-thiophenecarboxyaldehyde (5.4 mmol),
In compound 15 of Example 11, 5-hexyl-4-methylthiophene-2-carboxyaldehyde (5.4 mmol),
Compound 16 of Example 12 was converted to 5-hexyl-3-methylthiophen-2-carboxyaldehyde (5.5 mmol) in the same manner as in the synthesis of Compound 21, except that the compounds of Examples 1 to 12 were converted to 5-hexyl-3-methylthiophen-2-carboxyaldehyde (5.5 mmol). 1, 4-6, 8-10, 12-16 were synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 13: Synthesis of a compound having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
4-Nitrophenol (30 mmol) is converted to 2-methyl-4-nitrophenol (30 mmol),
Compound of Example 13 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-hexylthiophene-2-carboxyaldehyde (5.3 mmol). 17 was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Examples 14, 15, 17, 18: Synthesis of compound 17 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
5-Bromothiophene-2-carboxyaldehyde (5.7 mmol),
In Compound 19 of Example 14, 5-hexylthiophene-2-carboxyaldehyde (5.0 mmol),
In compound 20 of Example 15, 5-methylthiophene-2-carboxyaldehyde (5.1 mmol),
In compound 22 of Example 17, 5-methoxythiophene-2-carboxyaldehyde (5.2 mmol),
Compound 23 of Example 18, Compounds 19, 20, and Compounds 19, 20, 18 of Examples 14, 15, 17, and 18 were used in the same manner as in the synthesis of Compound 21, except that they were changed to 2-thiophenecarboxyaldehyde (5.3 mmol), respectively. 22 and 23 were synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 19: Synthesis of compound 25 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
4-Nitrophenol (30 mmol) is converted to 2-methoxy-4-nitrophenol (20 mmol),
Compound of Example 19 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-hexylthiophene-2-carboxyaldehyde (5.0 mmol). 25 was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 20: Synthesis of compound 27 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
Converting 4-nitrophenol (30 mmol) to 2-methyl-4-nitrophenol (30 mmol),
Converting 1-iodohexane (91 mmol) to 1-iodooctane (90 mmol),
Compound 27 of Example 20 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-hexylthiophene-2-carboxyaldehyde (5.6 mmol). Was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 21: Synthesis of compound 29 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
4-Nitrophenol (30 mmol) is converted to 2-methyl-4-nitrobenzoic acid (10 mmol),
Compound 29 of Example 21 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-hexylthiophene-2-carboxyaldehyde (5.7 mmol). Was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Examples 22 to 27: Synthesis of compounds 30 to 35 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
4-Nitrophenol (30 mmol) was changed to 2-methyl-4-nitrophenol (30 mmol) in Examples 22-24.
Further, 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 4-hexylthiophene-2-carboxyaldehyde (5.3 mmol) in Examples 22 and 25, and 4-methyl in Examples 23 and 26. It was changed to thiophene-2-carboxyaldehyde (5.2 mmol), and in Examples 24 and 27, it was changed to 4-bromothiophene-2-carboxyaldehyde (5.2 mmol) in the same manner as in the synthesis of compound 21. Compounds 30-35 of Examples 22-27 were synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Examples 28 to 35: Synthesis of compounds 36 to 43 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
The steps of Schemes 1 and 2 are omitted, and 4- (hexyloxy) aniline (5.7 mmol) is used in Scheme (Scheme) 3, and 3-methyl-4-hexylaniline (6 mmol) is used in Examples 28 to 31. In Examples 32 to 35, it was changed to 4-hexylaniline (6 mmol).
5-Bromothiophene-2-carboxyaldehyde (5.0 mmol) was changed to 5-hexylthiophene-2-carboxyaldehyde (5.1 mmol) in Examples 28 and 32, and 5-methylthiophene- in Examples 29 and 33. Example 28 in the same manner as in the synthesis of compound 21, except that it was changed to 2-carboxyaldehyde (5.2 mmol) and changed to 5-methoxythiophene-2-carboxyaldehyde (5.1 mmol) in Examples 31 and 35. Compounds 36 to 43 of ~ 35 were synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Examples 36 to 39: Synthesis of compounds 44 to 47 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
By omitting the steps of Schemes 1 and 2, in Scheme 3, 4-hexyloxybenzeneamine (5.7 mmol) was changed to 4-hexylaniline (6 mmol).
5-Bromothiophene-2-carboxyaldehyde (5.0 mmol) was changed to 4-hexylthiophene-2-carboxyaldehyde (5.3 mmol) in Example 36 and 4-methylthiophene-2-carboxyaldehyde (5.3 mmol) in Example 37. It was changed to (5.2 mmol), changed to 4-bromothiophene-2-carboxyaldehyde (5.1 mmol) in Example 38, and changed to 4-methoxythiophene-2-carboxyaldehyde (5.0 mmol) in Example 39. Except for the above, compounds 44 to 47 of Examples 36 to 39 were synthesized in the same manner as in the synthesis of compound 21. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 40: Synthesis of compound 48 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
4-Nitrophenol (30.2 mmol) is changed to 3-Nitrophenol (30 mmol),
The compound of Example 40 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-methylthiophene-2-carboxyaldehyde (5.5 mmol). 48 was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 41: Synthesis of compound 49 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
Compound of Example 41 in the same manner as in the synthesis of compound 21, except that 5-bromothiophene-2-carboxyaldehyde (5.7 mmol) was changed to 5-methylthiophene-3-carboxyaldehyde (5.0 mmol). 49 was synthesized. Similar to Compound 21, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

