阅读说明：本技术 光响应性材料、粘接剂、光开关材料、调色剂以及图像形成方法 (Light-responsive material, adhesive, photoswitch material, toner, and image forming method ) 是由 中井优笑子 须釜宏二 堀口治男 芝田豊子 早田裕文 于 2021-04-20 设计创作，主要内容包括：本发明提供一种在通过光照射而发生流体化并可逆地发生非流体化的光响应性材料中表现出更有效的流体化、非流体化的材料,即提供一种减少所需能源的材料。提供一种组合物,其包含异构化聚合物以及异构化低分子,该异构化聚合物含有具有异构化结构体的结构单元,该组合物从固体状态通过光照射而发生流体化并可逆地发生非流体化。(The present invention provides a material which exhibits more effective fluidization and non-fluidization in a light-responsive material which is fluidized by light irradiation and reversibly non-fluidized, that is, a material which requires less energy. Provided is a composition comprising an isomerized polymer containing a structural unit having an isomerized structure, and an isomerized low molecule, which is fluidized and reversibly non-fluidized from a solid state by light irradiation.)

1. A composition comprising an isomerized polymer containing structural units having an isomerized structure and an isomerized low-molecular compound, which composition is fluidized from a solid state by light irradiation and is reversibly non-fluidized.

2. The composition according to claim 1, wherein the isomerized polymer is a polymer containing a structural unit derived from an azobenzene derivative or a structural unit derived from an azoimine derivative, and the isomerized low-molecular compound is an azobenzene compound or an azoimine compound.

3. The composition according to claim 2, wherein the azobenzene derivative or the azomethine derivative contains a phenylene group having a linking moiety to a polymer main chain at a position para to a nitrogen-nitrogen double bond or a carbon-nitrogen double bond,

the azobenzene compound or the azoimine compound contains a phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms in a para-position to a nitrogen-nitrogen double bond or a carbon-nitrogen double bond.

4. The composition according to any one of claims 1 to 3, wherein the mixing ratio of the isomerized polymer to the isomerized low-molecular compound is 99:1 to 10:90 in terms of a mass ratio.

5. The composition according to any one of claims 1 to 4, wherein the wavelength of the light is 280nm or more and 480nm or less.

6. A toner comprising the composition according to any one of claims 1 to 5.

7. The toner according to claim 6, further comprising a binder resin.

8. The toner according to claim 7, wherein the binder resin contains at least one selected from styrene acrylic resins and polyester resins.

9. An image forming method, comprising:

a step of forming a toner image formed from the toner according to any one of claims 6 to 8 on a recording medium;

and a step of irradiating the toner image with light to soften the toner image.

10. The image forming method according to claim 9, wherein the wavelength of the light is 280nm or more and 480nm or less.

11. The image forming method according to claim 9 or 10, further comprising a step of pressurizing the toner image.

12. The image forming method according to claim 11, wherein in the pressing step, the toner image is further heated.

13. The image forming method according to any one of claims 9 to 12, wherein in the step of irradiating the toner image with light to soften the toner image, the toner image is heated while being irradiated with light.

14. A photo-responsive adhesive comprising the composition according to any one of claims 1 to 5.

15. An optical switching material comprising the composition according to any one of claims 1 to 5.

Technical Field

The present invention relates to a composition which is fluidized by light irradiation and reversibly fluidized and is a light-responsive material, an adhesive, a photoswitch material, and a toner using the composition, and an image forming method using the toner.

Background

A photoresponsive liquid crystal material is known, which changes its fluidity by light irradiation. For example, patent documents 1 and 2 propose a polymer liquid crystal material using an azobenzene derivative. These materials cause cis-trans allosteric reactions at azobenzene sites in response to light. It is considered that the resulting change in molecular structure induces a phase transition from a solid state to a fluid state. Further, the curing is performed again by irradiating light again with changing the wavelength, heating, or standing in the dark at room temperature, and a reverse reaction occurs.

Documents of the prior art

Patent document

Patent document 1, Japanese patent application laid-open No. 2011-256155

Patent document 2, Japanese patent laid-open publication No. 2011-

Disclosure of Invention

Problems to be solved by the invention

However, the phase transition of the azobenzene derivative described in the above patent documents 1 and 2 from the solid state to the fluid state, which is highly ordered, requires a sufficient amount of light energy to be able to break the ordered structure. Since these azobenzene derivatives are not efficiently propagated by structural changes due to photoisomerization, a large amount of energy is required for fluidization by light irradiation.

Accordingly, an object of the present invention is to provide a material that exhibits more effective fluidization and non-fluidization in a light-responsive material that is fluidized by light irradiation and reversibly non-fluidized, that is, a material that requires less energy.

Means for solving the problems

In view of the above technical problems, the inventors of the present invention have intensively studied. As a result, the present inventors have found that the above-mentioned technical problems can be solved by using a solid composition in which a polymer containing a structural unit derived from an isomerized structure and an isomerized low-molecular compound are mixed, and finally completed the present invention.

That is, the present invention is a composition comprising an isomerized polymer containing a structural unit having an isomerized structure and an isomerized low-molecular compound, which is fluidized from a solid state by light irradiation and reversibly non-fluidized.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a material exhibiting more effective fluidization, non-fluidization, that is, a material reducing the required energy source can be obtained among light-responsive materials which are fluidized by light irradiation and reversibly non-fluidized.

Drawings

Fig. 1 is a schematic configuration diagram showing an image forming apparatus 100 used in an image forming method according to an embodiment of the present invention.

Fig. 2 is a schematic configuration diagram of irradiation unit 40 in image forming apparatus 100.

Fig. 3 is a schematic view of an apparatus for measuring a change in adhesiveness of a composition used in a light-responsive adhesion experiment of examples with light irradiation.

Detailed Description

The present invention is a composition comprising an isomerized polymer containing a structural unit having an isomerized structure and an isomerized low-molecular compound, which is fluidized and reversibly non-fluidized from a solid state by light irradiation.

According to the present invention, a material can be obtained which exhibits more effective fluidization, non-fluidization by photoisomerization, i.e., a material which reduces the energy required.

The details of why the above-described effects can be obtained by the composition of the present invention are not clear, but the following mechanism can be considered. The following mechanism is assumed, but the present invention is not limited to the following mechanism.

In a polymer comprising a structural unit containing an isomer, the isomer absorbs light, and thermal energy released during photoexcitation and deactivation is transferred to a bonded repeating unit (structural unit) (photothermal conversion), whereby a reversible fluidization and non-fluidization phenomenon can be induced. In particular, if the isomerization structure in the polymer is a structure derived from a trans-isomer of a molecule exhibiting cis-trans photoisomerization, cis-trans photoisomerization by light irradiation is more likely to occur in addition to the above photothermal conversion, and a cis isomer having a low Tg is more likely to be generated. It is considered that the phase transition is caused by the destruction of the ordered structure by photoisomerization, and therefore, a more effective fluidization/non-fluidization phenomenon can be induced.

It can be considered that: when the isomerized low-molecular compound is mixed into the polymer containing an isomerized structure as described above, when the polymer contains an isomerized structure as a polymer side chain, the isomerized low-molecular compound is inserted into the interstitial space of the isomerized structure as a side chain, thereby forming pi-pi stacking. When light irradiation is performed, the isomerized low molecular weight compound having pi-pi stacking deviates from the ordered structure due to the structural change accompanying the isomerization of the isomerized structure of the polymer, and a free space is generated thereby, whereby the isomerization of the isomerized structure is more likely to occur, and the ordered structure can be more effectively destroyed, that is, the fluidization phenomenon is induced.

Further, it can also be considered that: when the isomerized low-molecular-weight compound is a trans isomer in a compound showing cis-trans photoisomerization, photoisomerization is likely to occur by light irradiation, and the isomerized low-molecular-weight compound is converted into a cis isomer, and is likely to deviate from an ordered structure by pi-pi stacking. This creates a free space in the polymer side chain, and the structure change of the isomerized structure of the polymer side chain is more easily induced, thereby enabling the induction of a more efficient fluidization phenomenon. In addition, by mixing the isomerized polymer with the isomerized low-molecular compound, a material having more excellent toughness can be obtained, as compared with the case where only the isomerized low-molecular compound is used.

Preferred embodiments of the present invention will be described below. In the present specification, "X to Y" indicating a range means "X or more and Y or less". In the present specification, unless otherwise specified, the operation and the measurement of physical properties are carried out under the conditions of room temperature (20 to 25 ℃) and relative humidity of 40 to 50% RH.

[ composition fluidized by light irradiation and reversibly non-fluidized ]

In the present specification, the term "fluidized and reversibly fluidized by light irradiation" means that the fluid is converted from a non-fluidized state to a fluidized state by light irradiation and is further returned to the non-fluidized state. That is, the composition of the present invention is in a solid state of non-fluidity at room temperature and under normal pressure without being irradiated with light, and softens and becomes fluid by irradiation with light. It is returned to a non-flowable solid state by stopping the irradiation of light, placing it in a dark place at room temperature or under irradiation of visible light, or by heating. In the present specification, the fluid state refers to a state of being deformed by a small external force.

Specific forms of the isomerized polymer and the isomerized low-molecular compound that can be used in the composition of the present invention will be described later, and the isomerized polymer that can be used in the composition of the present invention preferably contains a structural unit derived from an azobenzene derivative or a structural unit derived from an azobenzene derivative, and the isomerized low-molecular compound preferably contains an azobenzene compound or an azoimine compound.

Azobenzene derivatives and azomethine derivatives undergo cis-trans isomerization reaction by light irradiation, and a phase transition from a solid state to a fluid state is induced by a change in molecular structure. After the light irradiation is stopped, the derivative is placed in a dark place at room temperature or in a visible light irradiation environment, or heated, whereby the derivative is reversibly made non-fluidized (re-cured). Therefore, by using an azobenzene derivative (azobenzene compound) or an azomethine derivative (azomethine compound), and a polymer containing a structural unit derived from the above, fluidization due to light irradiation and reversible fluidization can be efficiently generated.

The composition of the present invention may be used in combination with a polymer containing a structural unit derived from an azobenzene derivative and an azobenzene compound, or may be used in combination with a polymer containing a structural unit derived from an azoimine derivative and an azoimine compound. In this case, the azobenzene derivative and the azobenzene compound contained in the structural unit of the polymer may have the same structure or different structures from each other. The azomethine derivative and the azomethine compound contained in the constitutional unit of the polymer may have the same structure or different structures from each other.

In the composition of the present invention, a polymer containing a structural unit derived from an azobenzene derivative and an azobenzene compound may be used in combination, or a polymer containing a structural unit derived from an azobenzene derivative and an azobenzene compound may be used in combination.

Further, a polymer having a structural unit derived from an azobenzene derivative and a polymer having a structural unit derived from an azobenzene derivative may be used in combination, or a polymer having a structural unit derived from an azobenzene derivative and a structural unit derived from an azobenzene derivative may be used.

In addition, the proportion of the polymer having a structural unit derived from an azobenzene derivative or a structural unit derived from an azobenzene derivative in the total mass of the isomerized polymer contained in the composition of the present invention is preferably 90 mass% or more, more preferably 95 mass% or more, and still more preferably 98 mass% or more. In addition, the total amount of the azobenzene compound and the azomethine compound in the total mass of the isomerized low molecular weight compounds contained in the composition of the invention is preferably 90 mass% or more, more preferably 95 mass% or more, and still more preferably 98 mass% or more.

[ isomerization of Low-molecular Compound ]

The isomerized low-molecular compound used in the composition of the present invention is a compound which is fluidized and reversibly non-fluidized by light irradiation, and is a compound having a molecular weight of less than 1000.

The isomerized low-molecular compound preferably has a molecular weight of 100 or more and less than 1000, more preferably 100 or more and 800 or less. In addition, the isomerized low molecular weight compound is free of polymer. In a preferred embodiment, the isomerized low molecular weight compound is composed without repeating structural units. In a preferred embodiment, the isomerized low molecular weight compound is not obtained by polymerizing a monomer containing a polymerizable group.

The isomerized low molecular weight compound is preferably a compound that exhibits photoisomerization. For example, compounds exhibiting cis-trans isomerization reaction by light irradiation, and the like can be cited. As such a compound showing a cis-trans isomerization reaction by light irradiation, an azobenzene derivative (azobenzene compound) or an azomethine derivative (azomethine compound) is preferably used. In addition, in the present specification, the azobenzene derivative (azobenzene compound) includes azobenzene.

(Azobenzene derivative)

The azobenzene derivative (azobenzene compound) used in the present invention is not particularly limited, and a preferred embodiment of the azobenzene derivative is an azobenzene derivative represented by the following chemical formula (1) because the softening rate by light irradiation is high and the fixing property of an image when used in a toner is excellent.

[ chemical formula 1]

In the above chemical formula (1), R₁～R₁₀Each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a hydroxyl group and a carboxyl group, and R₁～R₁₀At least two of them are selected from alkyl, alkoxy, halogen, hydroxyl and carboxyl, preferably R₁～R₅At least one of them is an alkyl group or an alkoxy group having 1 to 18 carbon atoms, and R₆～R₁₀At least one of the above groups is an alkyl group or an alkoxy group having 1 to 18 carbon atoms.

In the above chemical formula (1), R is preferably₃And R₈At least one of the above groups is an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. That is, a preferred embodiment of the azobenzene derivative used in the present invention is an azobenzene derivative containing a phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms in the para-position to the nitrogen-nitrogen double bond. It is believed that if R₃And R₈When at least one of the alkyl groups and the alkoxy groups has a carbon number within the above range, intermolecular stacking (pi-pi stacking) by an aromatic ring is exhibited in the trans form, and high thermal mobility is exhibited when the trans form is isomerized to the cis form, and thus a fluidization phenomenon is easily induced.

Among them, from the viewpoint of further improving the fixability of an image when used in a toner, R is₃And R₈Preferably, the alkyl groups are each independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. As described above, by having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at the para positions of the two benzene rings, the thermal mobility of the molecule is increased, and isotropic dissolution is easily caused in a chain manner in the entire system as described above. At this time, R₃And R₈They may be the same or different, and are preferably the same from the viewpoint of easy synthesis. In addition, for R₃And R₈The alkyl group or alkoxy group having 1 to 18 carbon atoms may be linear or branched, and is preferably linear from the viewpoint of constituting a structure of a rod-like molecule which is likely to cause optical phase transition.

Wherein R is₃And R₈Preferably, each of the alkyl groups and the alkoxy groups is an alkyl group or an alkoxy group having 6 to 12 carbon atoms. If R is₃And R₈In the case of an alkyl group or an alkoxy group having a carbon number within the above range, the alkyl-alkyl group interaction acting between molecules is weak even if it has high thermal mobility. Therefore, the crystals are easily disintegrated, the cis-trans isomerization is more easily performed, and the softening rate by light irradiation and the fixing property of the image when used in a toner are further improved.

In the above chemical formula (1), R₁、R₂、R₄、R₅、R₆、R₇、R₉、R₁₀At least one of them is preferably a group (hereinafter, also simply referred to as a substituent) selected from the group consisting of an alkyl group, an alkoxy group, a halogen group, a hydroxyl group and a carboxyl group. By having the above structure, a lattice is produced which advantageously functions for cis-trans isomerizationDefect generation, free volume expression, and reduction of pi-pi interactions. Therefore, cis-trans isomerization is more easily performed, and the softening speed by light irradiation and the fixability of an image when used in a toner are further improved. In particular, from the viewpoint of ensuring a free volume required for cis-trans isomerization, R₁、R₂、R₄、R₅、R₆、R₇、R₉、R₁₀At least one of the alkyl group, the alkoxy group, and the halogen group is more preferably an alkyl group, an alkoxy group, or a halogen group having 1 to 4 carbon atoms, which may have a branch, and is more preferably an alkyl group having 1 to 4 carbon atoms, and is even more preferably a methyl group, from the viewpoint of further improving the fixability of an image.

In the above chemical formula (1), R₁、R₂、R₄、R₅、R₆、R₇、R₉、R₁₀The number of the substituent(s) in (1) is preferably 1 to 8, more preferably 1 to 6. Among them, from the viewpoint of not excessively lowering the melting point of the azobenzene derivative and further improving the heat-resistant storage property of the toner, 1 to 4 is more preferable, and 1 to 3 is particularly preferable.

R₁、R₂、R₄、R₅、R₆、R₇、R₉、R₁₀The position where the substituent(s) is present is not particularly limited, but is preferably R in the above formula (1)₂、R₄、R₇And R₉At least a substituent is present in any one of (1), more preferably in R of the above chemical formula (1)₂、R₄、R₇And R₉At least a methyl group is present in any of them. The azobenzene derivative having the above structure has an improved image fixability due to a further increase in softening speed by light irradiation, and has an improved heat-resistant storage property of the toner due to a suitably high melting point.

The azobenzene derivative is preferably: for example, R in the formula (1) is 4,4 ' -dihexylazobenzene, 4 ' -dioctylazobenzene, 4 ' -didecylazobenzene, 4 ' -didodecylazobenzene, 4 ' -dihexadecylazobenzene, or the like₃And R₈Are each a carbon atom1-18 alkyl 4, 4' -dialkylazobenzene; or R in formula (1) such as 4,4 '-bis (hexyloxy) azobenzene, 4' -bis (octyloxy) azobenzene, 4 '-bis (dodecyloxy) azobenzene, 4' -bis (hexadecyloxy) azobenzene₃And R₈And 4, 4' -bis (alkoxy) azobenzenes each having an alkoxy group of 4 to 18 carbon atoms, wherein a hydrogen atom added to a benzene ring is mono-, di-or tri-substituted with a group selected from the group consisting of an alkyl group, an alkoxy group, a halogen group, a hydroxyl group and a carboxyl group. More specifically, the following azobenzene derivatives (1) to (12) can be mentioned.

