Resin composition, toner for developing electrostatic images, image forming method, photosensitive adhesive, and photoswitching material

Abstract

To provide a resin composition which can more efficiently induce fluidization by light irradiation and non-fluidization after that.SOLUTION: A resin composition comprises: a resin which has a first base that can form at least two hydrogen bonds; and a photoisomerization compound which has a second base that can form at least two hydrogen bonds complementarily with the first base and has a portion that is reversibly isomerized by the light.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition, a toner for developing electrostatic images, an image forming method, a photosensitive adhesive, and a photoswitching material. [Background technology]

[0002] Azobenzene compounds are known as compounds that reversibly become fluid / non-fluid as a result of a photoisomerization reaction. For example, Patent Documents 1 and 2 disclose toner particles containing an azobenzene compound. These documents disclose a technology in which the azobenzene compound is cis-trans isomerized by light irradiation to induce a reversible phase change between a crystalline phase and an isotropic phase, thereby fluidizing / non-fluidizing the azobenzene compound and melting / fixing the toner particles. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-191078 A [Patent Document 2] JP 2014-191077 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the techniques described in Patent Documents 1 and 2 are insufficient to cause a phase change (fluidization / non-fluidization) of the entire toner particle by cis-trans isomerization of the azobenzene compound, and there was a problem that in order to realize a phase change of the entire toner particle of this configuration, it is necessary to impart a large amount of energy, such as the amount of irradiation and the temperature during irradiation.

[0005] Therefore, an object of the present invention is to provide a resin composition capable of more efficiently inducing fluidization and subsequent non-fluidization by light irradiation. Another object of the present invention is to provide a toner containing a resin composition capable of more efficiently inducing fluidization and subsequent non-fluidization by light irradiation, the toner having excellent fixing properties and fine line reproducibility. [Means for solving the problem]

[0006] The present inventors have conducted extensive research in view of the above problems. As a result, they have found that a resin composition containing a specific resin and a specific photoisomerizable compound can more efficiently induce fluidization and subsequent non-fluidization by light irradiation. They have also found that the fixability and fine line reproducibility of a toner can be improved by incorporating the above resin composition in the toner, and have completed the present invention.

[0007] That is, the present invention is achieved by the resin compositions shown in the following items 1 to 19, the toner and image forming method containing the same, and the photosensitive adhesive and photoswitching material using the same.

[0008] 1. A resin composition comprising: a resin having a first group capable of forming at least two hydrogen bonds; and a photoisomerizable compound having a second group capable of forming at least two hydrogen bonds complementary to the first group, and having a site that is reversibly isomerized by light.

[0009] 2. The resin is represented by the following general formula (1):

[0010] [ka]

[0011] In general formula (1), M represents a linking group; B1 represents a first group capable of forming at least two hydrogen bonds, The structure includes The photoisomerizable compound is represented by the following general formula (2):

[0012] [ka]

[0013] In general formula (2), L1 and L2 each independently represent a linking group. A1 and A2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group; Z1 and Z2 each independently represent N or CH; B2 represents a second group capable of forming at least two hydrogen bonds complementary to the first group; n is an integer from 1 to 10, When n is 1, G represents a second group capable of forming at least two hydrogen bonds complementarily with the first group, and when n is 2 to 10, G represents an n-valent substituent or an n-valent third group capable of forming at least two hydrogen bonds complementarily with the first group. The resin composition according to the above item 1, wherein the compound is represented by the formula:

[0014] 3. The resin composition according to 1 or 2 above, wherein the resin has at least one main chain selected from the group consisting of acrylic resins, styrene-acrylic resins and polyester resins.

[0015] 4. The resin composition according to any one of 1. to 3. above, wherein in the general formula (2), Z1 and Z2 are each independently N or CH, and Z1≠Z2.

[0016] 5. The resin composition according to any one of 1. to 4. above, wherein the first group and the second group are each independently a residue of any one compound selected from the group consisting of adenine, thymine, 2,6-diacylaminopyridine, uracil, melamine, cyanuric acid, phthalimide, and 2,6-diamino-1,3,5-triazine.