Compounds 50 and 51 having an azomethine moiety in which the heterocycle of Chemical Formula 1 used in Examples 42 and 43 is a thiophene ring were synthesized by the same method as the synthesis of Compound 50 in Table 1 of Example 42 shown below. The method for synthesizing compound 50 of Example 42 is typically shown.

[Synthesis of compounds with azomethine moiety]
<Example 42: Synthesis of compound 50 in Table 1>

Scheme 4
4-Hydroxy-3-methylbenzaldehyde (3.0 g, 22.0 mmol), 1-iodohexane (14.0 g, 66.1 mmol) in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. , Potashium carbonate (7.6 g, 55.1 mmol, and 30 ml of dimethylformamide were added and refluxed by heating. The reaction solution was washed with water and then concentrated, and column chromatography (ethyl acetate: heptane = 1: 9 (volume ratio)). ) To obtain 4.1 g (84% yield) of 4-hexyloxy-3-methylbenzaldehyde.

Scheme 5
4-Hexyloxy-3-methylbenzaldehyde (1.0 g, 4.5 mmol) and 5-hexylthiophen-2-amine (0.8 g) in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. , 4.5 mmol) and 20 ml of ethanol were added, and the mixture was heated and stirred at 50 ° C. The reaction solution was suction filtered, and the obtained powder was washed with cooling ethanol. Further, recrystallization was carried out in a mixed solvent of methanol / ethanol to obtain 0.62 g (yield 35%) of the target compound 50.

¹ The formation of compound 50 was confirmed by ¹ H NMR. ¹ H NMR (400 MHz, CDCl ₃ ); 7.35 ppm (s, 1H, CH = N), 7.72 ppm (d, 2H, aryl), 7.38 ppm (s, 1H, thiophene), 7.00 ppm (d) , 1H, aryl), 6,76ppm (s, 1H, thiophene), 4.07ppm (t, 2H, methylene), 2.85ppm (t, 2H, methylene), 2.10ppm (s, 3H, methylene), 1.78 ppm (m, 2H, methylene), 1.70 ppm (m, 2H, methylene), 1.45 ppm (m, 2H, methylene), 1.32 ppm (m, 10H, methylene), 0.86 ppm (t, 6H, methyl).

<Example 43: Synthesis of compound 51 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring>
Compound 51 of Example 43 was synthesized in the same manner as in the synthesis of compound 50, except that 4-hydroxy-3-methylbenzaldehyde (22 mmol) was changed to 4-hydroxybenzaldehyde (20 mmol). Similar to compound 50, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

Compounds 55 to 57 having an azomethine moiety in which the heterocycle of Chemical Formula 1 of Examples 44 to 46 is a furan ring were also synthesized in the same manner as the compound having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring. The method for synthesizing compound 55 of Example 44 is typically shown.