[ chemical formula 2-1]

Azobenzene derivatives

(1)

(2)

(3)

(4)

(5)

(6)

(7)

[ chemical formula 2-2]

(8)

(9)

(10)

(11)

(12)

The method for synthesizing the azobenzene derivative is not particularly limited, and conventionally known methods can be used.

For example, as shown in the following reaction formula a, the azobenzene derivative (1) can be obtained by reacting 4-aminophenol with sodium nitrite in a cooled atmosphere to produce a diazonium salt, reacting the diazonium salt with o-cresol to synthesize an intermediate a (first stage), and then reacting n-bromohexane with the intermediate a.

[ chemical formula 3]

In the above reaction formula a, the desired azobenzene derivative can be obtained by changing the raw material (4-aminophenol, o-cresol and/or n-bromohexane) used to another compound. Further, by using the above production method, an azobenzene derivative having an asymmetric structure can be easily obtained.

For example, as shown in the following reaction formula B, the azobenzene derivative (4) can be obtained by changing o-cresol and n-bromohexane to 2-bromophenol and n-bromododecane, respectively.

[ chemical formula 4]

(reaction formula B)

Further, as shown in the following reaction formula C, the azobenzene derivative (5) can be obtained by reacting the azobenzene derivative (4) with methanol in the presence of a Pd catalyst and a base.

[ chemical formula 5]

(reaction formula C)

Alternatively, for example, as shown in the following reaction formula D, the azobenzene derivative (6) can be obtained by reacting manganese dioxide as an oxidizing agent with p-hexylaniline to synthesize 4, 4' -dihexylazobenzene, subsequently reacting N-bromosuccinimide, and reacting methylboronic acid in the presence of a Pd catalyst and a base.

[ chemical formula 6]

(reaction formula D)

In the above reaction formula D, the desired azobenzene derivative can be obtained by changing the raw material (p-hexylaniline and/or methylboronic acid) used to another compound.

The azobenzene derivative may be used alone or in combination of two or more.

(azomethine derivative)

The azomethine derivative (azomethine compound) preferably used as the isomerized low molecular weight compound is a compound having an aromatic hydrocarbon group or an aromatic heterocyclic group at each end of a C ═ N bond, and is a compound having cis-trans isomerization activation energy Ea of 60kJ/mol or more.

The activation energy of cis-trans isomerization is the difference between the total energy of the transition state represented by the following general formula (2) and the total energy of the cis form represented by the following general formula (3) in the photoresponsive compound represented by the following general formula (1).

[ chemical formula 7]

General formula (1)

[ chemical formula 8]

General formula (2)

General formula (3)

In the general formula (1), Z₁And Z₂Are each independently N or CH and Z₁≠Z₂A and B are each independently a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.

When the activation energy Ea of cis-trans isomerization is 60kJ/mol or more, the potential barrier for the isomerization reaction from the cis form to the trans form is sufficiently high, and after the cis form is isomerized by light irradiation, rapid return to the trans form can be suppressed, so that a fluidization phenomenon by light irradiation can be induced, and further, reversible non-fluidization can be realized.

The activation energy Ea is more preferably 63kJ/mol or more, still more preferably 64kJ/mol or more, and still more preferably 65kJ/mol or more. The activation energy Ea is preferably 100kJ/mol or less, more preferably 95kJ/mol or less, and still more preferably 90kJ/mol or less, from the viewpoint of easy return to the trans form.

Here, in order to calculate the molecular structure of the cis-isomer of the azomethine derivative and the total energy of the cis-isomer, and the molecular structure of the transition state and the total energy of the transition state, gaussian 16 (Reision B.01, M.J.Frisch, G.W.Trucks, H.B.Schlegel, G.E.Scuseria, M.A.Robb, J.R.Cheeseman, G.Schalmani, V.Barone, G.A.Petersson, H.Nakatsuji, X.Li, M.Caricato, A.V.Marenich, J.Blonio, B.G.Janesko, R.Goerts, B.Mennuucci, H.P.Hrathan, J.V.Ortiz, A.F.Izyl, J.L.Sonnenberg, D.Williams-Dieing, F.F.g, F.vrarini, A.Orientz, A.F.Izyl.J.S.F.J.S.S.J.S.S.S.D.C.S.S.J.S.S.J.S.E.S.S.S.S.J.S.S.S.S.J.S.S.S.J.S.S.S.S.S.S.S.J.J.J.S.S.S.J.S.J.S.S.S.S.S.S.H.J.J.S.S.S.S.J.J.S.J.J.H.S.H.H.S.S.S.S.S.S.S.S.S.S.J.J.S.S.S.S.S.J.J.J.J.H.S.S.S.J.S.J.H.H.S.S.S.S.S.S.S.S.S.S.S.S.H.H.J.J.S.S.S.J.S.S.J.J.S.S.S.S.H.H.H.S.H.H.H.J.H.S.S.H.H.S.S.H.H.H.S.S.S.S.S.S.S.J.H.H.H.S.S.H.J.S.S.S.S.S.S.S.S.S.J.J.J.S.H.S.S.S.S.S.S.H.H.H.H.H.S.S.S.S.S.S.S.S.S.S.S.C.H.S.S.S.S.S.H.S.S.S.H.H.H.H.H.S.H.H.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.H.S.S.S.S.S.S.S.H.H.H.S.S.S.S.S.S.S.S.S.S.S.S.H.H.S.S.S.S.S.H.H.H.S.S.S.S.H.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.H.H.S.H.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.H.H.H.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.. As the molecular structure of the cis-isomer, the most stable molecular structure of the isomer represented by the general formula (3), that is, the molecular structure having the lowest total energy was calculated, and the total energy was defined as the total energy of the cis-isomer. As the molecular structure of the Transition State (TS), the saddle point of the corresponding molecular structure is calculated for the transition state represented by the general formula (2), and the total energy obtained at that time is taken as the total energy of the transition state. Note that software or a calculation method is not particularly limited, and the same value can be obtained by using any of them. From the calculated values thus obtained, it is possible to obtain a value represented by the following formula (1): ea (kJ/mol) — (total energy of TS (kJ/mol)) - (total energy of cis (kJ/mol)) was calculated as a value of activation energy Ea.

By appropriately selecting the structures of A and B in the general formula (1), the activation energy Ea shown in the formula (1) can be controlled to 60kJ/mol or more.

Specifically, the activation energy Ea can be increased by introducing an electron donating structure into a compound having an azomethine moiety to increase the electron density of the azomethine moiety. For example, by using at least one of a and B as an aromatic heterocyclic group having a high electron donating property, the activation energy Ea can be increased. Further, the activation energy Ea can be increased by introducing a substituent having a high electron-donating property into the aromatic hydrocarbon group or aromatic heterocyclic group as a or B.

The aromatic hydrocarbon group is not particularly limited, and is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, or the like. Among them, phenyl is preferable because fluidization and non-fluidization efficiently occur.

The aromatic heterocyclic group is not particularly limited, and is preferably a group having 2 to 30 carbon atoms. Examples of the group having a high electron donating property include, but are not limited to, thienyl, pyrrolyl, furyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzothienyl, benzimidazolyl, indolyl, isoindolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, carbazolyl, and dibenzothienyl. In particular, a thienyl group, a pyrrolyl group, a furyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, and a carbazolyl group are preferable because the activation energy is high and fluidization and non-fluidization are efficiently caused.

The aromatic hydrocarbon group or the aromatic heterocyclic group may have a substituent, respectively. The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, a nitro group, an amino group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 10 carbon atoms, an acyl group having 2 to 19 carbon atoms, and an alkoxycarbonyl group having 2 to 19 carbon atoms. Preferably a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a dialkylamino group having 2 to 10 carbon atoms, an acyl group having 2 to 19 carbon atoms, and an alkoxycarbonyl group having 2 to 19 carbon atoms.

As described above, it can be considered that: like the azobenzene compound, the optical phase transition of the azomethine derivative occurs due to the disintegration of the crystal structure caused by cis-trans isomerization. In general, optical phase transition occurs only on the outermost surface of the crystal structure due to strong pi-pi interactions between molecules. Here, when the aromatic hydrocarbon group or aromatic heterocyclic group represented by a or B in the general formula (1) has a substituent, a specific crystal structure in which isotropically disturbed structures coexist is formed by thermal motion of the substituent in a periodic structure dominated by pi-pi interaction of the azomethine derivative. Therefore, when cis-trans isomerization reaction locally proceeds and pi-pi interaction at the azomethine site is weakened, dissolution occurs in a chain and isotropically in the entire system. Therefore, it is considered that cis-trans isomerization proceeds more easily and fluidization easily occurs.

Preferably, in the general formula (1), A and B are each independently a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aromatic heterocyclic group. By adopting the above-described configuration, fluidization and non-fluidization can be effectively generated.

Another preferred embodiment of the present invention is a compound represented by the general formula (1) above, wherein at least one of A and B is a phenyl group substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a dialkylamino group having 2 to 10 carbon atoms. In the compound, one of A and B is preferably a phenyl group substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a dialkylamino group having 2 to 10 carbon atoms, and the phenyl group is preferably a substituted or unsubstituted aromatic heterocyclic group. With the above configuration, the electron density of the azomethine moiety can be increased, the activation energy can be controlled, and fluidization and a reversible non-fluidization phenomenon can be effectively induced. In addition, phenomena such as the formation of lattice defects that contribute favorably to cis-trans isomerism, the expression of free volume, and the reduction of pi-pi interaction also occur. Therefore, it can be considered that: cis-trans isomerization proceeds more easily and fluidization appears more easily. The specific embodiments of the aromatic heterocyclic group and the substituents are the same as those described above.

In particular, it is preferable that in the general formula (1), at least one of A and B is relative to the Z₁Or Z₂A phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at the para-position of (A). It is considered that, due to this, the crystal is easily disintegrated, and fluidization due to light irradiation is more likely to occur.

In a preferred embodiment, it is a compound, which in the above general formula (1), at least one of A and B is chosen from among those mentioned with respect to Z₁Or Z₂The phenyl group in the para-position of (A) has an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and the other is a substituted or unsubstituted thienyl, pyrrolyl, pyrazolyl, furyl, imidazolyl or indolyl group. This makes it possible to achieve fluidization at a lower irradiation light intensity. In particular, when B is a substituted or unsubstituted thienyl, pyrrolyl, pyrazolyl, furyl, imidazolyl or indolyl group and Z is₁Is N, Z₂The above-mentioned effects can be more remarkably obtained when the compound is a CH compound.

As described above, it can be considered that: by setting the activation energy of photoisomerization to a prescribed range, an azomethine derivative as an isomerized low molecular compound can efficiently achieve fluidization and reversible non-fluidization. Further, in the above general formula (1), A, Z is appropriately selected₁、Z₂B, the size of the intermolecular interaction can be controlled, and the photofusibility can be controlled, whereby the effects of the present invention can be more remarkably obtained.

As shown in Table 1 below, A, Z can be appropriately selected from the general formula (1) as the azomethine derivative used in the present invention as an isomerized low molecular weight compound₁、Z₂And B to form compounds 1 to 5, 7 to 10.

[ tables 1-1]

TABLE 1-1

[ tables 1-2]

Tables 1 to 2

[ tables 1 to 3]

Tables 1 to 3

[ tables 1 to 4]

Tables 1 to 4

[ tables 1 to 5]

Tables 1 to 5

The method for synthesizing the azomethine derivative is not particularly limited, and conventionally known synthetic methods can be used. For example, if Z in the formula (1)₁Is N, Z₂For example, a compound wherein CH, A is 4-hexyloxyphenyl group and B is 5-methyl-2-thienyl group can be synthesized by the following scheme 1.

The intended azomethine compound was obtained by reacting 4- (hexyloxy) aniline and 5-methylthiophene-2-carbaldehyde in ethanol (EtOH) under heating and stirring, filtering the reaction solution, washing the resulting powder with cooled ethanol, and recrystallizing the washed powder with methanol/ethanol (see scheme 1 below). The temperature during heating and stirring is preferably in the range of 0 ℃ to 100 ℃, more preferably 30 ℃ to 70 ℃, and still more preferably 40 ℃ to 60 ℃.

[ chemical formula 9]

Scheme 1

Furthermore, for example, if Z is in the formula (1)₁Is N, Z₂For example, a compound wherein CH, A is a 4-hexyloxyphenyl group and B is an N-methyl-2-pyrrolyl group can be synthesized by the following scheme 2. In addition, for example, if Z is a group formed by reacting these compounds₁And Z₂Alternatively, the compound can be appropriately synthesized by referring to the above scheme 1 and the following scheme 2.

The target product, an azomethine compound, was obtained by reacting 4- (hexyloxy) aniline and N-methyl-pyrrole-2-carboxyformaldehyde in ethanol (EtOH) under heating and stirring, filtering the reaction solution, washing the resulting powder with ethanol, and recrystallizing the washed powder in methanol/ethanol (see scheme 2 below). The temperature during heating and stirring is preferably in the range of 0 ℃ to 100 ℃, more preferably 30 ℃ to 70 ℃, and still more preferably 40 ℃ to 60 ℃.

[ chemical formula 10]

Scheme 2

Other azomethine derivatives can be synthesized in the same manner by appropriately changing the starting materials with reference to schemes 1 and 2.

The above azomethine derivatives may be used alone or in combination of two or more.

[ isomerized Polymer ]

The isomerized polymer used in the composition of the present invention is a polymer which is fluidized by light irradiation and reversibly non-fluidized, and is not particularly limited as long as it has a structural unit containing an isomerized structure. In a preferred embodiment, the isomerized polymer has, as a repeating unit, a structural unit containing an isomerized structure. In a preferred embodiment, the isomerized polymer has a number average molecular weight of 1000 or more.

The isomerised polymer is preferably a molecular structure derived from a compound exhibiting photoisomerisation. For example, a molecular structure derived from a compound which exhibits a cis-trans isomerization reaction by light irradiation, and the like are mentioned. Examples of such a compound showing cis-trans isomerization by light irradiation include azobenzene derivatives and azomethine derivatives, and these compounds can be introduced into an isomerized polymer as the above-mentioned isomerized structure. That is, as the isomerized polymer in the composition of the present invention, a polymer containing a structural unit derived from an azobenzene derivative or a structural unit derived from an azomethine derivative may be used.

(Polymer containing a structural unit derived from an azobenzene derivative or a structural unit derived from an azomethine derivative)

The polymer containing a structural unit derived from an azobenzene derivative or a structural unit derived from an azobenzene derivative preferably has a group represented by any one of the following chemical formulae (i) to (iii) as a group having a polymerizable group. The following groups having a polymerizable group are preferably used because they are suitable for the synthesis of a block copolymer by living radical polymerization. Among these, from the viewpoint of easy softening and melting, a group having a polymerizable group of (ii) or (iii) is preferable, and a group having a polymerizable group of (iii) is more preferable.

[ chemical formula 11]

In formulae (i) to (iii), r₁Each independently and is a hydrogen atom or a methyl group. r is₂Each independently an alkylene group having 1 to 18 carbon atoms. Preferably r₂Is an alkylene group having 3 to 10 carbon atoms. The alkylene group may be linear or branched, and is preferably linear. A part of the above alkylene group may be substituted with a substituent. Examples of the substituent include a halogen group, a nitro group, a hydroxyl group, and a carboxyl group.

As the structural unit derived from the azobenzene derivative, a structural unit having a phenylene group having a linking portion to be linked to a polymer main chain at a position para to a nitrogen-nitrogen double bond is preferably used. By introducing the substituent into the para position of the nitrogen-nitrogen double bond, the crystal is easily disintegrated and easily photoisomerized, and can be melted or softened by irradiation with light having a lower energy. More preferably, the compound R represented by the formula (1) is the isomerized low molecular weight compound₃A structure substituted with a group having a polymerizable group represented by any one of the above formulae (i) to (iii). In the formula (1), R₁、R₂、R₄～R₁₀The preferred form of (2) is the same as the compound of formula (1) which is an isomerized low molecular compound.

In this case, it is preferable to use, as the isomerized polymer, a polymer containing a structural unit derived from an azobenzene derivative containing a phenylene group having a linking moiety to a polymer main chain at a position para to a nitrogen-nitrogen double bond, and it is preferable to use, as the isomerized low molecular weight compound, an azobenzene derivative or an azobenzene derivative having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at a position para to a nitrogen-nitrogen double bond or a nitrogen-carbon double bond. In this way, the crystal is easily disintegrated, and the effect of improving the optical fusibility can be more remarkably obtained. Therefore, fluidization due to light irradiation can be performed more efficiently.

In the polymer used in the present invention, the structural unit derived from the azomethine derivative preferably has the following structure: in the polymer represented by the following general formula (1a), A preferably has the following structure: the activation energy Ea of the compound represented by the following formula (1a) in which a hydrogen atom is bonded to A is 60kJ/mol or more instead of the oxygen atom bonded to A represented by the general formula (2 a).