[0017] 6. The resin composition according to any one of 1. to 5. above, wherein the first group and the second group are a pair of residues selected from adenine / thymine, 2,6-diacylaminopyridine / uracil, melamine / cyanuric acid, and 2,6-diamino-1,3,5-triazine / phthalimide.

[0018] 7. The resin composition according to any one of 1 to 6 above, which is rendered fluid by light irradiation and then rendered non-fluid.

[0019] 8. The resin composition according to 7 above, wherein the light irradiation has a wavelength of 250 nm to 480 nm.

[0020] 9. A toner comprising the resin composition according to any one of 1. to 8. above.

[0021] 10. The toner according to claim 9, further comprising a binder resin.

[0022] 11. The toner according to item 10 above, wherein the binder resin comprises at least one resin selected from the group consisting of styrene-acrylic resins and polyester resins.

[0023] 12. The toner according to any one of 9. to 11. above, further comprising a colorant.

[0024] 13. The toner according to any one of 9. to 12. above, further comprising a release agent.

[0025] 14. An image forming method comprising the steps of: forming a toner image made of the toner according to any one of 9. to 13. above on a recording medium; and irradiating the toner image with light to soften the toner image.

[0026] 15. The image forming method according to claim 14, wherein the wavelength of the light is 280 nm or more and 480 nm or less.

[0027] 16. The image forming method according to claim 14 or 15, further comprising a step of pressing the toner image.

[0028] 17. The image forming method according to claim 16, wherein the toner image is further heated in the pressurizing step.

[0029] 18. A photosensitive adhesive using the resin composition described in any one of 1. to 8. above.

[0030] 19. An optical switching material comprising the resin composition according to any one of 1. to 8. above. Effect of the Invention

[0031] According to the present invention, there is provided a resin composition in which fluidization and subsequent non-fluidization can be induced more efficiently by light irradiation. [Brief description of the drawings]

[0032] [Figure 1] FIG. 1 is a schematic diagram showing an image forming apparatus 100 used in an image forming method according to an embodiment of the present invention. [Diagram 2] 2 is a schematic configuration diagram of an irradiation unit 40 in the image forming apparatus 100. FIG. [Diagram 3] FIG. 1 is a schematic diagram of an apparatus for measuring changes in fluidity and non-fluidity (adhesiveness) accompanying light irradiation of the photoresponsive compounds synthesized in the Examples and Comparative Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] The resin composition of the present invention comprises a resin having a first group capable of forming at least two hydrogen bonds, and a photoisomerizable compound having a second group capable of forming at least two hydrogen bonds complementary to the first group, and having a site that is reversibly isomerized by light.

[0034] Here, the first group and the second group will be explained. The first group and the second group are groups capable of forming at least two hydrogen bonds between the two groups. Specifically, the first group and the second group are groups that form complementary multiple hydrogen bonds, which will be described later, and have a plurality of hydrogen bond acceptors and hydrogen bond donors in their structures, and are capable of forming two or more hydrogen bonds between molecules in a complementary manner. Hereinafter, such groups that form two or more hydrogen bonds between two groups in a complementary manner will also be referred to as "complementary multiple hydrogen bond groups."

[0035] In the present invention, complementary multiple hydrogen bonding groups are introduced into the resin and the photoisomerization compound contained in the resin composition. As a result, in the resin composition, two or more hydrogen bonds are formed between the complementary multiple hydrogen bonding groups of the resin and the complementary multiple hydrogen bonding groups of the photoisomerization compound. That is, in the resin composition, the resin and the photoisomerization compound are bonded via the complementary multiple hydrogen bonding groups that they have, so that a molecule larger than that of the resin blended in the resin composition is formed. In this case, the resin composition has a higher viscosity than the blended resin.