[Synthesis of compounds with azomethine moiety]
<Example 44: Synthesis of compound 55 in Table 1>

Scheme 6
2-Methyl-4-nitrophenol (3.1 g, 20 mmol), 1-iodohexane (12.9 g, 60.7 mmol), carbonate in a 100 ml 4-head flask equipped with a condenser, nitrogen inlet tube, and thermometer. Potassium (7.0 g, 50.6 mmol) and 30 ml of dimethylformamide were added, and the mixture was heated under reflux. The reaction mixture was washed with water, concentrated, and purified by column chromatography (ethyl acetate: heptane = 1: 9 (volume ratio)) to produce 3.8 g of 3-methyl-4- (hexyloxy) nitrobenzene (yield 79). %)Obtained.

Scheme 7
Erlenmeyer flask 500 ml, 3- methyl-4- (hexyloxy) nitrobenzene (3.3 g, 14 mmol) and palladium on carbon (0.07 g, 150 mmol), ethanol and tetrahydrofuran were placed 40ml respectively, enclosing a hydrogen _{(H 2)} It was stirred while stirring. Palladium on carbon was removed from the reaction solution, the obtained solution was concentrated, and then recrystallized from ethanol to obtain 2.1 g (yield 73%) of 3-methyl-4-hexyloxybenzeneamine.

Scheme 8
3-Methyl-4-hexyloxybenzeneamine (1.0 g, 5.0 mmol) and 5-bromo-2-flualdehyde (0.) in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. (9 g, 5.0 mmol) and 20 ml of ethanol were added, and the mixture was heated and stirred at 50 ° C. The reaction solution was suction filtered, and the obtained powder was washed with cooling ethanol. Further, recrystallization was carried out in a mixed solvent of methanol / ethanol to obtain 0.61 g (yield 33%) of the target compound 55.

¹ The formation of compound 55 was confirmed by ¹ H NMR. ¹ H NMR (400 MHz, CDCl ₃ ); 8.00 ppm (s, 1H, CH = N), 7.25 ppm (d, 1H, aryl), 7.21 ppm (s, 1H, aryl), 7.10 ppm (d). , 1H, furan), 6.95ppm (d, 1H, aryl), 6,82ppm (d, 1H, furan), 4.09ppm (t, 2H, methylene), 2.19ppm (s, 3H, methyl), 1.80 ppm (m, 2H, methylene), 1.46 ppm (m, 2H, methylene), 1.34 ppm (m, 4H, methylene), 0.91 ppm (t, 3H, methylene).

<Example 45: Synthesis of compound 56 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a furan ring>
Compound 56 of Example 45 was synthesized in the same manner as in the synthesis of compound 55, except that 5-bromo-2-flualdehyde (5.0 mmol) was changed to 4-bromo-2-flualdehyde (5.0 mmol). did. Similar to compound 55, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 46: Synthesis of compound 57 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a furan ring>
Compound 57 of Example 46 was synthesized in the same manner as in the synthesis of compound 55, except that 2-methyl-4-nitrophenol (20 mmol) was changed to 4-nitrophenol (20 mmol). Similar to compound 55, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

Compounds 70, 72, and 74 having an azomethine moiety in which the heterocycle of Chemical Formula 1 of Examples 47 to 49 is a pyrrole ring are also synthesized in the same manner as the compound having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a thiophene ring. did. The method for synthesizing compound 70 of Example 47 is typically shown.

[Synthesis of compounds with azomethine moiety]
<Example 47: Synthesis of compound 70 in Table 1>

Scheme 9
2-Methyl-4-nitrophenol (3.0 g, 20.0 mmol), 1-iodohexane (12.5 g, 58.8 mmol) in a 100 ml 4-head flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. , Potashium carbonate (6.8 g, 49.0 mmol), and 50 ml of dimethylformamide were added and refluxed by heating. The reaction mixture was washed with water, concentrated, and purified by column chromatography (ethyl acetate: heptane = 1: 9 (volume ratio)) to produce 3.6 g (yield 77%) of 4-hexyloxy-3-methylnitrobenzene. Obtained.

Scheme (Scheme) 10
In a 500 ml Erlenmeyer flask, put 4-hexyloxy-3-methylnitrobenzene (3.1 g, 13.1 mmol) and palladium carbon (0.06 g, 129 mmol), put 30 ml each of ethanol and tetrahydrofuran, and enclose hydrogen. Stirred. Palladium on carbon was removed from the reaction solution, the obtained solution was concentrated, and then recrystallized from ethanol to obtain 1.9 g (yield 70%) of 4-hexyloxy-3-methylbenzeneamine.