[ chemical formula 12]

General formula (1a)

In the general formula (1a), r₁Represents a hydrogen atom or a methyl group,

a is a group having an azomethine structure represented by the following general formula (2 a);

[ chemical formula 13]

General formula (2a)

In the general formula (2a), Z₁And Z₂Are each independently N or CH and Z₁≠Z₂，

B₁Is a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent aromatic heterocyclic group,

B₂is a substituted or unsubstituted monovalent aromatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group,

r₂is an alkylene group having 1 to 18 carbon atoms.

Formula (1 a): ea (kJ/mol) (Total energy of TS (kJ/mol)) - (Total energy of cis form (kJ/mol))

In the formula (1a), TS represents a transition state represented by the general formula (3a), and cis represents an isomer represented by the general formula (4 a).

[ chemical formula 14]

General formula (3a)

General formula (4a)

When the potential barrier (activation energy Ea) in the isomerization reaction from the cis form to the trans form of the compound having a structure represented by the general formula (2a) to which a hydrogen atom is bonded is 60kJ/mol or more, the reaction rate of the isomerization reaction from the cis form to the trans form decreases, the amount of the cis form increases upon light irradiation, and fluidization due to the photoisomerization reaction can be induced more effectively.

Further, it is considered that intermolecular stacking (pi-pi interaction) is exhibited in the methylimino moiety, and since higher thermal mobility is exhibited when isomerization from a trans form to a cis form is performed, strength as a material is improved and a fluidization phenomenon is easily induced.

The activation energy Ea is preferably 63kJ/mol or more, more preferably 65kJ/mol or more, and still more preferably 67kJ/mol or more. Further, the activation energy Ea is preferably 100kJ/mol or less, more preferably 95kJ/mol or less, and still more preferably 90kJ/mol or less, from the viewpoint of easy recovery to the trans form. In this way, the above-described effects can be more easily obtained.

When the activation energy Ea of the formula (1a) is calculated, the transition state structure can be represented by the general formula (3a) and the cis-form structure can be represented by the general formula (4a), respectively, and the general formulae (3a) and (4a) represent B₁And B₂Relative to Z₁＝Z₂Configuration (position) of the key H, r₂-H、O-r₂The position of the moiety of-H depends on having a moiety containing B₁Structure of group a of the structure of the methylimino structure.

In order to calculate the molecular structure and total energy of the cis-form of the compound and the molecular structure and total energy of the transition state, Gaussian 16 software manufactured by Gaussian company, USA, and a density functional method (B3LYP/6-31G (d)) can be used as a calculation method. As the molecular structure of the cis-isomer, the most stable molecular structure of the isomers represented by the general formula (4a), that is, the molecular structure having the lowest total energy was calculated, and the total energy was defined as the total energy of the cis-isomer. As the molecular structure of the transition state, saddle points of the corresponding molecular structure are calculated for the transition state represented by the general formula (3a), and the total energy obtained at that time is taken as the total energy of the transition state. In addition, software or a calculation method is not particularly limited, and the same value can be obtained by using any of them. From the calculated values thus obtained, the value of the activation energy Ea can be obtained by the formula (1 a).

By appropriate selection of Z in the above general formula (1a)₁、Z₂、B₁And B₂The structure of (3) can control the activation energy Ea shown in the formula (1a) to 60kJ/mol or more.

Specifically, the electron density of the azomethine moiety can be increased by introducing an electron donating structure into the group a having an azomethine structure, thereby increasing the activation energy Ea. For example, by mixing B₁And B₂At least one of them is an aromatic heterocyclic group having a high electron donating property, whereby the activation energy Ea can be increased. Furthermore, the molecular orientation is B₁And B₂The aromatic hydrocarbon group or aromatic heterocyclic group of (2) can be increased in the activation energy Ea by introducing a substituent having a high electron-donating property.

Here, preferred embodiments of the aromatic hydrocarbon group and the aromatic heterocyclic group and examples of the substituent group that can be introduced into the aromatic hydrocarbon group and the aromatic heterocyclic group are the same as those of the above-described azomethine derivative which is an isomerized low molecular weight compound.

In the structural unit represented by the general formula (1a), one polymerizable group is present for one group having the azomethine moiety. Thus, a polymer which is easily melted can be easily obtained even with a low irradiation energy.

The group having a polymerizable group in the monomer constituting the structural unit in the general formula (1a) preferably has a group represented by any one of the above (i) to (iii). The polymer having a group having such a polymerizable group corresponds to a polymer in which A in the general formula (1a) is represented by the general formulae (2a-a), (2a-b), and (2a-c), respectively.

The polymer represented by the above general formula (1a) is not particularly limited, and it can be produced by an arbitrary method, for example, by polymerizing a monomer represented by the following formula (i-2), (ii-2), or (iii-2), whereby a in the above general formula (1a) can be obtained as a polymer represented by the above general formula (2a-a), (2a-b), or (2a-c), respectively. In the following formulae (i-2), (ii-2), and (iii-2), Z₁、Z₂、B₁And B₂R is the same as the above general formula (1a)₁And r₂The same as in the above general formula (1a) and the above (i), (ii) and (iii). That is, in one embodiment of the present invention, the polymer contains a structural unit derived from an azomethine derivative having a polymerizable group represented by the following formulae (i-2), (ii-2), and (iii-2).

[ chemical formula 14-2]

In a preferred embodiment, in said general formula (1a), B₁Is in relation to Z₁Is bonded to an oxygen atom ((2a-a) or (2 a-c)) or r₂A phenylene group at (2 a-b). That is, a preferred embodiment of the structural unit derived from the azomethine derivative is a phenylene group having a linking moiety to the polymer main chain at a position para to the carbon-nitrogen double bond. It can be considered that: thus, the crystal is easily disintegrated and light irradiation is more easily causedThe fluidization is realized.

In this case, it is preferable to use, as the isomerized polymer, a polymer containing a structural unit derived from an azomethine derivative having a phenylene group having a part of a linkage to a polymer main chain at a para position relative to a carbon-nitrogen double bond, and it is preferable to use, as the isomerized low molecular compound, an azobenzene derivative or an azomethine derivative having a phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at a para position relative to a nitrogen-nitrogen double bond or a carbon-nitrogen double bond. In this way, the crystal is easily disintegrated, and the effect of improving the optical fusibility can be more remarkably obtained. Therefore, fluidization due to light irradiation can be performed more efficiently.

Other preferred embodiments of the present invention are: a polymer represented by the general formula (1a) above, wherein B is₁Is in relation to Z₁Para to the oxygen atom ((2a-a) or (2 a-c)) or₂(ii) bonded phenylene group of (2a-B), B₂The heterocyclic group is an unsubstituted aromatic heterocyclic group or an aromatic heterocyclic group substituted by any one of a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a dialkylamino group having 2 to 10 carbon atoms, an acyl group having 2 to 19 carbon atoms or an alkoxycarbonyl group having 2 to 19 carbon atoms.

With the above configuration, the electron density of the azomethine moiety can be increased, and fluidization and a reversible non-fluidization phenomenon due to light irradiation can be effectively induced. In addition, there may occur: the generation of lattice defects that exert a favorable effect on cis-trans isomerization, the expression of free volume, and the reduction of pi-pi interactions, and the like. Therefore, it can be considered that: cis-trans isomerization proceeds more easily and shows fluidization more easily.

Here, in B₁Is phenylene, B₂In the present embodiment, Z is preferably an aromatic heterocyclic group₁Is N, Z₂Is CH. In this embodiment, B is defined as₂The aromatic heterocyclic group of (A) is preferably a substituted or unsubstituted thienyl, pyrrolyl, pyrazolyl, furylImidazolyl or indolyl, particularly preferably substituted or unsubstituted thienyl, furyl, pyrazolyl or pyrrolyl.

In addition, in the polymer, the structural unit represented by the general formula (1a) may be one kind, or two or more kinds may be used in combination.

Specific examples of the structural unit represented by the general formula (1a) include structural units 1 to 4, 6, 7 and 18 shown in the following table 2.

[ Table 2-1]

(structural units contained in Polymer)

(Structure of group A having an azomethine Structure)

(B₁-Z₁＝Z₂-B₂Of (2)

TABLE 2-1

[ tables 2-2]

(B₁-Z₁＝Z₂-B₂Of (2)

Tables 2 to 2

[ tables 2 to 3]

(B₁-Z₁＝Z₂-B₂Is connected withStructure)

Tables 2 to 3

[ tables 2 to 4]

(B₁-Z₁＝Z₂-B₂Of (2)

Tables 2 to 4

[ tables 2 to 5]

(B₁-Z₁＝Z₂-B₂Of (2)

Tables 2 to 5

[ tables 2 to 6]

(B₁-Z₁＝Z₂-B₂Of (2)

Tables 2 to 6

< method for producing azobenzene derivative having polymerizable group or azomethine derivative having polymerizable group >

The method for producing the azobenzene derivative having a polymerizable group or the azomethine derivative having a polymerizable group is not particularly limited, and for example, the desired azobenzene derivative or azomethine derivative may be prepared first, and the resulting azobenzene derivative or azomethine derivative may be introduced with a group having a polymerizable group. An example of a method for producing the azomethine derivative having a polymerizable group is described below. Even azobenzene derivatives having a polymerizable group can be suitably produced by referring to the following scheme.

For example, in the case of producing an azomethine derivative having a thiophene ring, as a first step, an aniline derivative is reacted with a thiophene carboxy formaldehyde derivative which is a compound having a thiophene ring. In this case, when any one of the aniline derivative and the thiophenecarboxaldehyde derivative as the raw material has an OH group as a substituent, the polymerizable group can be easily introduced to the position of the OH group.

For example, if the azomethine derivative is Z of the above general formula (1a)₁Is N, Z₂Is CH, X is S, B₁Is a phenylene group into which a group Z is introduced₁A group having a polymerizable group at the para-position of (A), B₂Is 2-methylthiophenyl and is bonded to Z in the 5 position₂In this case, the intermediate a can be obtained by the following reaction formula.

Specifically, the desired target substance can be obtained by treating 4-hydroxyaniline and 5-methylthiophene-2-carbaldehyde (which is heated under reflux and allowed to react) in a solvent such as ethanol (EtOH) or methanol (MeOH), filtering the reaction solution, washing the resulting powder with cooled ethanol, and recrystallizing the powder with methanol/ethanol).

[ chemical formula 15]

Subsequently, as a second stage, a polymerizable group is introduced into the intermediate a. The method for introducing the polymerizable group is not particularly limited. For example, a connecting bond-C is introduced into the intermediate A₆H₁₂When, for example, Cl-C₆H₁₂the-OH group functions as a halohydrin compound, thereby obtaining the following intermediate B.

The reaction conditions are not particularly limited, and for example, the reaction is carried out in a solvent such as Dimethylformamide (DMF) in the presence of potassium carbonate and potassium iodide, preferably at 0 ℃ to 100 ℃, more preferably at 0 ℃ to 60 ℃, and still more preferably at 0 ℃ to 40 ℃.

[ chemical formula 16]

Subsequently, as a third stage, the intermediate B is reacted with a compound for constituting a group having a polymerizable group, for example, acrylic acid chloride or methacrylic acid chloride. The reaction conditions are not particularly limited. For example, the reaction is preferably carried out in a known organic solvent in the presence of a tertiary amine such as triethylamine or triethanolamine. Preferably, the mixture liquid containing the intermediate B, the tertiary amine and the solvent is maintained at 0 to 10 ℃, and a compound constituting a group having a polymerizable group, such as acrylic chloride or methacrylic chloride, is dropped into the mixture liquid and mixed. Subsequently, the mixed solution is reacted at room temperature for 5 to 10 hours, for example, to obtain an azomethine derivative having a polymerizable group.

[ Compound 17]

In addition, in the first stage, the method is carried out byThe starting materials of (a) are changed to other compounds, so that an azomethine derivative having a desired substituent can be obtained. For example, an azomethine derivative in which Z of the general formula (1a) is represented by₁Is CH, Z₂Is N, B₁Is phenylene, B₂Is thienyl. B can be obtained by using another aromatic hydrocarbon compound or an aromatic heterocyclic compound (formaldehyde derivative) as a raw material instead of the compound having a thiophene ring (thiophene formaldehyde derivative)₂Azomethine derivatives having different structures. Similarly, B can be obtained by changing the aniline derivative as a raw material to another aromatic hydrocarbon compound or aromatic heterocyclic compound having an amino group₁Azomethine derivatives having different structures.

Further, by changing the compound added in the second stage and the third stage, a group having a polymerizable group with a different structure can be introduced. The skilled person can synthesize a azomethine derivative having a desired polymerizable group by appropriately modifying the above and selecting appropriate reaction conditions.

In addition, by appropriately selecting the raw materials used in the first stage, a group having a polymerizable group can be introduced into the intermediate a without performing the second stage.

< structural units other than the structural unit containing an isomerized structure >

The polymer used in the present invention may contain a structural unit (other structural unit) other than the structural unit containing the isomerized structure. In the case of a copolymer containing other structural units, the arrangement form of the repeating units of the copolymer is not particularly limited, and it may be any of a random copolymer, a block copolymer and an alternating copolymer.

The other structural unit is not particularly limited as long as it is a structural unit containing no isomerized structure, and is more preferably a structural unit constituting a thermoplastic resin softened by heating.

The other structural unit is preferably a structural unit having an ethylene polymerizable group, from the viewpoint of ease of synthesis of the copolymer. Specifically, for example, a styrene derivative, a (meth) acrylic acid derivative, an olefin derivative, a vinyl ester derivative, a vinyl ether derivative, a vinyl ketone derivative, or the like can be used, and a structural unit derived from a styrene derivative, a (meth) acrylic acid derivative, or an olefin derivative is preferable.

Examples of the styrene derivative include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α -methylstyrene, p-phenylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, p-t-butylstyrene, p-n-hexylstyrene, n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, and p-n-dodecylstyrene.

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

Examples of the olefin derivatives include ethylene, propylene, n-butene, isobutylene, n-pentene, 3-methyl-1-pentene and the like. The olefin derivative may be linear or branched, and the number of carbon chains is not particularly limited.

Examples of the vinyl ester derivative include vinyl propionate, vinyl acetate, and vinyl benzoate. Examples of the vinyl ether derivative include vinyl methyl ether and vinyl ethyl ether. Examples of the vinyl ketone derivative include vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone.

The content of the other structural units in the polymer is not particularly limited and may be appropriately selected, and is preferably 70% by mass or less, more preferably 40% by mass or less, based on 100% by mass of the total of all the structural units constituting the polymer.

The number average molecular weight Mn of the polymer is not particularly limited, but is preferably 1000 or more, more preferably 3500 or more, further preferably 3500 to 100000, further preferably 3500 to 70000, further preferably 3500 to 50000, and particularly preferably 5000 to 50000. The number average molecular weight is preferably 3500 or more because the polymer has excellent toughness and can more easily obtain a toner image having excellent fixability when used as a toner. Further, a number average molecular weight of 100000 or less is preferable because the efficiency of isomerization and softening and melting becomes high.

The number average molecular weight of the polymer can be measured by Gel Permeation Chromatography (GPC). Specifically, the measurement can be performed by the method described in the examples described later.

< method for producing Polymer >

The method for synthesizing the polymer is not particularly limited, and a method of polymerizing a monomer such as a azobenzene derivative or a azoimine derivative having the above-mentioned polymerizable group can be obtained by using a known polymerization initiator such as anion polymerization, cation polymerization, or living radical polymerization. If necessary, a known chain transfer agent may be used.

As the polymerization initiator, for example, azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators shown below can be used.

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

Examples of the peroxide-based polymerization initiator include dibenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, 4-dichloroperoxybenzoyl, lauroyl peroxide, 2-bis- (4, 4-t-butylperoxycyclohexyl) propane, and tri- (t-butylperoxy) triazine.

Examples of the chain transfer agent include benzyl dithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenyltri-2-yldithiocarbonate, 1-acetoxyethyldithiobenzoate, hexa (thiobenzoylthiomethyl) benzene, 1, 4-bis (thiobenzoylthiomethyl) benzene, 1,2,4, 5-tetrakis (thiobenzoylthiomethyl) benzene, 1, 4-bis- (2- (thiobenzoylthio) tri-2-yl) benzene, 1- (4-methoxyphenyl) ethyldithiobenzoate, benzyldithioacetate; ethoxycarbonylmethyldithioacetate, 2- (ethoxycarbonyl) tri-2-yldithiocarbonate, 2-cyanotri-2-yldithiocarbonate, t-butyldithiobenzoate, 2,4, 4-trimethylpenta-2-yldithiocarbonate, 2- (4-chlorophenyl) tri-2-yldithiocarbonate, 3-vinylbenzyldithiobenzoate and 4-vinylbenzyldithiobenzoate, S-benzyldiethoxyphosphinyldithiocarbonate, t-butyltrithioperbenzoate, 2-phenyltri-2-yl-4-chlorodithiobenzoate, 2-phenyltri-2-yl-1-dithionaphthalate, di-or tri-thionaphthalate, di-or tri-thiobenzoate, di-or tri-2-yl-2-4-chlorodithiobenzoate, di-or tri-2-yl-1-dithionaphthalate, di-or tri-2-yl-or tri-2-vinyldithiobenzoate, di-or tri-2-yl-2-dithiobenzoate, di-or tri-thiobenzoate, or tri-2-thiobenzoate, or a, 4-cyanovaleric acid dithiobenzoate, dibenzyl tetrathioterephthalate, dibenzyl trithiocarbonate, carboxymethyl dithiobenzoate, etc. The polymerization temperature varies depending on the kind of the monomer and the polymerization initiator used, and is preferably 50 to 100 ℃ and more preferably 55 to 90 ℃. The polymerization time varies depending on the kind of the monomer and the polymerization initiator used, and is preferably 2 to 60 hours, for example.