[0036] It is believed that the fluidization caused by a photoisomerization compound having liquid crystal properties occurs when a non-fluid trans isomer (E) is irradiated with light and isomerized to a cis isomer (Z), which breaks down the regular structure of the crystal and induces a phase transition, thereby inducing fluidization. The mechanism is believed to be as follows. When a photoisomerization compound (trans isomer) is irradiated with light, the photoisomerization compound on the crystal surface is first isomerized from a trans isomer to a cis isomer. This breaks down the crystal structure of the photoisomerization compound and causes it to fluidize. The dissolved crystal surface layer undergoes a phase transition from a crystalline state to a liquid state, improving the light transmittance and allowing the light to reach the inside of the crystal. The crystal layer gradually breaks down from the outermost layer of the crystal, causing the entire layer to fluidize. However, when these photoisomerization compounds are mixed with resins (so-called binder resins) such as styrene acrylic resins and polyester resins to form resin compositions, there is a concern that the entire resin composition may not be sufficiently fluidized by the fluidization of the photoisomerization compound alone. That is, in order to induce fluidization / non-fluidization in a resin composition, it is necessary to increase the content of the photoisomerization compound in the resin composition, but if the amount of the photoisomerization compound, which has a smaller molecular weight than the resin, is increased, it acts like a plasticizer, causing the entire composition to have low elasticity, making it difficult to obtain the desired physical properties. Therefore, the inventors of the present invention came to the following idea.

[0037] It is known that when polymers are bonded together by a covalent bond (i.e., crosslinked), the elastic modulus of the resulting crosslinked polymer is improved, and the elastic modulus is improved even in areas with a low degree of crosslinking. Here, the current toner fixing by electrophotography uses the principle that the elastic modulus of the entire toner is reduced by heat and melted, the melted toner is attached to the fixing target, and then the toner is cooled and the elastic modulus is improved and fixed. Therefore, the inventors of the present invention thought that if it is possible to increase the elasticity by crosslinking a low-elasticity resin (e.g., styrene acrylic resin, polyester resin, etc.) with a photoisomerization compound with a non-covalent bond such as a hydrogen bond (complementary multiple hydrogen bond) like a supramolecule, the desired elastic modulus during melting and fixing can be achieved. In addition, since crosslinking is usually a covalent bond and therefore not reversible, the above-mentioned hydrogen bond (complementary multiple hydrogen bond) can be cut by applying external energy, and therefore the inventors thought that it would be possible to impart reversibility to the bond between the resin and the photoisomerization compound, and arrived at the present invention. Although the bond energy of each hydrogen bond is small, it is known that the use of multiple hydrogen bonds can result in bond energy comparable to that of covalent bonds, and as a result, physical properties such as elastic modulus can be improved. In the present invention, a resin and a photoisomerizable compound having a photoisomerizable site are hydrogen-bonded (complementary multiple hydrogen bonds) to enable the reversible formation and cleavage of hydrogen bonds by light. In other words, the present invention has discovered that it is possible to reduce or increase elasticity by light irradiation by introducing complementary multiple hydrogen bond sites that form multiple hydrogen bonds into the resin and the photoisomerizable compound having a photoisomerizable site.

[0038] It is believed that the photoisomerizable compound having liquid crystal properties undergoes crystallization promotion after isomerization from the cis form to the trans form, and thus undergoes non-fluidization from a fluidized molten state. This crystallization is difficult to proceed in the presence of impurities, so that if the isomerization rate to the trans form is low, crystallization may not proceed sufficiently, and non-fluidization may be insufficient. Even if the isomerization rate from the cis form to the trans form is low, the resin composition of the present invention is expected to have an improved elastic modulus due to the formation of hydrogen bonds between the complementary multiple bond groups of the resin and the photoisomerizable compound. Therefore, the resin composition of the present invention can achieve rapid and reliable non-fluidization.

[0039] From the above, it is believed that the resin composition of the present invention can reversibly induce the fluidization / immobilization phenomenon by isomerization by light, and can achieve rapid and reliable immobilization. In addition, by introducing the resin composition of the present invention into a toner, a toner with high fixing property and fine line reproducibility can be obtained.