Scheme 11
4-Hexyloxy-3-methylbenzeneamine (1.0 g, 5.0 mmol) and pyrrole-2-carboxyaldehyde (0.47 g,) in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. 5.0 mmol) and 20 ml of ethanol were added, and the mixture was heated and stirred at 50 ° C. The reaction solution was suction filtered, and the obtained powder was washed with cooling ethanol. Further, recrystallization was carried out in a mixed solvent of methanol / ethanol to obtain 0.71 g (yield 50%) of the target compound 70.

¹ The formation of compound 70 was confirmed by ¹ H NMR. ¹ H NMR (400 MHz, CDCl ₃ ); 9.3 ppm (s, 1H, NH), 8.06 ppm (s, 1H, CH = N), 7.26 ppm (d, 1H, aryl), 7.20 ppm (s). , 1H, aryl), 6.96ppm (d, 1H, pyrrole), 6.92ppm (d, 1H, pyrrole), 6.54ppm (d, 1H, pyrrole), 6.12ppm (t, 1H, pyrrole), 4.13 ppm (t, 2H, methylene), 2.15 ppm (s, 3H, methylene), 1.78 ppm (m, 2H, methylene), 1.40 ppm (m, 2H, methylene), 1.37 ppm (m, 4H, methylene), 0.85 ppm (t, 3H, methyl).

<Example 48: Synthesis of compound 72 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a pyrrole ring>
Compound of Example 48 in the same manner as in the synthesis of compound 70, except that pyrrole-2-carboxyaldehyde (5.0 mmol) was changed to 2-hexyl-1-methylpyrrole-5-carboxyaldehyde (5.0 mmol). 72 was synthesized. Similar to compound 70, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Example 49: Synthesis of compound 74 having an azomethine moiety in which the heterocycle of Chemical Formula 1 is a pyrrole ring>
Converting 2-methyl-4-nitrophenol (20 mmol) to 4-nitrophenol (20 mmol),
Compound of Example 49 in the same manner as in the synthesis of compound 70, except that pyrrole-2-carboxyaldehyde (5.0 mmol) was changed to 2-hexyl-1-methylpyrrole-5-carboxyaldehyde (5.0 mmol). 74 was synthesized. Similar to compound 70, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

<Comparative Example 1: Synthesis of Azobenzene Compound 75>
A compound represented by the following chemical formula (2) in the same manner as in "(1-1-1) Synthesis of UV softening material A" described in paragraphs "0217" to "0224" of JP-A-2014-191078. (Azobenzene compound 75) was obtained. Similar to compound 70, the formation of the compound was confirmed by ¹ H NMR, and it was found that the target compound was obtained.

The numbers of the compounds obtained in Examples 1-49 and Comparative Example 1 and their structures are shown in Tables 2-1 and 2-2 below.

[Optical response adhesion test]
The changes in adhesiveness of the compounds synthesized in Examples 1 to 49 and Comparative Example 1 with light irradiation were evaluated by the following photoresponsive adhesion test using the apparatus shown in FIG. As shown in FIG. 4, 2 mg of the compound is placed on an 18 mm square cover glass 1 within a radius of 6 mm from the center of the glass, and the cover glass 2 of the same size is displaced by about 4 mm in the direction parallel to the cover glass 1. All the compounds were covered so as to cover them. This was heated to melt the sample, and the cover glass 1 and the cover glass 2 were adhered to each other. Each of the obtained samples was subjected to the following non-fluidity-> fluidity test, and then subjected to the following fluidity-> non-fluidity test.

<Non-fluidity → Liquidity test (fluidity test)>
The part (A) shown in FIG. 4 was fixed to the table with cellophane tape, and the part (C) was fixed with a vinyl string having a length of 30 cm with a weight of 100 g attached. The portion (B) was irradiated with light having a wavelength of 365 nm at an irradiation amount of 30 J / cm ² , and it was confirmed whether the cover glass 2 was peeled off from the cover glass 1, and the determination was made according to the following evaluation criteria. The results obtained are shown in Table 2-1 and Table 2-2.

− Non-fluidity → Evaluation criteria for fluidity test (fluidity test) −
〇: The cover glass 2 was completely peeled off from the cover glass 1. Δ: The cover glass 2 was displaced ×: The cover glass 2 did not move.