Further, the method for producing the copolymer containing a structural unit other than the structural unit containing the isomerized structure (other structural unit) is not particularly limited.

For example, in the case of producing a random copolymer, as a raw material monomer, in addition to a monomer for constituting a structural unit containing an isomerized structure, a monomer for constituting the other structural unit described above may be mixed with a chain transfer agent, a polymerization initiator, or the like and subjected to a polymerization reaction to obtain a desired copolymer. The specific form of the monomer for constituting the other structural unit is as described above.

One preferable embodiment of the polymer used in the composition of the present invention is a polymer (block copolymer) represented by the following general formula (5).

[ chemical formula 18]

General formula (5)

In the above general formula (5), α is a polymer block containing a structural unit having an isomerized structure, and β is a polymer block containing no structural unit having an isomerized structure.

The heat energy released from the isomerized structure during photoexcitation/inactivation is conducted to the bonded repeating units (structural units) by high molecular weight polymerization, thereby enabling melting or softening in the polymer. Further, it can be considered that: by forming a block copolymer, portions of the isomerized structures tend to form domains within the polymer, more effectively inducing softening/melting. Therefore, the effects of the present invention can be obtained more remarkably.

From the viewpoint of ease of softening and melting of the block copolymer structure and image strength when used as a toner, the block copolymer structure of α - β - α (may be expressed as 2 α - β) or β - α - β (may be expressed as 2 β - α) is preferable, and the block copolymer structure of α - β - α is more preferable.

The specific form of the structural unit constituting the copolymer block α and containing an isomerized structure is as described above.

The structural units constituting the copolymer block beta are free of isomerization structures. Specifically, the embodiments described as the other constituent units can be preferably used. In particular, a structural unit having an ethylene-based polymerizable group is preferable from the viewpoint of being suitable for synthesizing a copolymer by a living radical polymerization method such as an ATRP method, ARGET-ATRP method, or RAFT method. Specific examples thereof include styrene derivatives, (meth) acrylic acid derivatives, olefin derivatives, vinyl ester derivatives, vinyl ether derivatives, vinyl ketone derivatives, etc., and styrene derivatives, (meth) acrylic acid derivatives, or olefin derivatives are preferable. The specific forms of these substances are the same as those described above.

The number average molecular weight (total number average molecular weight) of the polymer block α contained in the polymer represented by the general formula (5) is not particularly limited, but is preferably 1000 or more, more preferably 1000 to 100000, still more preferably 1000 to 70000, yet still more preferably 1000 to 50000, and particularly preferably 3000 to 50000. When the total number average molecular weight of the polymer block α is 1000 or more, a toner image having excellent fixability can be more easily obtained when used as a toner, and therefore, the total number average molecular weight is preferable. Further, it is preferable that the number average molecular weight of the polymer block α is 100000 or less because the efficiency of softening and melting increases. Here, the number average molecular weight of the polymer block α means the number average molecular weight of the polymer block α when the polymer represented by the general formula (5) contains a single polymer block α, and means the sum of the number average molecular weights of the polymer blocks α when the polymer represented by the general formula (5) contains a plurality of polymer blocks α.

The number average molecular weight (total number average molecular weight) of the polymer block β contained in the polymer represented by the general formula (5) is not particularly limited, but is preferably 1000 or more, more preferably 1000 to 100000, still more preferably 1000 to 70000, yet still more preferably 1000 to 50000, and particularly preferably 3000 to 50000. The total number average molecular weight of the polymer blocks β is 1000 or more, and therefore, a toner image having excellent fixing properties can be more easily obtained when the toner is used. Further, it is preferable that the number average molecular weight of the polymer block β is 100000 or less because the efficiency of softening and melting becomes high. Here, the total number average molecular weight of the polymer block β means the number average molecular weight of the polymer block β when the polymer represented by the general formula (5) contains a single polymer block β, and means the sum of the number average molecular weights of the polymer blocks β when the polymer represented by the general formula (5) contains a plurality of polymer blocks β.

The total number average molecular weight Mn of the polymer represented by the general formula (5) is preferably 3500 or more, more preferably 3500 to 100000, still more preferably 3500 to 70000, still more preferably 3500 to 50000, and particularly preferably 5000 to 50000. The total number average molecular weight of the polymer represented by the general formula (5) is preferably 3500 or more, since a toner image having excellent fixing properties can be more easily obtained when the polymer is used as a toner. Further, the total number-average molecular weight is preferably 100000 or less because the efficiency of softening and melting becomes high.

Therefore, according to a preferred embodiment of the present invention, the total number average molecular weight of the polymer blocks α contained in the polymer represented by the general formula (5) is 1000 or more, the total number average molecular weight of the polymer blocks β is 1000 or more, and the total number average molecular weight Mn of the polymer represented by the general formula (5) is 3500 or more.

In the polymer represented by the general formula (5), the ratio of the total number average molecular weight of the polymer block α to the total number average molecular weight of the polymer block β is not particularly limited, and the ratio of the total number average molecular weight of the polymer block α to the total number average molecular weight of the polymer block β is preferably 1:20 to 20:1, more preferably 1:15 to 15:1, from the viewpoints of easy softening and melting and image strength.

The total number average molecular weight of the polymer represented by the general formula (5), the total number average molecular weight of the polymer block α and the polymer block β can be measured by Gel Permeation Chromatography (GPC). Specifically, the measurement can be performed by the method described in the examples described later.

The method for synthesizing the block copolymer represented by the general formula (5) is not particularly limited, and known methods such as anionic polymerization, cationic polymerization, living radical polymerization and the like can be used. In particular, as a simple synthesis method, a living radical polymerization method such as an atom transfer radical polymerization method (ATRP method), ARGET-ATRP method, RAFT method, or the like is preferably used.

Taking the ATRP method as an example, the following can be mentioned: the initiator is synthesized by a method of polymerizing a monomer as a structural unit of the polymer block α or β in the presence of a catalyst using a compound containing a monofunctional, bifunctional, trifunctional or tetrafunctional halogen element as a starting material.

In the stage of polymerizing the monomers, for example, the monomers that are structural units of either the polymer block α or β (block that is the core of the block copolymer) are polymerized in the presence of an initiator, a catalyst, and a ligand to prepare a macroinitiator.

Examples of the initiator include, but are not limited to, butyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, ethylene bis (ethyl 2-bromoisobutyrate), 1,1, 1-tris (2-bromoisobutyryloxymethyl) ethane, pentaerythritol tetraalkyl (ethyl 2-bromoisobutyrate), α' -dibromo-p-xylene, ethyl bromoacetate, 2-bromoisobutyryl bromide, and a mixture thereof.

Examples of the catalyst include a copper (I) catalyst and an iron (ii) catalyst, and examples thereof include Cu (I) Cl, Cu (I) Br, Fe (ii) Cl, Fe (ii) Br, and a mixture thereof.

As the ligand, a known ligand can be used, and preferably, at least one selected from the group consisting of 2,2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 4' -tert-butyl-2, 2 '-bipyridine, 1,4,7,10, 10-hexamethyltriethylenetetramine, N', N "-pentamethyldiethylenetriamine, cycloalkane (1,4,8, 11-tetraazacyclotetradecane), 1,4,8, 11-tetramethylcycloalkane (1,4,8, 11-tetramethyl-1, 4,8, 11-tetraazacyclotetradecane), and tris [2- (dimethylamino) ethyl ] amine is used.

The amount of the catalyst and the ligand used is not particularly limited, and may be determined as appropriate by a conventionally known method.

Next, the macroinitiator obtained by the above polymerization is isolated and used as an initiator, and monomers not used for synthesizing the macroinitiator among monomers constituting the structural unit of the polymer block α or β are polymerized again in the presence of a catalyst and a ligand. Alternatively, monomers not used for synthesizing the macroinitiator may be directly added to continue the polymerization without isolating the macroinitiator at a stage where almost all of the monomers have been consumed in the process of synthesizing the macroinitiator. By this operation, a desired block copolymer can be obtained.

The above-mentioned reactions are preferably carried out in an inert gas atmosphere of a rare gas such as nitrogen or argon. The above-mentioned reactions can be carried out at a temperature of, for example, 25 to 160 ℃ and preferably 35 to 130 ℃. The above-mentioned reactions may be carried out without using a solvent, or may be carried out in an organic solvent or the like.

In the reaction of polymerizing a monomer constituting a structural unit of either one of the polymer blocks α and β to obtain a macroinitiator and the reaction of reacting the macroinitiator with a monomer constituting a structural unit of the other polymer block to obtain a block copolymer, the kind and amount of the catalyst and ligand used and the conditions such as the temperature during the reaction may be the same or different.

[ mixing ratio of isomerized polymer to isomerized Low-molecular Compound ]

In the composition of the present invention, the mixing ratio of the isomerized polymer to the isomerized low-molecular compound is not particularly limited, and is preferably in the range of 99:1 to 10:99 in terms of the mass ratio. When the isomerized polymer is 99 mass% or less with respect to 100 mass% of the total amount of the isomerized polymer and the isomerized low-molecular compound, the effect of suppressing the light irradiation amount required for fluidization is excellent. Further, when the content is 10% by mass or more, a composition having excellent adhesiveness can be more easily obtained. In particular, the ratio of the isomerized polymer to the isomerized low-molecular-weight compound is more preferably 40:60 to 80:20, and still more preferably 40:60 to 80: 20.

The composition of the present invention may contain components other than the isomerized polymer and the isomerized low-molecular compound. The specific form and content of the components other than the isomerized polymer and the isomerized low-molecular compound are not particularly limited as long as the composition can be fluidized from a solid state by light irradiation and can be reversibly non-fluidized.

In one embodiment, the total amount of the isomerized polymer and the isomerized low-molecular compound is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more, of the total composition. The composition provided in the present embodiment can be used as an adhesive directly or by adding an appropriate amount of any known additive. Similarly, the composition provided in this embodiment can be used as an optical switching material directly or by adding an appropriate amount of any known additive. As described later, a toner can be prepared by using the composition provided in the present embodiment and further using a binder resin, a colorant, and the like as needed.

[ combination of isomerized Polymer with isomerized Low molecular Compound ]

As the isomerized polymer and the isomerized low-molecular compound that can be used in the composition of the present invention, a polymer and a compound that are fluidized by light irradiation and reversibly fluidized can be used in combination as appropriate. However, particularly when used in a toner, it is preferable to use a polymer containing a structural unit derived from an azomethine derivative in combination with an azomethine compound.

Among them, it is preferable to use a polymer containing a structural unit derived from an azomethine derivative, wherein the polymer containing a structural unit derived from an azomethine derivative contains a phenylene group having a linking moiety to a polymer main chain at a position para to a carbon-nitrogen double bond, and the azomethine compound contains a phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at a position para to a carbon-nitrogen double bond, in combination with an azomethine compound. This enables fluidization by light irradiation to be more effectively performed.

In addition, it is preferable that any one of the structural unit derived from the azomethine derivative and the azomethine compound in the polymer contains a thiophene ring or a pyrrole ring. This enables fluidization by light irradiation to be more effectively performed.

[ method for producing composition ]

The method for preparing the composition of the present invention is not particularly limited. For example, a method of preparing an isomerized polymer and an isomerized low-molecular compound separately, dissolving the isomerized polymer and the isomerized low-molecular compound in a solvent capable of dissolving them at a desired mixing ratio, and then removing the solvent to dry and solidify the resulting mixture may be mentioned.

< fluidization and reversible non-fluidization by light irradiation >

The wavelength of the irradiation light when fluidizing the composition of the present invention by light irradiation is preferably in the range of 280nm to 480nm, more preferably in the range of 300nm to 420nm, and still more preferably in the range of 330nm to 420 nm. When the amount is within the above range, the crystals are liable to collapse (good light-melting property), and the fixing property is improved. In addition, when fluidizing the particles, heat or pressure may be applied in addition to the light irradiation to promote the fluidization. By irradiating the irradiation light of the above wavelength, fluidization can be performed with less heat or pressure even when heat or pressure is applied. Therefore, by introducing the composition of the present invention into a toner, fixation at the above-mentioned wavelength can be achieved, and a toner having excellent fixability and high color reproducibility can be obtained.

In addition, a part of visible light is included in the above wavelength range. Therefore, the composition of the present invention is preferably not fluidized when it receives only light from illumination such as sunlight (natural light) or fluorescent light, and is preferably further fluidized at low cost while the irradiation amount and irradiation time are suppressed as much as possible. From the above-mentioned viewpoint, the irradiation amount of the irradiation light for fluidizing the composition may be, for example, 0.1J/cm²Above and 200J/cm²In the following range, 0.1J/cm is preferable²Above and 100J/cm²More preferably 0.1J/cm in the following range²Above and 50J/cm²More preferably 0.1J/cm in the following range²Above and 30J/cm²Within the following ranges.

In fluidizing the composition, the composition may be irradiated with light and heated. This makes it possible to fluidize the material with a low irradiation dose. The heating temperature in this case may be, for example, 20 ℃ to 200 ℃, and preferably 20 ℃ to 150 ℃.

On the other hand, the conditions for non-fluidizing (re-curing) the composition of the present invention are preferably left at room temperature (in the range of 25. + -. 15 ℃), heated or irradiated with visible light. The wavelength of visible light and irradiation conditions when the composition of the present invention is non-fluidized by irradiation with visible light are not particularly limited, and light having a wavelength longer than that of irradiation light when the composition of the present invention is fluidized is preferable.

When the composition is heated to be non-fluidized, the heating temperature is preferably in the range of 0 ℃ to 200 ℃, more preferably in the range of 20 ℃ to 150 ℃, and still more preferably in the range of 20 ℃ to 140 ℃.

[ Structure of toner ]

One embodiment of the present invention is: a toner comprising the composition of the present invention. By introducing the composition of the present invention into a toner, the toner can be fixed by light irradiation with less energy, and a toner having excellent fixability can be obtained. Further, the toner refers to toner base particles or an aggregate of toner particles. The toner particles are preferably toners in which an external additive is added to the toner matrix particles, but the toner matrix particles may be used as the toner particles as they are. In the present invention, when there is no particular need to distinguish between the toner base particles, the toner particles, and the toner, they are simply referred to as "toner".

The content of the composition in the toner varies depending on the types of the isomerized polymer and the isomerized low-molecular compound, but from the viewpoint of achieving effective fluidization and image strength, the total amount of the isomerized polymer and the isomerized low-molecular compound is preferably in the range of 5 to 95 mass% with respect to the total amount of the binder resin, the colorant, the release agent, the isomerized polymer, and the isomerized low-molecular compound constituting the toner.

When the composition of the present invention is used for a toner, the isomerized polymer is preferably a polymer containing a structural unit derived from an azomethine derivative, and the isomerized low-molecular compound is preferably an azomethine derivative. Since the azomethine derivative is not significantly colored, a toner having a high color reproducibility of the colorant can be obtained.

< adhesive resin >

The toner of the present invention may further contain a binder resin. The binder resin is a resin having no structure derived from an isomerized structure or a structure derived from an isomerized low-molecular compound, and a resin generally used as a binder resin constituting a toner can be used without limitation. As the adhesive resin, for example, a styrene resin, an acrylic resin, a styrene acrylic resin, a polyester resin, a silicone resin, an olefin resin, an amide resin, an epoxy resin, or the like can be used. These binder resins may be used alone or in combination of two or more.

Among the above resins, the adhesive resin preferably contains at least one selected from the group consisting of styrene resins, acrylic resins, styrene acrylic resins, and polyester resins, and more preferably contains at least one selected from the group consisting of styrene acrylic resins and polyester resins, particularly from the viewpoint that the adhesive resin has a low viscosity after melting and has a high clear melting point.

(styrene acrylic resin)

The styrene acrylic resin in the present invention is a polymer containing at least a structure derived from a styrene monomer and a structural unit derived from a (meth) acrylate monomer. Here, the styrene monomer is represented by the formula CH₂＝CH-C₆H₅The term "styrene monomer" refers to a structure having a known side chain or functional group in the styrene structure, in addition to styrene monomers.

Examples of the styrene monomer include the same monomers as the styrene monomer that can constitute the polymer.

The (meth) acrylate monomer is a monomer having a functional group containing an ester bond in a side chain. Specifically, except from CH₂The acrylic acid ester monomer represented by ═ CHCOOR (R is an alkyl group) may further contain CH₂＝C(CH₃) And (C) a methacrylate monomer represented by COOR (R is an alkyl group). In addition, (meth) acrylic acid in the (meth) acrylate monomer means acrylic acid and methacrylic acid.

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

The styrene monomer and the (meth) acrylate monomer may be used alone or in combination of two or more.

The content of the structural unit derived from a styrene monomer and the content of the structural unit derived from a (meth) acrylate monomer in the styrene acrylic resin are not particularly limited, and are appropriately adjusted from the viewpoint of controlling the softening point and the glass transition temperature of the adhesive resin. Specifically, the content of the structural unit derived from a styrene monomer is preferably 40 to 95% by mass, and more preferably 50 to 90% by mass, based on the total structural units constituting the styrene acrylic resin. The content of the structural unit derived from the (meth) acrylate monomer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total structural units constituting the styrene acrylic resin.