[0040] The complementary multiple hydrogen bonding group is not particularly limited as long as it has a structure that forms two or more hydrogen bonds, and examples thereof include residues of nucleic acid bases such as adenine and guanine, which are purine derivatives, and cytosine, thymine, and uracil, which are pyrimidine derivatives, and derivatives thereof; urea, thiourea, melamine, cyanuric acid, barbituric acid, 2,6-diacylaminopyridines such as 2,6-diacetylaminopyridine and 2,6-dipropionylaminopyridine, 4,6-diamino-2-pyrimidinone, 2-amino-4,6-pyrimidinedinone, 2,4,6-triaminopyrimidine, phthalimide, 2,6-diamino-1,3,5-triazine, 2-ureido-4-amino-1,3,5-triazine, and 2-ureido-4-pyrimidinone, and residues of derivatives thereof (monovalent group, n-valent group). Among these, the complementary multiple hydrogen bonding group B is preferably a residue of adenine, thymine, 2,6-diacylaminopyridine, uracil, melamine, cyanuric acid, phthalimide, 2,6-diamino-1,3,5-triazine and derivatives thereof, which form a pair of nucleic acid bases.

[0041] Here, in the resin composition of the present invention, the first group (more preferably B1) possessed by the resin, the second group (more preferably B2 and G when n is 1) possessed by the photoisomerization compound, and the third group (G when n is 2 to 10) which may be possessed by the photoisomerization compound correspond to complementary multiple hydrogen bonding groups. For example, B1 and B2 are monovalent groups, G when n is 1 is a monovalent group, and G when n is 2 to 10 is an n-valent group. Thus, B1 and B2 are monovalent residues of complementary multiple hydrogen bonding groups, G when n is 1 is a monovalent residue of complementary multiple hydrogen bonding groups, and G when n is 2 to 10 is an n-valent residue of complementary multiple hydrogen bonding groups.

[0042] In the resin composition of the present invention, the complementary multiple hydrogen bonding groups essentially consist of a first group possessed by the resin and a second group possessed by the photoisomerizable compound. In a preferred embodiment, the first group and the second group are each independently a residue of any one compound selected from the group consisting of adenine, thymine, 2,6-diacylaminopyridine, uracil, melamine, cyanuric acid, phthalimide, and 2,6-diamino-1,3,5-triazine.

[0043] In addition, the complementary multiple hydrogen-bonding group is a pair of a first group carried by the resin and a second group carried by the photoisomerizable compound, and forms a hydrogen bond between the first group and the second group. Examples of such pairs of complementary multiple hydrogen-bonding groups (combinations of a first group and a second group) include adenine / thymine, adenine / uracil, guanine / cytosine, melamine / barbituric acid, melamine / cyanuric acid, 2,6-diacylaminopyrimidine / uracil, 4,6-diamino-2-pyrimidinone / 2-amino-4,6-pyrimidinone, 2,4,6-triaminopyrimidine / barbit ... Examples of suitable amines include 1,3,5-triazine / phthalimide, 2,4,6-triaminopyrimidine / barbituric acid, 2,4,6-triaminopyrimidine / phthalimide, and derivatives thereof, and urea, thiourea, 2,6-diamino-1,3,5-triazine, 2-ureido-4-amino-1,3,5-triazine, and 2-ureido-4-pyrimidinone, and derivatives thereof, which can form pairs with the same structure. Among these, preferred are adenine / thymine, which form a pair of nucleic acid bases, and 2,6-diacylaminopyrimidine / uracil, melamine / cyanuric acid, and 2,4,6-triaminopyrimidine / barbituric acid / phthalimide, which have a highly symmetric structure and can form stable hydrogen bonds.

[0044] Thus, in a preferred embodiment, the first group and the second group are pairs of residues selected from adenine / thymine, 2,6-diacylaminopyridine / uracil, melamine / cyanuric acid, and 2,6-diamino-1,3,5-triazine / phthalimide.