<Liquidity → Non-fluidity test (non-fluidity test)>
Non-fluidity → After 1 hour from the start of the fluidity test (1 hour was left in the natural environment, that is, at room temperature), the sample portion ((B) portion) of the cover glass 1 used in the above test was covered so as to cover it. Glass 3 (same size as cover glasses 1 and 2) was placed, and it was confirmed whether the cover glass 1 and the cover glass 3 adhered to each other, and the determination was made according to the following evaluation criteria. The results obtained are shown in Table 2-1 and Table 2-2.

-Liquidity → Evaluation criteria for non-fluidity test (non-fluidization test)-
〇: Did not adhere (it was non-fluidized)
Δ: Partially adhered (partially kept in a fluidized state)
X: Adhesive (the fluidized state was maintained).

“Group of formula 2” in R ₃ and R ₄ of Tables 2-1 to 2-2 refers to “group represented by chemical formula 2”. In addition, compound No. in Table 2-2. “75” in the column refers to the azobenzene compound 75 synthesized in Comparative Example 1.

[Preparation of binder resin]
(Preparation of Styrene Acrylic Resin Particle Dispersion 1 Containing Styrene Acrylic Resin 1)
(First stage polymerization)
A solution prepared by dissolving 8 parts by mass of sodium dodecyl sulfate in 3000 parts by mass of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, and stirred at a stirring speed of 230 rpm under a nitrogen stream. However, the internal temperature was raised to 80 ° C. After the temperature was raised, a solution prepared by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added to bring the liquid temperature to 80 ° C. again, and 480 parts by mass of styrene, 250 parts by mass of n-butyl acrylate, 68 parts of methacrylic acid. A polymerizable monomer solution consisting of 0 parts by mass and 16.0 parts by mass of n-octyl-3-mercaptopropionate was added dropwise over 1 hour, and then polymerized by heating and stirring at 80 ° C. for 2 hours to carry out polymerization and styrene. A styrene acrylic resin particle dispersion solution (1A) containing the acrylic resin particles (1a) was prepared.

(Second stage polymerization)
In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, a solution prepared by dissolving 7 parts by mass of polyoxyethylene-2-dodecyl ether sodium sulfate in 800 parts by mass of ion-exchanged water was charged and heated to 98 ° C. After heating, 260 parts by mass of the above styrene acrylic resin particle dispersion solution (1A), 245 parts by mass of styrene, 120 parts by mass of n-butyl acrylate, 1.5 parts by mass of n-octyl-3-mercaptopropionate, and a release agent. As a result, a polymerizable monomer solution prepared by dissolving 67 parts by mass of paraffin wax "HNP-11" (manufactured by Nippon Seiwa Co., Ltd.) at 90 ° C. was added, and a mechanical disperser "CREARMIX" (M Technique Co., Ltd.) having a circulation path was added. A dispersion containing emulsified particles (oil droplets) was prepared by mixing and dispersing for 1 hour.

Next, an initiator solution prepared by dissolving 6 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added to this dispersion, and the system was 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 prepared by dissolving 11 parts by mass of potassium persulfate in 400 parts by mass of ion-exchanged water was added to the above styrene acrylic resin particle dispersion (1B), and under a temperature condition of 82 ° C., 435 parts by mass of styrene and n-butyl A polymerizable monomer solution consisting of 130 parts by mass of 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 dropping, polymerization was carried out by heating and stirring for 2 hours, and then the mixture was cooled to 28 ° C. to obtain a styrene acrylic resin particle dispersion 1 containing a styrene acrylic resin 1. Moreover, when the glass transition point Tg of this styrene acrylic resin 1 was measured, it was 45 degreeC.

(Preparation of Polyester Resin Particle Dispersion Solution 1 Containing Polyester Resin 1)
In a 10 liter capacity four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, 524 parts by mass of bisphenol A propylene oxide 2 mol addition, 105 parts by mass of terephthalic acid, 69 parts by mass of fumaric acid, And 2 parts by mass of tin octylate (esterification catalyst) was added, and a polycondensation reaction was carried out at a temperature of 230 ° C. for 8 hours. Further, the polycondensation reaction was continued at 8 kPa for 1 hour and then cooled to 160 ° C. to obtain a polyester resin 1. 100 parts by mass of polyester resin 1 is crushed with "Randelmill 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 super-used with stirring. Using a sonic homogenizer "US-150T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), ultrasonic dispersion was performed with V-LEVEL at 300 μA for 30 minutes to obtain a polyester resin particle dispersion liquid 2. Moreover, when the glass transition point Tg of this polyester resin 1 was measured, it was 42 degreeC.