The styrene acrylic resin may further contain a structural unit derived from a monomer other than the styrene monomer and the (meth) acrylate monomer, as required. Examples of the other monomers include vinyl monomers. The following are examples of vinyl monomers that can be used in combination in forming the styrene acrylic copolymer described in the present invention, and the vinyl monomers that can be used in combination are shown below, but are not limited thereto.

(1) Olefins and process for their preparation

Ethylene, propylene, isobutylene and the like

(2) Vinyl esters

Vinyl propionate, vinyl acetate, vinyl benzoate and the like

(3) Vinyl ethers

Vinyl methyl ether, vinyl ethyl ether and the like

(4) Vinyl ketones

Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, and the like

(5) N-vinyl compounds

N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like

(6) Others

Vinyl compounds such as vinylnaphthalene and vinylpyridine; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

In addition, a polyfunctional vinyl monomer may also be used to prepare a resin having a crosslinked structure. Further, a vinyl monomer having an ionic dissociation group in a side chain can be used. Specific examples of the ion-dissociating group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specific examples of the vinyl monomer having the above-mentioned ionic dissociation group will be listed below.

Specific examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl maleate, monoalkyl itaconate and the like.

The method for producing the styrene acrylic resin is not particularly limited, and examples thereof include a method of polymerizing monomers using a known oil-soluble or water-soluble polymerization initiator. If necessary, a known chain transfer agent such as n-octylmercaptan, n-octyl-3-mercaptopropionate, or the like may be used. As the oil-soluble polymerization initiator, for example, azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators can be used. The specific embodiments of the azo-based or diazo-based polymerization initiator and the peroxide-based polymerization initiator are the same as those described in the above-mentioned method for producing a polymer.

In addition, when the styrene acrylic resin is formed using an emulsion polymerization method, a water-soluble radical polymerization initiator may be used. Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminopropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

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

The styrene acrylic resin particles formed by the emulsion polymerization method may have a structure of two or more layers made of resins having different components. As a production method in such a case, a multistage polymerization method may be employed in which a polymerization initiator and a polymerizable monomer are added to a dispersion of resin particles prepared by emulsion polymerization treatment (first-stage polymerization) according to a conventional method, and the system is subjected to polymerization treatment (second-stage and third-stage polymerization).

(polyester resin)

The polyester resin is obtained by polycondensation reaction of a dibasic or higher carboxylic acid (polycarboxylic acid component) and a dibasic or higher alcohol (polyhydric alcohol component). The polyester resin may be amorphous or crystalline.

The number of elements of the polycarboxylic acid component and the polyhydric alcohol component is preferably 2 to 3, more preferably 2. That is, the polycarboxylic acid component preferably contains a dicarboxylic acid component, and the polyol component preferably contains a diol component.

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

Also, trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides thereof, or alkyl esters having 1 to 3 carbon atoms can be used.

Examples of the diol component include saturated aliphatic diols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, 1, 14-tetradecanediol, 1, 18-octadecanediol, 1, 20-eicosanediol, and neopentyl glycol; unsaturated aliphatic diols such as 2-butene-1, 4-diol, 3-butene-1, 4-diol, 2-butyne-1, 4-diol, 3-butyne-1, 4-diol and 9-octadecene-7, 12-diol; bisphenols such as bisphenol a and bisphenol F, and aromatic diols such as ethylene oxide adducts and alkylene oxide adducts of bisphenols such as propylene oxide adducts thereof, 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 above-mentioned polycarboxylic acid component and polyhydric diol component using a known esterification catalyst.

Examples of the catalyst usable in the production of the polyester resin include alkali metal compounds such as sodium and lithium; compounds containing a group II element such as magnesium and calcium; compounds of metals such as aluminum, zinc, manganese, antimony, titanium, tin, zirconium, and germanium; a phosphorous acid compound; a phosphoric acid compound; and amine compounds and the like. Specifically, examples of the tin compound include dibutyl tin oxide (dibutyl tin oxide), tin octylate, tin dioctoate, and salts thereof. As the titanium compound, tetra-n-butyl titanate (Ti- (O-n-Bu)₄) Titanium alkoxides such as tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as poly (poly) hydroxystearic acid titanium;titanium chelates such as titanium tetraacetylacetonate, titanium lactate, and titanium triethanolamine. Examples of the germanium compound include germanium dioxide. Further, examples of the aluminum compound include polyaluminum hydroxide, aluminum alkoxide, and tributylaluminum. These may be used alone or in combination of two or more.

The polymerization temperature is not particularly limited, and is preferably 70 to 250 ℃. The polymerization time is not particularly limited, but is preferably 0.5 to 10 hours. During the polymerization, the pressure in the reaction system may be reduced as necessary.

When the toner of the present invention contains a binder resin in addition to the composition of the present invention, the content ratio of the composition to the binder resin is not particularly limited.

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

< coloring agent >

The toner of the present invention may further contain a colorant. As the colorant, known dyes and pigments can be used.

As a colorant for obtaining a black toner, carbon black, magnetic materials, iron/titanium composite oxide black, and the like are cited, and examples of the carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black. Further, as the magnetic material, ferrite ore, magnetite, and the like can be cited.

As the colorant for obtaining a Yellow toner, dyes such as c.i. solvent Yellow19, c.i. solvent Yellow44, c.i. solvent Yellow77, c.i. solvent Yellow79, c.i. solvent Yellow81, c.i. solvent Yellow82, c.i. solvent Yellow93, c.i. solvent Yellow98, c.i. solvent Yellow103, c.i. solvent Yellow104, c.i. solvent Yellow112, c.i. solvent Yellow162, and the like; pigment such as c.i.pigment Yellow14, c.i.pigment Yellow17, c.i.pigment Yellow74, c.i.pigment Yellow93, c.i.pigment Yellow94, c.i.pigment Yellow138, c.i.pigment Yellow155, c.i.pigment Yellow180, c.i.pigment Yellow185, and the like.

As colorants for obtaining magenta-colored toners, dyes such as c.i. solvent Red1, c.i. solvent Red49, c.i. solvent Red52, c.i. solvent Red58, c.i. solvent Red63, c.i. solvent Red111, c.i. solvent Red122, and the like; c.i.pigment Red5, c.i.pigment Red48:1, c.i.pigment Red53:1, c.i.pigment Red57:1, c.i.pigment Red122, c.i.pigment Red139, c.i.pigment Red144, c.i.pigment Red149, c.i.pigment Red166, c.i.pigment Red177, c.i.pigment Red178, c.i.pigment Red222 and the like.

Examples of the colorant used for obtaining the toner of cyan include dyes such as c.i.pigment Blue25, c.i.pigment Blue36, c.i.pigment Blue60, c.i.pigment Blue70, c.i.pigment Blue93, and c.i.pigment Blue 95; pigments such as c.i.pigment Blue1, c.i.pigment Blue7, c.i.pigment Blue15, c.i.pigment Blue15:3, c.i.pigment Blue60, c.i.pigment Blue62, c.i.pigment Blue66, c.i.pigment Blue76, and the like.

The colorant used for obtaining each color toner may be used in combination of one kind or two or more kinds for each color.

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

< Release agent >

The toner of the present invention may further contain a release agent. When the releasing agent is introduced into the toner, the toner can be more excellent in fixability and high in color reproducibility when heat fixing is performed simultaneously with light irradiation.

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

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

< Charge control agent >

The toner according to the present invention may contain a charge control agent. The charge control agent to be used is a substance that can be positively or negatively charged by triboelectric charging, and is not particularly limited if it is colorless, and various known positively and negatively charged charge control agents can be used.

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

< external additive >

In order to improve fluidization, chargeability, cleanability, and the like of the toner, an external additive such as a fluidizing agent or a cleaning assistant, which is a so-called post-treatment agent, may be added to the toner base particles to constitute the toner of the present invention.

Examples of the external additive include inorganic particles such as inorganic oxide particles including silica particles, alumina particles, and titanium oxide particles, inorganic stearic acid compound particles including aluminum stearate particles and zinc stearate particles, and inorganic titanic acid compound particles including strontium titanate particles and zinc titanate particles. These inorganic particles may be subjected to a hydrophobization treatment as needed. These inorganic particles may be used alone, or two or more kinds may be used in combination.

Among these, the external additive is preferably sol-gel silica particles, silica particles (hydrophobic silica particles) having a surface subjected to hydrophobic treatment, or titanium oxide particles (hydrophobic titanium dioxide particles), and more preferably two or more of the above external additives are used.

The number average primary particle diameter of the external additive is preferably in the range of 1 to 200nm, more preferably 10 to 180 nm.

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

< average particle diameter of toner >

The average particle diameter of the toner (and the average particle diameter of the toner base particles) is preferably 4 to 20 μm, and more preferably 5 to 15 μm, in terms of a volume-based median particle diameter (D50). When the volume-based median particle diameter (D50) is in the above range, the transfer efficiency is low, the image quality of halftone is improved, and the image quality of thin lines, dots, and the like is improved.

The volume-based median particle diameter (D50) was measured and calculated using a measuring apparatus in which a computer system (manufactured by BECKMAN COULTER) having data processing Software "Software V3.51" connected to a "particle counter 3" (manufactured by BECKMAN COULTER corporation) was installed.

Specifically, 0.02g of the measurement sample (toner or toner base particles) was added to 20mL of a surfactant (a surfactant solution diluted 10 times with pure water, for example, a neutral detergent containing a surfactant component for the purpose of dispersing toner particles) to be mixed, followed by ultrasonic dispersion for 1 minute to prepare a dispersion liquid. The dispersion was poured into a beaker containing "ISOTONII" (manufactured by BECKMAN COULTER corporation) in the sample stage until the indicated concentration of the measuring device was 8%.

Here, by setting the indicated concentration to the above-described value, a measurement value with reproducibility can be obtained. In addition, in the measuring apparatus, the frequency value was calculated by dividing the range of 1 to 30 μm as the measurement range into 256 parts with the number of measured particles set to 25000 and the pore diameter set to 50 μm, and the particle diameter of 50% from the start of the larger volume cumulative percentage was set as the volume-based median diameter (D50).

[ method for producing toner ]

The method for producing the toner of the present invention is not particularly limited. For example, when the composition of the present invention is used alone as a toner, the composition is pulverized by a device such as a hammer mill, a screen crusher, or a reverse jet mill, and then a dry classifier such as an air rotating pulley, an efficient precision air classifier, or a dry air classifier is used to obtain a desired particle size. When a toner further containing a colorant is produced, the composition and the colorant are dissolved in a solvent to prepare a solution, and then the solvent is removed, followed by pulverization/classification using the same method as described above.

In particular, the composition of the present invention and the toner containing a binder resin and a colorant as necessary are preferably produced by a production method using an emulsion aggregation method in which the particle diameter and shape are easily controlled.

The above production method preferably includes the steps of:

(1A) a bonding resin particle dispersion liquid preparation step of preparing a dispersion liquid of bonding resin particles as required;

(1B) a composition particle dispersion preparation step of preparing a dispersion of particles of the composition of the present invention;

(1C) a colorant particle dispersion liquid preparation step of preparing a dispersion liquid of colorant particles, if necessary;

(2) an association step of adding a coagulant to the composition particles and, if necessary, an aqueous medium containing the adhesive resin particles and the colorant particles, and performing coagulation and precipitation simultaneously with salting out to form associated particles;

(3) a ripening step of forming toner matrix particles by controlling the shape of the associated particles;

(4) a filtration and cleaning step of filtering toner base particles from an aqueous medium and removing a surfactant and the like from the toner base particles;

(5) a drying step of drying the toner base particles subjected to the cleaning treatment;

(6) and an external additive adding step of adding an external additive to the toner base particles subjected to the drying treatment.

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

(1A) Process for producing adhesive resin particle Dispersion

In this step, resin particles are formed by a conventionally known method such as emulsion polymerization, and the resin particles are aggregated and precipitated to form adhesive resin particles. As one example, a dispersion of adhesive resin particles is prepared by adding and dispersing polymerizable monomers constituting an adhesive resin into an aqueous medium, and polymerizing these polymerizable monomers by using a polymerization initiator.

In addition, as a method for obtaining the adhesive resin particle dispersion liquid, in addition to the above-described method of polymerizing the polymerizable monomer in the aqueous medium using the polymerization initiator, for example, a method of performing dispersion treatment in the aqueous medium, a method of forming a solution of a crystalline resin solvent into a solvent such as ethyl acetate, emulsifying and dispersing the solution into the aqueous medium using a disperser, and then removing the solvent, and the like can be given.

In this case, the binder resin may contain a release agent in advance, if necessary. For dispersion, it is preferable to carry out polymerization in the presence of an appropriate known surfactant (for example, an anionic surfactant such as sodium polyoxyethylene (2) lauryl ether sulfate, sodium lauryl sulfate, or dodecylbenzenesulfonic acid).

The volume-based median particle diameter (D50) of the binder resin particles in the dispersion is preferably 50 to 300 nm. The volume-based median particle diameter (D50) of the binder resin particles in the dispersion can be measured by a dynamic light scattering method using "Microtrac UPA" (manufactured by japan electronics and electronics industries, inc.).

(1B) Process for producing composition particle Dispersion

The composition particle dispersion liquid preparation step is a step of dispersing the composition of the present invention in an aqueous medium in the form of fine particles to prepare a dispersion liquid of particles of the composition.

In preparing a dispersion of the particles of the composition, first, an emulsion of the composition is prepared. The emulsion of the composition includes, for example, a method of dissolving the composition in the solvent and then emulsifying the resulting solution in an aqueous medium, and the like.

The method for dissolving the composition in the organic solvent is not particularly limited, and for example, a method in which the composition is added to the organic solvent and stirred and mixed to dissolve the composition may be mentioned. The amount of the composition to be added 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, relative to 100 parts by mass of the organic solvent.

Next, the obtained solution of the composition is mixed with an aqueous medium, and stirred by using a known disperser such as a homogenizer. Thereby, the composition is formed into a droplet shape, and emulsified in an aqueous medium to prepare an emulsion of the composition.

The amount of the solution added to the composition is preferably 10 parts by mass or more and 110 parts by mass or less per 100 parts by mass of the aqueous medium.

The temperature of the composition solution and the aqueous medium when the composition solution and the aqueous medium are mixed are each within a temperature range of less than the boiling point of the organic solvent, preferably 20 ℃ to 80 ℃, more preferably 30 ℃ to 75 ℃. The temperature of the composition solution and the temperature of the aqueous medium at the time of mixing the composition solution and the aqueous medium may be the same or different from each other, and preferably, they are the same.

For example, when the volume of the stirring vessel is 1 to 3L, the stirring conditions of the disperser are preferably 7000rpm to 20000rpm, and the stirring time is preferably 10 minutes to 30 minutes.

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

As an example, the emulsion of the composition is preferably 25 ℃ or more and 90 ℃ or less, more preferably 30 ℃ or more and 80 ℃ or less, in an inert gas atmosphere such as nitrogen gas, and the organic solvent is removed by heating, for example, until the amount of the organic solvent in the initial stage becomes about 80 mass% or more and 95 mass% or less. Thereby, a dispersion of the particles of the composition is prepared, which has the organic solvent removed from the aqueous medium and the particles of the composition dispersed in the aqueous medium.

The mass average particle diameter of the particles of the composition in the dispersion of the particles of the composition is preferably 90nm or more and 1200nm or less. The mass average particle diameter can be set within the above range by appropriately adjusting the viscosity when the composition is mixed into an organic solvent, the mixing ratio of a solution of the composition and an aqueous medium, the dispersion speed of a disperser when preparing an emulsion of the composition, and the like. The mass-average particle diameter of the particles of the composition in the dispersion of the particles of the polymer can be measured using an electrophoresis light scattering photometer "ELS-800" (manufactured by Otsuka electronics Co., Ltd.).

< organic solvent >

The organic solvent used in the present step is not particularly limited as long as it can dissolve the polymer and the compound in the composition. Specific examples thereof include 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, and halogenated hydrocarbons such as dichloromethane, dichloroethane and carbon tetrachloride.

These organic solvents may be used alone or in combination of two or more. Of these organic solvents, ketones and halogenated hydrocarbons are preferable, and methyl ethyl ketone and methylene chloride are more preferable.

< aqueous Medium >

The aqueous medium used in this step includes, for example: water, or an aqueous medium containing water as a main component and an aqueous solvent such as alcohols and glycols, and an optional component such as a surfactant and a dispersant. The aqueous medium is preferably a mixture of water and a surfactant.

Examples of the surfactant include cationic surfactants, anionic surfactants, and nonionic surfactants. Examples of the cationic surfactant include dodecylammonium chloride, dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, and hexadecyltrimethylammonium bromide. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium laurate, sodium dodecylbenzenesulfonate and sodium dodecylsulfate. Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, and sucrose monodecanoate.

These surfactants may be used alone, or two or more of them may be used in combination. Among the surfactants, anionic surfactants are preferably used, and sodium dodecylbenzenesulfonate is more preferably used.

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

(1C) Process for producing colorant particle Dispersion

The colorant particle dispersion liquid preparation step is a step of preparing a colorant particle dispersion liquid by dispersing a colorant in an aqueous medium in the form of fine particles.

The dispersion of the colorant can be carried out using mechanical energy. The colorant particles in the dispersion preferably have a number-based median particle diameter of 10 to 300nm, more preferably 50 to 200 nm. The median particle diameter based on the number of the colorant particles can be measured by using an electrophoresis light scattering photometer "ELS-800" (manufactured by Otsuka electronics Co., Ltd.).