[0045] Here, multiple hydrogen bonds in the present invention will be described using as examples guanine / cytosine and adenine / thymine that form hydrogen bonds between nucleic acid bases. As described above, the first group (more preferably B1) possessed by the resin, the second group (more preferably B2 and G when n is 1) possessed by the photoisomerizable compound, and the third group (G when n is 2 to 10) that may be possessed by the photoisomerizable compound correspond to complementary multiple hydrogen bonding groups. These first and second groups form two or more hydrogen bonds between two molecules, such as the pairs of guanine / cytosine and adenine / thymine shown below.

[0046] [ka]

[0047] In guanine, the hydrogen atoms of NH and N-H2 are acceptors, and the lone electron pair of the oxygen of the carbonyl group is the donor, while in its counterpart, cytosine, the hydrogen atom of N-H2 is the acceptor, and the lone electron pair of the nitrogen atom and the lone electron pair of the oxygen of the carbonyl group are donors. The donor of guanine and the acceptor of cytosine form hydrogen bonds, and the acceptor of guanine and the donor of cytosine form hydrogen bonds, forming multiple complementary hydrogen bonds.

[0048] For example, in a compound having a guanine residue at one end and a cytosine residue at the other end in a molecule, the guanine and cytosine residues form complementary multiple hydrogen bonds in solution to form a supramolecular polymer. Although the bond energy of each hydrogen bond is small, the formation of multiple multiple hydrogen bonds gives rise to the physical properties of a polymer.

[0049] That is, in the resin composition of the present invention, a supramolecular polymer is formed by forming complementary multiple hydrogen bonds between the first group of the resin and the second group of the photoisomerizable compound. Moreover, this hydrogen bond can be reversibly cut and formed by applying energy such as light irradiation. This is how the effects of the present invention are achieved.

[0050] For example, the resin composition is used in a state in which a supramolecular polymer is formed. Then, when fluidization is required, the hydrogen bonds between the resin and the photoisomerization compound formed in the resin composition are broken by light irradiation, thereby reducing the viscosity (reducing elastic pressure) of the resin composition. Thereafter, when non-fluidization is required, the complementary multiple hydrogen bonding groups of the resin and the complementary multiple hydrogen bonding groups of the photoisomerization compound in the resin composition are formed with hydrogen bonds by light irradiation, thereby increasing the viscosity (reducing elastic pressure) of the resin composition. Thus, the resin composition of the present invention can be fluidized by light irradiation and then non-fluidized.

[0051] <Resin> The resin contained in the resin composition of the present invention has complementary multiple hydrogen bonding groups and preferably has a structure represented by the following general formula (1).

[0052] [ka]

[0053] In general formula (1), M represents a linking group, and B1 represents a first group (complementary multiple hydrogen bonding first group) capable of forming at least two hydrogen bonds. M is a linking group that links the first group B1 to the main chain portion, and the structure represented by general formula (1) is also referred to as the "side chain portion" below. Thus, the resin includes a main chain portion and a side chain portion (-M-B1). In a preferred embodiment, the resin preferably has a "unit (S) that does not have a complementary multiple hydrogen bonding group (first group)" (hereinafter also simply referred to as the "unit S") and a "unit (T) that has a complementary multiple hydrogen bonding group (first group)" (hereinafter also simply referred to as the "unit T") in the main chain portion. In this case, the "unit (T) that has a complementary multiple hydrogen bonding group" has a side chain portion represented by the above general formula (1).

[0054] In general formula (1), the complementary multiple hydrogen bonding groups which can constitute B1 are omitted here because the above-mentioned complementary multiple hydrogen bonding groups can be similarly applied.