[Example 51: Preparation of toner 51]
(Preparation of cyan dispersion)
11.5 parts by mass of sodium n-dodecyl sulfate was dissolved in 1600 parts by mass of pure water, and 25 parts by mass of copper phthalocyanine (CI Pigment Blue 15: 3) was gradually added, and then "Clearmix (registered trademark)" was added. ) W Motion CLM-0.8 (manufactured by M Technique Co., Ltd.) ”was used to prepare a cyan dispersion.

(Preparation of compound particle dispersion 1 having an azomethine moiety)
80 parts by mass of dichloromethane and 20 parts by mass of compound 1 were mixed and stirred while heating at 50 ° C. to obtain a liquid containing compound 1. To 100 parts by mass of this liquid, a mixed liquid 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 dodecylbenzene sulfonate aqueous solution was added. Then, it was emulsified by stirring at 16000 rpm for 20 minutes with a homogenizer (manufactured by Heidorff) equipped with a shaft generator 18F to obtain an emulsified solution 1 of a compound having an azomethine moiety.

The obtained emulsion 1 of the compound having an azomethine moiety is put into a separable flask, and the organic solvent is removed by heating and stirring at 40 ° C. for 90 minutes while sending nitrogen into the gas phase to have the azomethine moiety. Compound particle dispersion 1 was obtained.

(Agglomeration, fusion)
The styrene acrylic resin particle dispersion 1 prepared above is 504 parts by mass in terms of solid content, the compound particle dispersion having an azomethine moiety is 216 parts by mass in terms of solid content, 900 parts by mass of ion-exchanged water, and the cyan dispersion is solid. 70 parts by mass in terms of minutes was charged into a reaction device equipped with a stirrer, a temperature sensor, and a cooling tube. The temperature inside the container was maintained at 30 ° C., and a pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution.

Next, an aqueous solution prepared 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 with stirring, and then the temperature was raised, and this system was heated over 60 minutes to 70. The temperature was raised to ° C., and the particle growth reaction was continued while maintaining 70 ° C. In this state, the particle size of the associated particles was measured with "Multisizer 3" (manufactured by Beckman Coulter, Inc.), and when the median diameter (D50) on a volume basis reached 6.5 μm, 190 parts by mass of sodium chloride. Was added to 760 parts by mass of ion-exchanged water to stop particle growth. After stirring at 70 ° C. for 1 hour, the temperature was further raised, and the particles were fused by heating and stirring at 75 ° C. Then, the mixture was cooled to 30 ° C. to obtain a dispersion of toner particles.

The dispersion liquid of the toner particles obtained above was solid-liquid separated by a centrifuge to form a wet cake of the toner particles. The wet cake is washed with ion-exchanged water at 35 ° C. in the centrifuge until the electrical conductivity of the filtrate reaches 5 μS / cm, and then transferred to a “flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.)” to obtain a water content. Was dried to 0.5% by mass to prepare a toner 51.

[Preparation of Toners 52 to 108 of Examples 52 to 108 and Toner 109 of Comparative Example 2]
In the same manner as in the production of the toner 51 of Example 51, the toners 52 to 109 were produced by appropriately changing the contents shown in Table 3-1 and Table 3-2.

[Preparation of developer]
With respect to the toners 51 to 109 produced 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) are provided with a toner particle concentration of 6 mass. The mixture was mixed so as to obtain%, and developers 51 to 109 were obtained. Mixing was carried out for 30 minutes using a V-type mixer.

<Evaluation method>
[Image formation method]
Using each of the obtained developing agents, a toner image was formed on plain paper as a recording medium to obtain a printed matter. Specifically, the developer is placed between a pair of parallel flat plate (aluminum) electrodes on which one developer and gloss-coated paper (basis weight: 128 g / m ² ) are placed, while sliding the developer by magnetic force, and the electrodes. The toner is developed under the condition that the gap is 0.5 mm and the toner adhesion amount between DC bias and AC bias is 4 g / m ² , a toner layer is formed on the surface of plain paper, and the printed matter is fixed by a fixing device. Obtained.