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

The flocculant used in the association step (2) is not particularly limited, and preferably a flocculant selected from metal salts is used. Examples of the metal salt include monovalent metal salts such as salts of alkali metals such as sodium, potassium, and lithium; divalent metal salts such as calcium, magnesium, manganese, and copper; trivalent metal salts such as iron and aluminum, and the like. Specific examples of the metal salt include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate, and among the above metal salts, a divalent metal salt is particularly preferably used because the coagulation can be performed in a smaller amount. These metal salts may be used alone or in combination of two or more.

[ developer ]

It is considered that the toner according to the present invention can be used, for example, as a one-component magnetic toner containing a magnetic substance, can be used as a two-component developer by mixing with a so-called carrier, or can be used alone as a non-magnetic toner, and any of the above can be preferably used.

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

As the carrier included in the two-component developer, magnetic particles of a conventionally known material selected from metals such as iron, steel, nickel, cobalt, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used.

The carrier may be a coated carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, or may be a resin-dispersed carrier in which magnetic substance powder is dispersed in a binder resin. The resin used for coating is not particularly limited, and for example, olefin resin, acrylic resin, styrene acrylic resin, silicone resin, polyester resin, fluororesin or the like can be used. The resin used to form the resin-dispersed carrier particles is not particularly limited, and known resins, for example, acrylic resins, styrene acrylic resins, polyester resins, fluorine resins, phenol resins, and the like can be used.

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

The total mass of the toner and the carrier is set to 100% by mass, and the mixing amount of the toner is preferably 2 to 10% by mass.

[ image Forming method ]

The toner of the present invention can be used in various known image forming methods of an electrophotographic system. For example, it can be used for a monochrome image forming method and a full-color image forming method. In the full-color image forming method, it may be used in any one of the following methods: a four-cycle image forming method constituted by four types of color developing devices relating to respective colors of yellow, magenta, cyan, and black, and one photoreceptor; and a random image forming method in which an image forming unit having a color developing device and a photoreceptor for each color is mounted for each color.

In one embodiment of the present invention, there is provided an image forming method including: 1) a step of forming a toner image made of the toner of the present invention on a recording medium, and 2) a step of irradiating the toner image with light to soften the toner image. With the embodiments, the fixing property is excellent and the image quality is higher.

Related procedure 1)

In this step, a toner image containing the toner of the present invention is formed on a recording medium.

(recording Medium)

The recording medium is a member for holding a toner image. Examples of the recording medium include plain paper, conventional starch (previous), double coated paper (アート), coated printing paper such as coated paper (コート), commercially available japanese paper or postcard paper, resin film for OHP or packaging material, and cloth.

The recording medium may have a sheet shape (single sheet shape) having a predetermined size, or may have a long sheet shape wound in a roll shape after the toner is fixed.

The toner formation can be performed, for example, by transferring a toner image on the photoreceptor to a recording medium, as described later.

Related procedure 2)

In this step, the formed toner image is irradiated with light to soften the toner image. Thereby, the toner image can be adhered to the recording medium.

The wavelength of the light irradiated with light is not particularly limited as long as the light can be converted into light and heat by the compound and the polymer contained in the composition in the tonerThe wavelength is preferably 280nm to 480nm, for example, so that the toner image can be sufficiently softened. Within the above range, the toner image can be softened more effectively. From the same viewpoint, the dose of light irradiation is preferably 0.1 to 200J/cm²More preferably 0.1 to 100J/cm²More preferably 0.1 to 50J/cm²。

As described later, light irradiation may be performed using a light source such as a Light Emitting Diode (LED) or a laser light source. As described later, the heating may be further performed simultaneously with the light irradiation.

After the step 2), a step of 3) pressurizing the softened toner image may be further performed as necessary. With this embodiment, the fixing property is improved.

Concerning step 3)

In this step, the softened toner image is pressurized.

The pressure at which the toner image on the recording medium is pressurized is not particularly limited, but is preferably 0.01 to 5.0MPa, and more preferably 0.05 to 1.0 MPa. When the pressure is set to 0.01MPa or more, the amount of deformation of the toner image can be increased, and therefore, the contact area between the toner image and the recording sheet S is increased, and the fixing property of the image is likely to be further improved. Further, by setting the pressure to 5.0MPa or less, the impact sound generated at the time of pressurization can be suppressed.

This pressurizing step may be performed before or simultaneously with the step of softening the image by light irradiation, but is preferably performed after the light irradiation because the pressurizing step can pressurize the toner in a pre-softened state, and as a result, the fixing property of the image is further improved.

In the step of applying pressure, the softened toner image may be further heated. That is, the pressurizing step may be performed while heating the toner image. The temperature at this time (for example, the temperature of the pressing member) is preferably 15 ℃ or higher, more preferably 20 ℃ or higher, still more preferably more than 20 ℃, still more preferably 30 ℃ or higher, and still more preferably 40 ℃ or higher. By performing this embodiment, the fixing property is significantly improved. The upper limit is not particularly limited, and may be, for example, 200 ℃ or lower, 150 ℃ or lower, or 100 ℃ or lower.

When the glass transition temperature of the toner is T, the heating temperature of the toner image (the surface temperature of the toner image during heating) is preferably (Tg +20) to (Tg +100) deg.c, and more preferably (Tg +20) to (Tg +80) deg.c. When the surface temperature of the toner is (Tg +20) ° c or more, the toner image is easily deformed by pressurization, and when it is (Tg +100) ° c or less, thermal compensation is easily suppressed. The thermal compensation is a phenomenon in which a part of the toner is transferred to a pressing member such as a roller in a fixing process, and a toner layer is broken.

Further, prior to the step 2), a step of 4) heating the toner image in advance may be further performed as necessary. As described above, by further performing the step of 4) heating the toner image in advance before the step 2), the sensitivity of the compound of the present invention to light can be further improved. This makes it difficult for the polymer to lose sensitivity to light, and therefore, melting or softening of the toner image by light irradiation is facilitated.

Fig. 1 is a schematic configuration diagram showing an image forming apparatus 100 used in an image forming method according to an embodiment of the present invention. However, the image forming apparatus used in the present invention is not limited to the following embodiments and examples. In fig. 1, a monochrome image forming apparatus 100 is shown as an example, but the present invention can be applied to a color image forming apparatus.

The image forming apparatus 100 is an apparatus for forming an image on a recording sheet as a recording medium, and includes an image reading apparatus 71 and an automatic document feeder 72, and forms an image on the recording sheet S conveyed by a sheet conveyance system 7 by an image forming portion 10, an irradiation portion 40, and a pressure-bonding portion 9.

As the recording medium, recording paper S is used in the image forming apparatus 100, and the medium on which an image can be formed may be a medium other than paper as described above.

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

The sheet conveyance system 7 includes a plurality of trays 16, a plurality of sheet feeding portions 11, conveyance rollers 12, a conveyance belt 13, and the like. The trays 16 each accommodate a recording sheet S of a specified size, and the paper feed portion 11 of the specified tray 16 is activated in accordance with an instruction from the control portion 90 to supply the recording sheet S. The transport roller 12 transports the recording sheet S fed from the tray 16 or the recording sheet S transported from the manual paper feed unit 15 to the image forming portion 10.

The image forming section 10 is configured to surround the photoreceptor 1 along the rotation direction of the photoreceptor 1, and is configured by arranging the charger 2, the exposer 3, the developing section 4, the transfer section 5, the static charge removing section (not shown), and the cleaning section 8 in this order.

The photoreceptor 1 as an image carrier is an image carrier having a photoconductive layer formed on the surface thereof and is configured to be rotatable in the direction of an arrow in fig. 1 by a driving device not shown. A thermo-hygrometer 17 that detects the temperature and humidity inside the image forming apparatus 100 is provided near the photoconductor 1.

The charger 2 uniformly and uniformly applies electric charge to the surface of the photoreceptor 1, and uniformly charges the surface of the photoreceptor 1. The exposure unit 3 includes a light emitting source such as a laser diode, and irradiates the charged surface of the photoreceptor 1 with a light beam to remove charges in the irradiated portion, thereby forming an electrostatic latent image corresponding to image data on the photoreceptor 1. The developing section 4 supplies the toner contained therein to the photoreceptor 1, and forms a toner image on the surface of the photoreceptor 1 based on the electrostatic latent image.

The transfer portion 5 faces the photoreceptor 1 through the recording paper S, and transfers the toner image onto the recording paper S. The static charge removing portion removes static charge of the photoreceptor 1 after the toner image is transferred. The cleaning unit 8 includes a blade 85, and the blade 85 cleans the surface of the photoreceptor 1 and removes the developer remaining on the surface of the photoreceptor 1.

The recording paper S on which the toner image is transferred is conveyed to the nip 9 by the conveyance 13. The pressure-contact portion 9 may be provided arbitrarily, and fixes an image on the recording sheet S by applying only pressure, or applying heat and pressure to the recording sheet S on which a toner image is transferred by the pressure members 91 and 92 to perform a fixing process. The recording paper S on which the image is fixed is conveyed to the paper discharge portion 14 by the transport rollers, and discharged outside the apparatus by the paper discharge portion 14.

The image forming apparatus 100 includes a paper reversing unit 24 that conveys the recording paper S subjected to the heat fixing process to the paper reversing unit 24 before the paper discharge unit 14, and discharges the recording paper S with its front and back surfaces reversed, or conveys the recording paper S with its front and back surfaces reversed again to the image forming unit 10, and thereby can form images on both surfaces of the recording paper S.

< irradiation part >

Fig. 2 is a schematic configuration diagram of irradiation unit 40 in image forming apparatus 100.

An image forming apparatus 100 according to an embodiment of the present invention includes an irradiation unit 40. The irradiation unit 40 includes a light source 41 and a heating member 93. Examples of the device constituting the light source 41 include a Light Emitting Diode (LED), a laser light source, and the like.

The light source 41 irradiates the toner image formed on the recording medium with light to soften the toner image. The conditions for light irradiation are not particularly limited as long as the combination of the present invention contained in the toner of the developer can be melted and fluidized. The wavelength of light to be irradiated to the toner image is only required to be sufficient to fluidize the composition, and is preferably in the range of 280nm to 480nm, more preferably 300nm to 420nm, and still more preferably 330nm to 420 nm. The amount of light irradiated from the light source 41 may be 0.1J/cm, for example, as long as the composition is sufficiently fluidized²Above and 200/cm²In the following range, preferably 0.1J/cm²Above and 100/cm²More preferably in the range of 0.1J/cm²Above and 50/cm²More preferably, it is in the range of 0.1J/cm²Above and 30/cm²Within the following ranges.

When the toner image is further irradiated with light by the light source 41 to soften the toner image, the toner image may be heated by the heating member 93 while the light is irradiated. This makes it possible to more effectively soften and melt the toner image. The heating temperature in this case may be, for example, in the range of 20 ℃ to 200 ℃, preferably in the range of 20 ℃ to 150 ℃.

The toner image after softening may be cured and fixed on a recording medium by leaving the toner image at room temperature (in the range of 25 ± 15 ℃), heating, or irradiating with visible light. As described later, the step of fixing the toner image preferably further includes a step of pressurizing the softened toner image. In the pressing step, it is preferable to further heat the softened toner image.

The light source 41 is a device for irradiating light toward a first surface of the recording sheet S holding a toner image, which is on the photosensitive side, and is disposed on the photosensitive side with respect to the surface of the recording sheet S kneaded between the photosensitive body 1 and the transfer roller 5 as a transfer portion. The light source 41 and the heating member 93 are arranged along the conveyance direction (paper conveyance direction) of the recording paper S.

The light source 41 and the heating member 93 are disposed on the downstream side in the sheet conveying direction and on the upstream side in the sheet conveying direction with respect to the pressure-bonding section 9 with respect to the nip position between the photoreceptor 1 and the transfer roller 5.

According to an image forming method provided by an embodiment of the present invention, after the photoreceptor 1 is charged by applying the same potential to the charging body 2, a light beam irradiated by the exposure device 3 is scanned on the photoreceptor 1 based on original image data to form an electrostatic latent image. Subsequently, a developer having a toner containing the composition of the present invention is supplied onto the photoreceptor 1 through the developing section 4.

The toner image carried on the surface of the photoreceptor 1 is conveyed from the tray 16 to the image forming section 10 in accordance with the timing when the toner image reaches the position of the transfer roller 5 as a transfer section by the rotation of the photoreceptor 1, and at this time, the image on the photoreceptor 1 is transferred to the recording sheet S kneaded by the photoreceptor 1 and the transfer roller 5 as a transfer section due to the transfer bias applied to the transfer roller 5.

The transfer portion 5 also functions as a pressing member that can reliably bring the toner image into close contact with the recording sheet S when the toner image is transferred from the photoreceptor 1 onto the recording sheet S.

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

While the recording sheet S on which the toner image is transferred is conveyed to the pressure-bonding section 9 by the conveying belt 13, the light source 41 irradiates the toner image transferred on the recording sheet S with light. Since the light source 41 irradiates the toner image on the first surface of the recording sheet S with light, the toner image can be more reliably melted, and the fixing property of the toner image to the recording sheet S can be improved.

When the recording sheet S holding the toner image is conveyed to the pressure-contact portion 9 by the conveying belt 13, the pressure members 91 and 92 press the toner image onto the first surface of the recording sheet S. Before the fixing process is performed at the pressure-contact portion 9, the toner image is further softened by being irradiated with light from the light source 41, and therefore, energy required for pressure-contacting the image on the recording sheet S can be saved. Further, in the step of solidifying and fixing the toner image on the recording medium, the fixing property of the toner image to the recording sheet S is further improved by pressurizing the toner image with the pressurizing members 91 and 92.

The pressure at which the toner image on the recording medium is pressurized is not particularly limited, but is preferably 0.01 to 5.0MPa, and more preferably 0.05 to 1.0 MPa. By setting the pressure to 0.01MPa or more, the amount of deformation of the toner image can be increased, and therefore the contact area between the toner image and the recording sheet S is increased, and the fixing property of the image is more easily improved. Further, by setting the pressure to 5.0MPa or less, impact sound during pressurization can be suppressed.

In the step of pressing, it is preferable that the toner image is further heated. By applying pressure and heat using the pressure members 91 and 92, the fixing property of the toner image to the recording sheet S is further improved. Specifically, when the recording sheet S passes between the pressing members 91 and 92, the pressing member 91 further heats and presses the toner image softened by the light irradiation in a further softened state, thereby further improving the fixing property of the toner image to the recording sheet S.

The heating temperature at the time of further heating in the pressurizing step is preferably 15 ℃ or higher, more preferably 20 ℃ or higher, further preferably more than 20 ℃, further preferably 30 ℃ or higher, and further preferably 40 ℃ or higher. By implementing this embodiment, the fixing property is significantly improved. The upper limit is not particularly limited, but is, for example, 200 ℃ or lower, 150 ℃ or lower, or 100 ℃ or lower.

The toner image is pressed by the pressing members 91 and 92 and cured, and fixed on the recording sheet S.

That is, in one embodiment of the present invention, the fixing device includes a pressure-contact portion having a pressure member. In one embodiment of the present invention, the pressing member has a heating system.

In one embodiment of the present invention, the temperature of the pressing member is preferably 15 ℃ or higher, more preferably 20 ℃ or higher, further preferably more than 20 ℃, further preferably 30 ℃ or higher, and further preferably 40 ℃ or higher. The upper limit is not particularly limited, but is, for example, 200 ℃ or lower, 150 ℃ or lower, or 100 ℃ or lower.

When forming images on both sides of the recording paper S, the recording paper S subjected to the pressure bonding process is conveyed to the paper reversing section 24 in front of the paper discharge section 14, and is discharged with its front and back sides reversed, or the recording paper S with its front and back sides reversed is conveyed again to the image forming section 10.

(light responsive adhesive)

Since the composition of the present invention is fluidized and reversibly non-fluidized by light irradiation, a reusable light-responsive adhesive (photosensitive adhesive) can be produced using the composition of the present invention. For example, the adhesive can be applied to various adhesive techniques as a light-responsive adhesive which can be repeatedly subjected to light attachment and detachment depending on a change in viscosity (coefficient of friction). That is, one embodiment of the present invention is a light-responsive adhesive comprising the composition of the present invention.

The light-responsive adhesive of the present invention can be used for temporary fixing that can be repeatedly used, and is also suitable for recycling, but is not limited thereto.

(optical switch material)

The composition of the present invention is fluidized and reversibly non-fluidized by light irradiation, and thus an optical switching material can be prepared using the composition of the present invention. For example, changes in color and polarity, material movement, changes in orientation, changes in viscosity, changes in surface tension, which are associated with photoisomerization, can be used to prepare optical switching materials. For example, in a liquid crystal material or the like, it can be applied to pattern drawing which is rewritable repeatedly in response to a change in molecular orientation accompanying photoisomerization. Further, for example, the surface of the polymer film may be finely processed by utilizing a change in surface tension caused by light irradiation and a substance movement caused thereby. That is, one embodiment of the present invention is an optical switching material comprising the composition of the present invention.

The optical switch material of the present invention can be used for surface processing of liquid crystal displays and polymer films, but is not limited thereto.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

First, polymers 1 to 3, 5 to 18 in the following Table 3 containing compounds 1,2, 6 and 10 described in the above Table 1 and structural units 1 to 3, 5 and 18 of the above Table 2 were prepared.