[0055] In general formula (1), examples of the linking group that may constitute M include a group selected from the group consisting of alkylene groups (e.g., methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, cyclohexane-1,4-diyl, etc.), alkenylene groups (e.g., ethene-1,2-diyl, butadiene-1,4-diyl, etc.), alkynylene groups (e.g., ethyne-1,2-diyl, butane-1,3-diyne-1,4-diyl, etc.), linking groups derived from a compound containing at least one aromatic group (e.g., substituted or unsubstituted benzene, condensed polycyclic hydrocarbons, aromatic heterocycles, aromatic hydrocarbon ring assemblies, aromatic heterocycle assemblies, etc.), and linking groups containing a heteroatom (oxygen atom, sulfur atom, nitrogen atom, silicon atom, phosphorus atom, etc.), or a group consisting of a combination of one or more types selected from the group. Among these, the linking group that can constitute M is preferably a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), an arylene group having 6 to 10 carbon atoms, and a heteroatom linking group (preferably oxygen, sulfur, nitrogen), or a group combining two or more types selected from this group. These linking groups may be further substituted with a substituent described later, and may be combined to form a composite group.

[0056] Here, examples of the heteroatom-containing linking group include -NH-, -NHCO-, -CO-, -COO-, -OOC-, -NHCOO-, -O-, -S-, etc. Among these, -NH-, -S-, -CO- and -COO- are preferred.

[0057] In this specification, "substituted" means that the functional group or partial structure of interest is substituted with a substituent that may be optionally possessed. The optionally possessed substituent is selected from a deuterium atom, a halogen group (fluoro group, chloro group, bromo group, iodo group), a cyano group, an unsubstituted monovalent alkyl group having 1 to 20 carbon atoms, a monovalent alkyl group substituted with a halogen, an unsubstituted monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or an unsubstituted monovalent aromatic heterocyclic group having 5 to 30 ring atoms. Here, the unsubstituted alkyl group having 1 to 20 carbon atoms, the unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and the unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms are not particularly limited. For example, in general formula (2) described later, examples of monovalent groups include the monovalent groups of the compounds exemplified as the unsubstituted divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, the unsubstituted divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the unsubstituted divalent unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms, which may respectively constitute A1 and A2.

[0058] The main chain portion of the resin constituting the resin composition is not particularly limited, and examples thereof include polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyurethane, polytetrafluoroethylene, styrene-butadiene-acrylonitrile resin (ABS resin), styrene resin (polystyrene), acrylonitrile-styrene resin (AS resin), acrylic resin such as polymethyl methacrylate (PMMA), styrene acrylic resin, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, glass fiber reinforced polyethylene terephthalate, polyester resin such as polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyether sulfone, amorphous polyarylate, liquid crystal polymer, polyether ether ketone, polyimide, polyamide imide, polylactic acid, silicone resin, olefin resin, amide resin, epoxy resin, and copolymers thereof. These resins can be used alone or in combination of two or more. Of these, the resin is preferably one or more selected from acrylic resin, styrene acrylic resin, and polyester resin. In the present invention, the resin is preferably a styrene-acrylic resin or a polyester resin, and more preferably a styrene-acrylic resin.

[0059] Therefore, the main chain portion composed of the "unit (S) not having a complementary multiple hydrogen bonding group B" and the "unit (T) having a complementary multiple hydrogen bonding group B" is preferably selected from an acrylic resin, a styrene acrylic resin, and a polyester resin.

[0060] In all units of the resin according to the present invention, the ratio (S / T) of the number of moles of units (S) not having a complementary multiple hydrogen bonding group B to the number of moles of units (T) having a complementary multiple hydrogen bonding group B is not particularly limited as long as the desired physical properties are achieved, but is preferably 99 / 1 to 1 / 99, more preferably 97 / 3 to 50 / 50, and even more preferably 95 / 5 to 80 / 20.

[0061] (Acrylic resin) The acrylic resin in the present invention is formed by polymerization using at least a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomer has a functional group having an ester bond in the side chain. Specifically, in addition to an acrylic acid ester monomer represented by CH2=CHCOOR (R is an alkyl group), it includes vinyl ester compounds such as a methacrylic acid ester monomer represented by CH2=C(CH3)COOR (R is an alkyl group).