[Evaluation: Fixability test]
A 1 cm square image of this printed matter was rubbed 10 times with a pressure of 50 kPa with "JK Wiper (registered trademark)" (manufactured by Nippon Paper Crecia Co., Ltd.), and evaluated by the fixing rate of the image. A retention rate of 50% or more is considered acceptable. The evaluation results (fixation rate) of the obtained fixability test are shown in Table 3 below. The image fixation rate is the reflection density of a solid image after rubbing by measuring the density of the image after printing and the image after rubbing with a reflection densitometer "RD-918" (manufactured by Sakata Inks Engineering Co., Ltd.). Is divided by the reflection density of the solid image after printing, and is expressed as a percentage.

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

Fixing device No. 1: There is no crimping portion 9 in FIG. 2, the wavelength of ultraviolet light emitted from the irradiation portion 40 is 365 nm (light source: LED light source having an emission wavelength of 365 nm ± 10 nm), and the irradiation amount is 10 J / cm ² . Further, the toner softened by ultraviolet light irradiation was solidified (non-fluidized compound) and fixed in a natural environment, that is, left at room temperature (20 ° C.) until the paper ejection portion 14 (see FIG. 1). ..

Fixing device No. 2: There is a crimping portion 9 in FIG. 2, the temperature of the pressurizing member 91 is 20 ° C., and the pressure at the time of pressurization is 0.2 MPa. The light source and irradiation amount of the irradiation part are No. It is the same as 1. The toner softened by ultraviolet light irradiation is fixed by pressurization by the pressurizing member 91, and then solidified (compounds) in a state of being left at room temperature (20 ° C.) until the paper ejection portion 14 (see FIG. 1). (Demobilized).

Fixing device No. 3: There is a crimping portion 9 in FIG. 2, and the temperature of the pressurizing member 91 is 80 ° C. The light source and irradiation amount of the irradiation part are No. It is the same as 1. Further, the pressure at the time of pressurization by the pressurizing member 91 is No. It is the same as 2. Further, the toner softened by ultraviolet light irradiation was further softened and fixed by pressurization and heating by the pressurizing member 91. Then, the compound was solidified (compound fluidized) while being left at room temperature (20 ° C.) until the paper ejection section 14 (see FIG. 1) was reached.

[Color reproducibility evaluation]
The color reproducibility of the example images obtained above was evaluated according to the following evaluation criteria by visual evaluation by 10 monitors. Specifically, as a sample for evaluation comparison, a toner containing only a binder resin was prepared for the toners described in each example, developed in the same manner as in (image formation), and table 3-1 and 3-2. Fixing device No. shown in Fixation was performed in 1-3.

The evaluation comparison sample and the sample described in the examples were shown in order to 10 monitors, and asked if the colors of the two images were clearly different. The judgment results based on the following color reproducibility evaluation criteria are shown in Tables 3-1 and 3-2 below.

-Evaluation criteria for color reproducibility-
⊚: 2 or less responded that they were clearly different ○: 3-4 responded that they were clearly different △: 5-7 responded that they were clearly different ×: 8 or more responded that they were clearly different ..

The configuration of each toner, the type of fixing device, and the evaluation results are shown in Tables 3-1 and 3-2 below.

“Azomethine derivative” in Table 3-1 and Table 3-2 refers to a compound having an azomethine moiety represented by Chemical Formula 1. The compound number refers to the number of the compound having an azomethine moiety in Tables 1-1 to 1-3 and Tables 2-1 to 2-2. “Azomethine derivative: binder resin (mass ratio)” in Tables 3-1 and 3-2 indicates a compound having an azomethin moiety: a binder resin (mass ratio) in the toner. “Azomethine derivative: binder resin (mass ratio)” in Comparative Example 2 in Table 3-2 indicates “azobenzene compound: binder resin (mass ratio)”.

As is clear from Tables 3-1 and 3-2 above, the toners of Examples 51 to 108 showed high fixability and excellent color reproducibility. On the other hand, it was found that the toner of Comparative Example 2 had good fixability but low color reproducibility. Since the ultraviolet light source and the ultraviolet irradiation conditions used in the fixability test are constant throughout Examples 51 to 108 and Comparative Example 2, the toner of the example is reversible by light irradiation as compared with the toner of the comparative example. It can be said that the effect of the compound having an azomethine moiety that is fluidized and non-fluidized and has no significant coloring is fully exhibited.