[ Synthesis of Compound 1]

4-hexyloxyaniline (7.7mmol), 5-methylthiophene-2-carbaldehyde (7.7mmol) and 20ml of ethanol were placed in a 100ml four-necked flask equipped with a cooling tube, a nitrogen inlet tube and a thermometer, followed by heating and stirring. The reaction solution was aspirated and filtered, and the resulting powder was washed with cooling ethanol. Subsequently, recrystallization was performed under methanol/ethanol to obtain compound 1 as the objective substance at a rate of recovery of 42%.

[ chemical formula 19]

In that¹Formation of compound 1 was confirmed by H NMR.¹H NMR(400MHz、CDCl₃)；8.35ppm(s,1H,CH＝N)、7.39ppm(d,2H,aryl)、7.08ppm(d,1H,thiophene)、6.69ppm(d,2H,aryl)、6.67ppm(d,2H,thiophene)、4.11ppm(t,2H,methylene)、2.44ppm(s,3H,methyl)、1.80ppm(m,2H,methylene)、1.47ppm(m,2H,methylene)、1.37(m,4H,methylene)、0.89ppm(m,3H,methyl)、

[ Synthesis of Compound 2]

In the synthesis of the above compound 1, compound 2 was synthesized in the same manner as in the synthesis of compound 1, except that 5-methylthiophene-2-carbaldehyde (7.7mmol) was changed to N-methylpyrrole-2-carbaldehyde (7.7 mmol). Similarly, in¹The formed compound was confirmed by H NMR, and it was found that the target compound was obtained.

[ Synthesis of Compound 10]

Compound 10 was synthesized in the same manner as compound 1 except that 5-methylthiophene-2-carbaldehyde (7.7mmol) was changed to 1-methyl-1H-pyrazole-4-carbaldehyde (7.7mmol) in the synthesis of compound 1. Similarly, in¹The formed compound was confirmed by H NMR, and it was found that the target compound was obtained.

[ Synthesis of Compound 6]

To 4-aminophenol (6.54g, 60mmol) was added 75mL of 2.4N hydrochloric acid, followed by cooling and stirring at 0 ℃ and adding a solution of sodium nitrite (4.89g, 72mmol) dissolved in 6mL of distilled water, followed by stirring at 0 ℃ for 60 minutes. To the solution were added o-cresol (6.48g, 60mmol) and 24mL of a 20% aqueous solution of sodium hydroxide, followed by stirring for 20 hours. The precipitated precipitate was filtered and the solid was washed with water. The obtained solid was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as a developing solvent, and was recrystallized by a mixed solution of acetone and hexane to obtain intermediate a. To intermediate A (2.28g, 10mmol) were added 100mL of DMF, 1-bromohexane (9.9g, 60mmol) and potassium carbonate (6.9g, 50mmol), and after stirring at 80 ℃ for two hours, stirring was continued at room temperature for 20 hours. The solvent was evaporated under reduced pressure, and the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the obtained solid component was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as a developing agent, whereby compound 6 as an azobenzene derivative was obtained.

[ chemical formula 20]

First stage

Second stage

[ synthetic Polymer 1]

(Synthesis of an azomethine derivative monomer 1)

4-aminophenol (5g, 0.046mol), 5-methylthiophene-2-carbaldehyde (5.8g, 0.046mol) and 100ml of ethanol were charged into a 100ml four-necked flask, and heated with stirring. The reaction solution was aspirated and filtered, and the resulting powder was washed with cooling ethanol. Subsequently, recrystallization was performed under methanol/ethanol to obtain the target substance 1 at a recovery rate of 42%.

[ chemical formula 21]

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

[ chemical formula 22]

Next, the target substance 2(3g, 0.001mol) obtained above, 1.34ml of triethylamine (0.001mol) and 30ml of dichloromethane were charged into a 100ml four-necked flask. At this time, the raw material substances are in a dispersed state. The internal temperature of the raw material was maintained at 0 ℃, and a solution obtained by dissolving 1.04g of acrylic acid chloride (0.011mol) in 10ml of methylene chloride was maintained at 0 to 5 ℃ and added dropwise. After the dropwise addition, the raw materials were dissolved.

After completion of the dropwise addition, the reaction solution was returned to room temperature and stirred. After completion of the reaction, dichloromethane was concentrated and removed, and the dichloromethane was dissolved in ethyl acetate, washed with dilute hydrochloric acid, an aqueous sodium bicarbonate solution, and a saturated saline solution, and the organic layer was dried over magnesium sulfate and then concentrated. The obtained orange crystals were purified by silica gel column (ethyl acetate/heptane ═ 1/5), thereby obtaining an azomethine derivative monomer 1 having a structural unit 1.

[ chemical formula 23]

In a 100ml four-necked flask, 1.5g of the above-obtained azomethine derivative monomer 1(4.096mmol), 5mg of 4-cyanovaleric acid dithiobenzoate (0.023mmol) and 1mg of AIBN (0.006mmol) were dissolved in 4ml of anisole. Subsequently, after an argon atmosphere was generated by freeze degassing, the temperature was raised to 75 ℃, and polymerization was performed by stirring. After 40ml of methanol was gradually added dropwise to the resulting polymer solution, THF was added to remove unreacted azomethine derivative monomer 1. The separated polymer solution was dried in a vacuum drying oven at 40 ℃ for 24 hours to obtain polymer 1. The number average molecular weight Mn of the resulting polymer 1 was measured by the GPC method and found to be 12000.

[ chemical formula 24]

Polymer 1:

[ synthetic polymers 2, 3, 18]

Polymers 2, 3, 18 having structural units 2, 3, 18 were obtained using the respective starting materials in the same manner as in the synthesis of polymer 1.

Specifically, polymer 2 was synthesized in the same manner as in polymer 1, except that 4-aminophenol was changed to 3-aminophenol in the synthesis of the azomethine derivative monomer 1.

Polymer 3 was synthesized in the same manner as Polymer 1, except that 5-methylthiophene-2-carbaldehyde was changed to N-hexylpyrrole-3-carbaldehyde in the synthesis of the azomethine derivative monomer 1.

Polymer 18 was synthesized in the same manner as in Polymer 1, except that 5-methylthiophene-2-carbaldehyde was changed to 1-methyl-1H-pyrazole-4-carbaldehyde and 6-chloro-1-hexanol was changed to 10-chloro-1-decanol in the synthesis of the azomethine derivative monomer 1.

The amounts of the raw materials and the reaction conditions were appropriately adjusted as necessary in the production of the polymers 2, 3 and 18 and the following polymers.

[ synthetic Polymer 5]

4-hexylaniline (11g, 0.0643mol) and 100ml of acetone were added under argon flow in a dark room, and 26ml of HClaq was added dropwise after cooling. Further, NaNO was added dropwise₂aq.(NaNO₂ 4.6g/H₂O10 ml) was added thereto, and stirred at 0 ℃ or lower for 30 minutes. To the preparation solution, 26ml of 20% naohaq and 6g of phenol were added dropwise, and the mixture was stirred at room temperature. Subsequently, 64ml of hclaq was added dropwise, and liquid separation treatment was performed with toluene/water. The obtained organic layer was purified in a silica gel column (toluene), and the objective substance 1' was obtained.

[ chemical formula 25]

Next, in the synthesis of the above-mentioned azomethine derivative monomer 1, azomethine derivative monomer 5 was synthesized in the same manner as in the synthesis of azomethine derivative monomer 1, except that the target substance 1' prepared as described above was used instead of the target substance 1, and 10-chloro-1-decanol was used instead of 6-chloro-1-hexanol. A polymer 5 was obtained in the same manner as in the synthesis of polymer 1, except that the above-mentioned azomethine derivative monomer 5 was used instead of azomethine derivative monomer 1.

[ synthetic polymers 6 to 9]

Polymers 6 to 8 were prepared in the same manner as synthetic polymer 1 except that the amount of the azomethine derivative monomer 1 was changed from 1.5g to 1.2g, and 0.3g of styrene, ethyl acrylate, and n-butyl methacrylate were added to the synthetic polymer 1. Further, a polymer 9 was produced in the same manner as in the synthetic polymer 1 except that the amount of the azomethine derivative monomer 1 was changed from 1.5g to 1.2g, and 0.15g of styrene and 0.15g of methyl acrylate were added to the synthetic polymer 1.

[ synthetic Polymer 10]

< Synthesis of macroinitiator 10>

In a 100ml eggplant-shaped flask, 2' -bipyridine (230mg, 1.47mmol) was charged, and further Cu (I) Br (95mg, 0.66mmol), styrene (15g, 144mmol), ethyl 2-bromoisobutyrate (35mg, 0.18mmol) were charged in a glove box under a nitrogen atmosphere and sealed. It is placed in an oil bath at 100 ℃ and heated and stirred. Subsequently, an appropriate amount of tetrahydrofuran was added and passed through a neutral alumina column. This was again precipitated/centrifuged using methanol and then purified to obtain macroinitiator 10. The number average molecular weight (β Mn) of the macroinitiator 10 measured by the GPC method was 1100.

< synthetic Polymer 10>

A100 ml eggplant-shaped flask was charged with the above-obtained azomethine derivative monomer 1(16g, 38mmol) and the above-mentioned macroinitiator 10(0.92g, 0.18mmol), and further charged with Cu (I) Cl (29mg, 0.29mmol), 1,4,7,10, 10-hexamethyltriethylenetetramine (136mg, 0.59mmol) and anisole (4.9g, 41.1mmol) as a solvent in a glove box under a nitrogen atmosphere, and sealed. Subsequently, the mixture was stirred with heating in an oil bath at 80 ℃. Next, an appropriate amount of chloroform was added and passed through an alkaline alumina column. This was again precipitated/centrifuged using methanol and then purified to obtain polymer 10. The total number-average molecular weight Mn of the polymer 10 measured by the GPC method was 5600. From this, the number average molecular weight (α Mn) of the structural unit derived from the azomethine derivative was 4500.

[ synthetic Polymer 11]

< Synthesis of macroinitiator 11>

In the synthesis of macroinitiator 10, macroinitiator 11 was obtained in the same manner except that ethyl 2-bromoisobutyrate was changed to α, α' -dibromo-p-xylene.

< synthetic Polymer 11>

In synthesizing the polymer 10, the polymer 11 was obtained in the same manner except that the macroinitiator 10 was changed to the macroinitiator 11.

[ synthetic Polymer 12]

< Synthesis of macroinitiator 12>

In the synthesis of the macroinitiator 10, the macroinitiator 12 was obtained in the same manner except that ethyl 2-bromoisobutyrate was changed to ethylene bis (2-bromoisobutyrate), 2' -bipyridine was changed to 1,1,4,7,10, 10-hexamethyltriethylenetetramine, styrene was changed to the methane imine derivative monomer 1, and anisole was added.

< synthetic Polymer 12>

In synthesizing the polymer 10, the polymer 12 was obtained in the same manner except that the macroinitiator 10 was changed to the macroinitiator 12, 1,4,7,10, 10-hexamethyltriethylenetetramine was changed to 2, 2' -bipyridine, the azomethine derivative monomer 1 was changed to styrene, and anisole was removed.

[ synthetic Polymer 13]

< Synthesis of macroinitiator 13>

In synthesizing the macroinitiator 10, by appropriately adjusting the heating stirring time in an oil bath at 100 ℃, the macroinitiator 13 having the same structure as the macroinitiator 10 and the number average molecular weight (. beta.Mn) of 7000 was obtained.

< synthetic Polymer 13>

In the synthesis of polymer 10, by appropriately adjusting the heating stirring time in an oil bath at 80 ℃, large polymer 13 composed of the same structural units as polymer 10 and having a total number average molecular weight Mn of 7500 was obtained. In the polymer 13, the number average molecular weight (α Mn) of the structural unit derived from the azomethine derivative was 500.

[ synthetic Polymer 14]

< Synthesis of macroinitiator 14>

In synthesizing the macroinitiator 11, the macroinitiator 14 was obtained in the same manner except that styrene was changed to methyl acrylate.

< synthetic Polymer 14>

In synthesizing the polymer 11, the polymer 14 was obtained in the same manner except that the macroinitiator 11 was changed to the macroinitiator 14.

[ synthetic Polymer 15]

< Synthesis of macroinitiator 15>

In the synthesis of macroinitiator 11, macroinitiator 15 was obtained in the same manner except that styrene was changed to n-hexyl methacrylate.

< synthetic Polymer 15>

In synthesizing the polymer 11, the polymer 15 was obtained in the same manner except that the macroinitiator 11 was changed to the macroinitiator 15.

[ synthetic Polymer 16]

< Synthesis of macroinitiator 16>

In the synthesis of the macroinitiator 11, the macroinitiator 16 was obtained in the same manner except that styrene was changed to 3-methyl-1-pentene.

< synthetic Polymer 16>

In synthesizing the polymer 11, the polymer 16 was obtained in the same manner except that the macroinitiator 11 was changed to the macroinitiator 16.

[ synthetic Polymer 17]

< Synthesis of macroinitiator 17>

In synthesizing the macroinitiator 11, the macroinitiator 16 was obtained in the same manner except that styrene was changed to a mixture of styrene and methyl acrylate in a molar ratio of 5: 5.

< synthetic Polymer 17>

In synthesizing the polymer 11, the polymer 17 was obtained in the same manner except that the macroinitiator 11 was changed to the macroinitiator 17.

[ preparation of compositions 1 to 25]

The compounds 1,2, 6 and 10 and the polymers 1 to 3 and 5 to 18 prepared in the above manner were dissolved in an appropriate amount of THF at the ratios (mass ratios) in the following table 3, and dried and cured to obtain compositions 1 to 25.

The compounds and polymers constituting compositions 1 to 25 are shown in Table 3 below. In table 3, compounds 1,2, 6, 10 are compounds 1,2, 6, 10 in table 1 above. Further, the structural unit Nos. of the polymers 1 to 3 and 5 to 18 are structural unit Nos. in Table 2.

[ preparation of toner 1]

< preparation of composition particle Dispersion 1>

80 parts by mass of methylene chloride and 20 parts by mass of composition 1 obtained as described above were heated at 50 ℃ and mixed with stirring, to obtain a solution containing composition 1. To 100 parts by mass of the obtained solution, 99.5 parts by mass of a mixture of distilled water heated to 50 ℃ and 0.5 part by mass of a 20% by mass aqueous solution of sodium dodecylbenzenesulfonate was added. Subsequently, the mixture was emulsified by stirring at 16000rpm for 20 minutes using a homogenizer (manufactured by Heidolph) equipped with a shaft generator 18F to obtain an emulsion of composition 1.

The resulting emulsion was put into a glass seperator bottle, nitrogen gas was sent into the gas phase and heated and stirred at 40 ℃ for 90 minutes, and the organic solvent was removed to obtain composition particle dispersion 1. The particle diameter of the composition particles in the composition particle dispersion 1 was measured to be a mass average particle diameter of 155nm using an electrophoresis light scattering photometer "ELS-800" (manufactured by Otsuka electronics Co., Ltd.).

(preparation of Black colorant particle Dispersion (Bk-1))

11.5 parts by mass of sodium n-dodecyl sulfate was dissolved in 160 parts by mass of pure water, and 25 parts by mass of carbon black (Mogal L (manufactured by Cabot corporation)) was gradually added thereto, followed by dispersion treatment using "Clearmix (registered trademark) W motion CLW-0.8 (manufactured by M Technique corporation)", thereby preparing a black colorant particle dispersion (Bk-1). The volume-based median particle diameter of the colorant particles in the black colorant particle dispersion (Bk-1) was 110 nm.

< preparation of toner 1>

602 parts by mass of the composition particle dispersion 1 as a solid content, 52 parts by mass of the black colorant particle dispersion (Bk-1) as a solid content, and 900 parts by mass of ion-exchanged water prepared as described above were placed in a reaction apparatus equipped with a stirring device, a temperature sensor, and a cooling tube. The temperature in the vessel was maintained at 30 ℃ and a 5 mol/l aqueous solution of sodium hydroxide was added to adjust the pH to 10.

Subsequently, after the completion of dropwise addition of an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved into 1000 parts by mass of ion-exchanged water over 10 minutes with stirring, temperature rise was started, the system was allowed to rise to 70 ℃ over 60 minutes, and the particle growth reaction was continued while maintaining the temperature at 70 ℃. In this state, the particle diameter of the associated particles was measured using a "Multisizer 3" (manufactured by Beckman Coulter corporation), and when the volume-based median particle diameter (D50) was 6.5 μm, an aqueous solution prepared by dissolving 190 parts by mass of sodium chloride in 760 parts by mass of ion-exchanged water was added to stop the growth of the particles. After stirring at 70 ℃ for 1 hour, the temperature was further raised, and the particles were fused by heating and stirring at 75 ℃. Subsequently, cooling was performed to 30 ℃, thereby obtaining a dispersion liquid of toner matrix particles.

The obtained dispersion liquid of the toner base particles was subjected to solid-liquid separation using a centrifugal separator to form a wet cake of the toner base particles. The wet cake was washed with ion-exchanged water at 35 ℃ by a centrifuge until the conductivity of the filtrate reached 5. mu.S/cm, and then transferred to a "spin flash dryer" (manufactured by Seishin corporation) and dried to have a water content of 0.5 mass%, to prepare toner base particles.

To 100 mass% of the obtained toner base particles, 1 mass% of hydrophobic silica (number average primary particle diameter: 12nm) and 0.3 mass% of hydrophobic titania (number average primary particle diameter: 20nm) were added and mixed using henshel Mix (registered trademark), thereby obtaining toner 1.

[ preparation of toners 2 to 23, 26 and 27 and preparation of toners of comparative examples 1 and 2]

Toners 2 to 23, 26 and 27 were obtained in the same manner as in the above-described toner 1 preparation except that the composition 1 was changed to compositions 2 to 25. Toners of comparative examples 1,2 were prepared according to the components described in table 4 below.

[ preparation of toner 24]

In the above-described preparation of toner 1, toner 24 was obtained in the same manner except that polymer particle dispersion 1 was changed from 602 parts by mass in terms of solid content to 421 parts by mass, and the following styrene acrylic resin particle dispersion was added in terms of solid content of 181 parts by mass.

< preparation of styrene acrylic resin particle Dispersion >

(first stage polymerization)

A solution obtained by dissolving 8 parts by mass of sodium lauryl sulfate into 3000 parts by mass of ion exchange water was added to a reaction vessel equipped with a stirring device, a temperature sensor, a cooling tube, and a nitrogen introduction device, and stirred at a stirring speed of 230rpm under a nitrogen stream, and the internal temperature was raised to 80 ℃. After the temperature was raised, a solution obtained by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added, the liquid temperature was adjusted to 80 ℃ again, and a polymerizable monomer solution containing 480 parts by mass of styrene, 250 parts by mass of n-butyl acrylate, 68.0 parts by mass of methacrylic acid, and 16.0 parts by mass of n-octyl 3-mercaptoacrylate was added dropwise over 1 hour, followed by heating and stirring at 80 ℃ for 2 hours to carry out polymerization, thereby preparing a styrene acrylic resin particle dispersion (1A) containing styrene acrylic resin particles (1A).

(second stage polymerization)

A solution obtained by dissolving 7 parts by mass of sodium polyoxyethylene (2) lauryl ether sulfate in 800 parts by mass of ion-exchanged water was added to a reaction vessel equipped with a stirring device, a temperature sensor, a cooling tube, and a nitrogen gas introduction device, and after heating to 98 ℃, a polymerizable monomer solution obtained as follows was added: 260 parts by mass of the styrene acrylic resin particle dispersion (1A) obtained in the above manner, 245 parts by mass of styrene, 120 parts by mass of n-butyl acrylate, 1.5 parts by mass of n-octyl 3-mercaptoacrylate, and 67 parts by mass of paraffin wax "HNP-11" (manufactured by japan ceresin corporation) as a release agent were dissolved at 90 ℃, and mixed and dispersed for 1 hour using a mechanical disperser "crearm mix (registered trademark)" (manufactured by M Technique corporation) having a circulation path, to prepare a dispersion containing emulsified particles (oil droplets). Subsequently, an initiator solution prepared by dissolving 6 parts by mass of sodium persulfate in 200 parts by mass of ion-exchanged water was added to the dispersion, and the system was heated and stirred at 82 ℃ for 1 hour to polymerize the same, thereby preparing a styrene acrylic resin particle dispersion (1B) containing styrene acrylic resin particles (1 a).

(third stage polymerization)

To the obtained styrene acrylic resin particle dispersion (1B), a solution obtained by dissolving 11 parts by mass of potassium persulfate in 400 parts by mass of ion exchange water was added, followed by dropwise adding a polymer monomer solution containing: 435 parts by mass of styrene, 130 parts by mass of n-butyl acrylate, 33 parts by mass of methacrylic acid, and 8 parts by mass of n-octyl 3-mercaptoacrylate. After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to carry out polymerization, and then cooled to 28 ℃ to obtain a styrene acrylic resin particle dispersion containing styrene acrylic resin 1.

[ preparation of toner 25]

In the above-described preparation of toner 1, toner 25 was obtained in the same manner except that polymer particle dispersion 1 was changed from 602 parts by mass in terms of solid content to 421 parts by mass, and that polyester resin particle dispersion was added in terms of solid content of 181 parts by mass.

(preparation of polyester resin particle Dispersion containing polyester resin)

To a 10-liter four-neck flask equipped with a nitrogen gas inlet tube, a dehydration tube, a stirrer, and a thermocouple, 524 parts by mass of a bisphenol a propylene oxide 2 mol adduct, 105 parts by mass of terephthalic acid, 69 parts by mass of fumaric acid, and 2 parts by mass of tin octylate (esterification catalyst) were added, and a polycondensation reaction was performed at a temperature of 230 ℃ for 8 hours. Further, after the polycondensation reaction was continued for 1 hour at 8kPa, cooling was performed to 160 ℃ to obtain a polyester resin 1. 100 parts by mass of polyester resin 1 was pulverized using "Randelville RM form" (manufactured by Deshou, K.K.), mixed with 638 parts by mass of a 0.26 mass% aqueous solution of sodium lauryl sulfate prepared in advance, and ultrasonically dispersed at 300 μm and V-LEVEL for 30 minutes using an ultrasonic homogenizer "US-150T" (manufactured by Nippon Seiki Seisaku-Sho K.K.) while stirring to obtain a polyester resin particle dispersion. The particle diameter of the polyester resin particles in the polyester resin particle dispersion was measured by a dynamic light scattering method using "Microtrac UPA" (manufactured by japan electronics and electronics industries, ltd.), and the volume-based median particle diameter thereof was 135 nm.

(number average molecular weight Mn)

The number average molecular weight Mn of the polymers 1 to 3, 5 to 18 prepared in the above manner was measured according to the GPC method. Specifically, using an apparatus "HLC-8120 GPC" (manufactured by Tosoh Corp.) and a column "TSKguardcolumn + TSKgelSuperHZ-M3 series" (manufactured by Tosoh Corp.), the column temperature was maintained at 40 ℃ and Tetrahydrofuran (THF) was flowed at a flow rate of 0.2 mL/min as a carrier solvent. The measurement sample was dissolved in tetrahydrofuran to reach a concentration of 1 mg/ml. The solution was prepared by treatment at room temperature for five minutes using an ultrasonic disperser. Subsequently, a sample solution was obtained by treatment using a membrane filter having a pore size of 0.2 μm, and 10 μ L of the sample solution was injected into the apparatus together with the carrier solvent and detected using a refractive index detector (RI detector). The molecular weight distribution of the measurement sample was calculated from a calibration curve prepared using monodisperse polystyrene standard particles. Polystyrene was used as a detection amount curve at 10 points or more.

In addition, in polymers 10 to 17, the number average molecular weight of the macroinitiator was measured in accordance with the above method except for the total number average molecular weight. Further, the number average molecular weight of the macroinitiator is defined as the number average molecular weight of the polymer block α or β, and the total number average molecular weight of the other polymer block (number average molecular weight of the other polymer block × the number of blocks) is obtained by subtracting (number average molecular weight of macroinitiator × the number of blocks) from the total number average molecular weight of the polymer for each block structure. The results are shown in Table 3. In table 3, Mn represents the total number average molecular weight of the polymer, α Mn represents the total number average molecular weight of the polymer block α, and β Mn represents the total number average molecular weight of the polymer block β.

[ evaluation: light-responsive adhesion test of composition

The changes in adhesion with light irradiation of the compositions 1 to 25 prepared in the respective examples were evaluated by the following light-responsive adhesion test using the apparatus shown in FIG. 3. As shown in FIG. 3, 2mg of the composition was placed on an 18mm square glass coverslip 1 within a 6mm radius from the center of the glass and the entire composition was covered with the same size glass coverslip 2 at a position offset in the parallel direction by about 4mm relative to the glass coverslip 1. The composition was heated to melt the sample and bond cover glass 1 to cover glass 2. The resulting sample was subjected to the following non-fluidic → fluidic experiment, followed by the fluidic → non-fluidic experiment.

< non-fluidic → fluidic experiment (fluidization experiment) >

A portion (A) shown in FIG. 3 was fixed to a stand with a transparent adhesive tape, and a plastic string having a length of 30cm and a weight of 100g was fixed to a portion (C) with a transparent adhesive tape. Irradiating the part (B) with an irradiation dose of 30J/cm²The cover glass 2 was confirmed to be peeled from the cover glass 1 by irradiating light having a wavelength of 365nm, and the result was judged according to the following evaluation criteria.

Evaluation criteria for non-fluidic → fluidic experiment (fluidization experiment)

O: the cover glass 2 is completely separated from the cover glass 1

And (delta): the cover glass 2 is moved

X: the cover glass 2 is not moved.

< fluidity → non-fluidity test >

After the experiment of non-fluidities → fluidities is completed, the following experiment was performed on the sample in which the cover glass 2 completely detached and the sample in which the displacement occurred. In addition, for the displaced sample, cover glasses 1 and 2 were torn off by hand. After completion of the light irradiation for 5 minutes (5 minutes in the room temperature (range of 25 ± 15 ℃) and under visible light irradiation conditions such as a fluorescent lamp) in the non-fluidic → fluidic experiment, the laminated cover glass 3 (having the same size as the cover glasses 1 and 2) was placed so as to cover the sample portion ((B) portion) of the cover glass 1 used in the above experiment, and whether or not the cover glasses 1 and 3 were adhered was checked and judged according to the following evaluation criteria.

Evaluation criteria for fluidic → non-fluidic experiments (non-fluidic experiments)

O: not adhered (non-fluidized occurred)

And (delta): a part of the adhesive is adhered (a part of the adhesive is kept in a fluidized state)

X: bonding occurs (maintaining the fluidized state).

The evaluation results of the compositions 1 to 25 containing the isomerized polymer and the isomerized low-molecular compound in both the fluidization experiments and the non-fluidization experiments were all o, and it was confirmed that fluidization was caused by light irradiation and non-fluidization was reversibly caused.

[ evaluation: fixability test)

(preparation of developer)

The toners 1 to 27 prepared in the above manner and the developers of comparative examples 1 and 2 were obtained by mixing ferrite carrier particles having a volume average particle diameter of 30 μm coated with a copolymer resin of cyclohexyl methacrylate and methyl methacrylate (monomer mass ratio of 1:1) and making the toner particles 6 mass%. Mixing was performed for 30 minutes using a V-type mixer.

(fixation test)

The developers 1 to 27 obtained above and the developers of comparative examples 1 and 2 were used to perform a fixing property test in a normal temperature and normal humidity environment (temperature 20 ℃ C., relative humidity 50% RH). Specifically, a developer is provided on one side and plain paper is provided on the other side as a recording medium (weight per square meter: 64 g/m)²) The developer was placed between a pair of parallel flat (aluminum) electrodes, and the developer was made to slide by magnetic force, the gap between the electrodes was 0.5mm, and the DC bias and the AC bias were set at a toner adhesion amount of 6g/m²The toner is developed under the conditions of (1), a toner image is formed on the surface of the above plain paper, and fixed in each apparatus, thereby obtaining a printed matter (image formation).

The printed matter was folded by a folding machine so as to apply a load thereto, and then compressed air of 0.45MPa was blown onto the image portion. The fold was evaluated in grades according to the following evaluation criteria, and a grade of 3 or more was regarded as passed.

6: completely without creases

5: there is slight peeling along the fold

4: partial peeling along the fold

3: with thin lines of peel along the folds

2: with thick lines along the folds

1: there is greater peeling along the fold.

The fixing device used the following four fixing devices configured by appropriately changing the device shown in fig. 2:

no.1 No.2 shows a heating part 93 having a temperature of 20 ℃ without the pressure-bonding part 9 of FIG. 2, and an ultraviolet ray irradiated from the light source 41 having a wavelength of 365nm (light source: LED light source having an emission wavelength of 365 nm. + -. 10 nm) in an irradiation amount of 7J/cm²And 11J/cm²。

No.2 in the pressure-bonding section 9 of FIG. 2, the temperature of the heating member 93 was 20 ℃, the temperature of the pressing member 91 was 20 ℃, the pressure during pressing was 0.2MPa, and the wavelength and the dose of the light source 41 were the same as those of No. 1.

No.3 in which the pressure-bonding section 9 of FIG. 2 was present, the temperature of the heating member 93 was 20 ℃, the temperature of the pressing member 91 was 80 ℃, the pressure during pressing was 0.2MPa, and the wavelength and the dose of the light source 41 were the same as those of No. 1.

No.4 No.2 shows that the temperature of the heating member 93 was 80 ℃ without the pressure-bonding section 9, and the wavelength and the dose of the light source 41 were the same as those of No. 1.

[ evaluation of color reproducibility ]

The color reproducibility of the images of the examples and comparative examples obtained above was evaluated by visual evaluation by 10 inspectors based on the following criteria. Specifically, as a sample for evaluation, a toner was prepared in which all of polymer 1 in example 1 was changed to a styrene acrylic resin. A developer was prepared using this toner in the same manner as described above, developed in the same manner as in the image formation in the above-described fixability test, and fixed in the following fixing device No.5:

no.5 in the pressure-bonding section 9 of FIG. 2, the temperature of the heating member 93 was 20 ℃ and the temperature of the pressing member 91 was 150 ℃ and the pressure at the time of pressing was 0.2MPa, and light irradiation was not performed.

Ten monitors were given a question of whether or not there was a significant difference in color between the evaluation comparison sample and the images obtained in the above examples and comparative examples. The results of determination made according to the following evaluation criteria for color reproducibility are shown in table 4 below:

evaluation criterion for color reproducibility

Very good: 2 answers below are clearly different

O: 3-4 answers are obviously different

And (delta): 5-7 answers with obvious difference

X: more than 8 answers are obviously different

The results are shown in tables 3 and 4.

As shown in table 4, toners 1 to 27 using the compositions of the present invention all showed high fixability by fixing by light irradiation.

Toners 1 to 3, 26 and 27 using compositions 1 to 3, 24 and 25 containing a polymer derived from a structural unit of an azobenzene derivative and an azobenzene compound, toner 4 using composition 4 containing a polymer derived from a structural unit of an azobenzene derivative and an azobenzene compound, toner 5 using composition 5 containing a polymer derived from a structural unit of an azobenzene derivative and an azobenzene compound, and toner 6 using composition 6 containing a polymer derived from a structural unit of an azobenzene derivative and an azobenzene compound all exhibited high fixability by light irradiation.

On the other hand, as described in comparative examples 1 and 2, the toner prepared using only the polymer 5 or the compound 6 was insufficient in fixability. It was found that the fixability was low particularly in the case where the light irradiation amount was low. Thus, by using the polymer and the compound in combination, fixing can be performed at a lower light irradiation amount than when each is used alone.

The structural unit in the polymers of the compositions 1 to 6 contains a phenylene group having a linking part to a polymer main chain at a para position relative to a nitrogen-nitrogen double bond or a carbon-nitrogen double bond of an azobenzene derivative or the azobenzene derivative, and the azobenzene compound or the azobenzene compound contains a phenyl group having an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms at a para position relative to a nitrogen-nitrogen double bond or a carbon-nitrogen double bond, and it has been found that toners 1 to 6 using the compositions 1 to 6 can have more excellent fixing property at a low irradiation dose than a toner 11 using a composition 11 containing a polymer 2 containing a phenylene group having a linking part at a meta position.

The mixing ratio of the polymer to the compound in the composition is in the range of 99:1 to 10:90 (mass ratio) of the polymer to the compound, and good fixing properties can be obtained in all cases (examples 1,7 to 10). Among them, when the polymer-to-compound ratio is in the range of 30:70 to 90:10, the fixing property is more excellent, and when the polymer-to-compound ratio is in the range of 40:60 to 80:20, the fixing property is further excellent.

Good fixing property is obtained when any of homopolymer, random copolymer, and block copolymer is used as the polymer. Among these, toners 1 to 6, 16 to 18, 20 to 23, and 26 to 27 using a composition using a homopolymer or a block copolymer as a polymer tend to have more excellent fixing properties at a low irradiation dose than toners 12 to 15 using a random copolymer. When the number average molecular weight of the polymer is 3500 or more and when the polymer is a block copolymer, the total number average molecular weight of the respective polymer blocks is 1000 or more, and more excellent fixing property can be obtained.

The toner may contain not only the composition but also a binder resin. As shown in toners 24 and 25, when a binder resin is further used, good fixing property can be similarly obtained.

When the fixing devices were compared and the same type of toner 1 was used and irradiated with ultraviolet rays under the same conditions, it was found that the fixing device of No.2 in which pressure was applied by the pressure member and the fixing device of No.3 in which pressure was applied by heat by the pressure member were more excellent in fixing properties than the fixing device of No.1 in which no pressure member was used (comparative examples 1, 26, and 27). Further, by using the same toner 1 and irradiating ultraviolet rays under the same conditions, the fixing device using No.4 heated by the heating member 93 obtained better fixing performance than the fixing device of No.1 which was not heated at the time of ultraviolet ray irradiation (examples 1 and 28).

Further, it was found that the toners 1 to 3, 7 to 27 using the compositions 1 to 3, 7 to 25 containing a polymer of a structural unit derived from an azomethine derivative and an azomethine compound exhibited excellent color reproducibility.

Description of the figures

1 photosensitive body

2 electrified device

3 Exposure device

4 developing part

5 transfer printing part

7 paper conveying part

8 cleaning part

9 crimping part

10 image forming part

11 paper feeding part

12 transport roller

13 conveyor belt

14 paper discharge part

15 Manual paper feeding part

16 tray

17 hygrothermograph

20 image processing part

24 paper turning part

40 irradiating part

41 light source

71 image reading apparatus

72 automatic document feeder

85 scraping blade

90 control part

91. 92 pressing part

93 heating element

100 image forming apparatus

d original manuscript

S recording paper