A comparison of the fixing devices shows that the same toner 1 is used, ultraviolet rays are irradiated under the same conditions, and no pressure member is used. No. 1 pressurized with a pressurizing member rather than the fixing device of 1. No. 2 was pressurized while being heated by the fixing device and the pressurizing member. It was found that higher fixability could be obtained by using the fixing device of No. 3 (comparison of Examples 51, 107 and 108).

Looking at the compounds used in Examples 51 to 99 in which the compound having an azomethine moiety in the toner was changed, the detailed reason is not clear, but the suitable compound is Compound No. 1, 4-5, 9, 12, 19-23, 30-35, 40-47.

1 Photoreceptor,
2 Charger,
3 exposed device,
4 developing unit,
5 Transfer section (transfer roller),
7 Paper transport system,
8 Cleaning department,
9 Crimping part,
10 Image forming part,
11 Paper feed section,
12 Conveyor roller,
13 Conveyance belt,
14 Paper output section,
15 Manual paper feed section,
16 trays,
17 Thermo-hygrometer,
20 Image processing unit,
24 Paper reversing part,
40 Irradiated part,
71 Image reader,
72 Automatic document feeder,
85 blades,
90 Control unit,
91, 92 Pressurizing member,
100 image forming device,
d Manuscript,
S Recording paper.

Claims (16)

Compounds represented by the following chemical formula 1 that are reversibly fluidized and non-fluidized by light irradiation:
In the chemical formula 1,
X is NR ₁₀ , O or S,
Z ₁ and Z ₂ are independently N or CH, and Z ₁ ≠ Z ₂ , respectively.
R ₁ and R ₂ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
R ₃ and R ₄ are independently a group represented by the chemical formula 2, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group. ,
At this time, either one of R ₃ and R ₄ is a group represented by the chemical formula 2.
R ₁₀ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group or a hydroxy group.
In the chemical formula 2,
R _{5 to} R ₉ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.
At this time, at least one of R _{5 to} R ₉ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is. At least one of R _{1 to} R ₄ in the chemical formula 1 is a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 2 to 19 carbon atoms. an acyl group or an alkoxycarbonyl group having a carbon number of 2 to 19, and / or R ₁₀ is a halogen atom, hydroxy group according an alkoxycarbonyl group alkyl or 2 to 19 carbon atoms having 1 to 18 carbon atoms Item 2. The compound according to Item 1. The first or second claim, wherein R ₇ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Compound. Any of claims 1 to 3, wherein R ₇ is an alkyl group having 4 to 12 carbon atoms, an alkoxy group having 4 to 12 carbon atoms, an acyl group having 5 to 13 carbon atoms, or an alkoxycarbonyl group having 5 to 13 carbon atoms. The compound according to item 1. At least one of the above R ₅ , R ₆ , R ₈ and R ₉ has an alkyl group having 1 to 4 carbon atoms which may have a branch, and 1 to 4 carbon atoms which may have a branch. The compound according to any one of claims 1 to 4, which is an alkoxy group or a halogen atom. The compound according to any one of claims 1 to 5, wherein the wavelength of the irradiation light when the compound is fluidized by light irradiation is 280 nm or more and 480 nm or less. A toner containing the compound according to any one of claims 1 to 6. The toner according to claim 7, further comprising a binder resin. The toner according to claim 8, wherein the binder resin contains at least one selected from the group consisting of a styrene acrylic resin and a polyester resin. The toner according to any one of claims 7 to 9, further comprising a colorant. The toner according to any one of claims 7 to 10, further comprising a mold release agent. Image formation including a step of forming a toner image made of the toner according to any one of claims 7 to 11 on a recording medium and a step of irradiating the toner image with light to soften the toner image. Method. The image forming method according to claim 12, wherein the wavelength of the light when irradiating the toner image with light to soften the toner image is 280 nm or more and 480 nm or less. The image forming method according to claim 12 or 13, further comprising a step of pressurizing the toner image. The image forming method according to claim 14, wherein in the pressurizing step, the toner image is further heated. A photosensitive adhesive using the compound according to any one of claims 1 to 6.