[0062] Representative (meth)acrylic acid ester monomers include, but are not limited to, the acrylic acid ester monomers and methacrylic acid ester monomers shown below. Examples of the acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate phenyl. Examples of the methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate.

[0063] These acrylic acid ester monomers or methacrylic acid ester monomers can be used alone or in combination of two or more kinds.

[0064] (styrene acrylic resin) The styrene-acrylic resin in the present invention is formed by polymerization of at least a styrene monomer and a (meth)acrylic acid ester monomer. Here, the styrene monomer includes styrene represented by the structural formula CH2=CH-C6H5, as well as those having a structure having a known side chain or functional group in the styrene structure.

[0065] As the (meth)acrylic acid ester monomer, the compounds described above for the acrylic resin can be used in the same manner.

[0066] Specific examples of styrene monomers capable of forming styrene-acrylic resins are shown below, but are not limited to those shown below. Examples of styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene.

[0067] These styrene monomers, acrylic acid ester monomers, and methacrylic acid ester monomers can be used alone or in combination of two or more kinds.

[0068] In addition to the copolymers formed only from the above-mentioned styrene monomer and (meth)acrylic acid ester monomer, styrene-acrylic resins also include those formed by using a general vinyl monomer in addition to the styrene monomer and (meth)acrylic acid ester monomer. The following are examples of vinyl monomers that can be used in combination when forming the styrene-acrylic resin of the present invention, but the vinyl monomers that can be used in combination are not limited to those shown below.

[0069] (1) Olefins Ethylene, propylene, isobutylene, etc. (2) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (3) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (4) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc. (6)Other Vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide, and the like.

[0070] It is also possible to prepare a resin having a crosslinked structure by using a polyfunctional vinyl monomer. Furthermore, it is also possible to use a vinyl monomer having an ionic dissociation group in the side chain. Specific examples of the ionic dissociation group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specific examples of the vinyl monomer having these ionic dissociation groups are shown below.

[0071] Specific examples of vinyl monomers having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl esters, and itaconic acid monoalkyl esters.

[0072] The method for forming the styrene-acrylic resin is not particularly limited, and may be a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. If necessary, a known chain transfer agent such as n-octyl-3-mercaptopropionate may be used.

[0073] When forming the styrene-acrylic resin used in the present invention, the contents of the styrene monomer and the acrylic acid ester monomer are not particularly limited, and can be appropriately adjusted from the viewpoint of controlling the softening temperature and the glass transition temperature of the binder resin. Specifically, the content of the styrene monomer is preferably 40 to 95 mass% and more preferably 50 to 80 mass% based on the total monomers. The content of the acrylic acid ester monomer is preferably 5 to 60 mass% and more preferably 20 to 50 mass% based on the total monomers.

[0074] The method for forming the styrene-acrylic resin is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include the following azo- or diazo-based polymerization initiators and peroxide-based polymerization initiators.

[0075] Examples of the azo or diazo polymerization initiator include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile.

[0076] Examples of the peroxide polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane, and tris-(t-butylperoxy)triazine.

[0077] In addition, when forming styrene-acrylic resin particles by emulsion polymerization, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

[0078] The amount of the polymerization initiator to be added varies depending on the target molecular weight and molecular weight distribution, but specifically, it can be within the range of 0.1 to 5.0% by mass based on the amount of the polymerizable monomer to be added.

[0079] The polymerization temperature varies depending on the types of monomers and polymerization initiators used, but is preferably 50 to 100° C., and more preferably 55 to 90° C. The polymerization time varies depending on the types of monomers and polymerization initiators used, but is preferably, for example, 2 to 12 hours.

[0080] The styrene-acrylic resin particles formed by the emulsion polymerization method can be configured to have two or more layers made of resins with different compositions. In this case, the manufacturing method can be a multi-stage polymerization method in which a polymerization initiator and a polymerizable monomer are added to a dispersion of resin particles prepared by a conventional emulsion polymerization treatment (first stage polymerization), and this system is polymerized (second stage polymerization).

[0081] (polyester resin) The polyester resin is a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (a polyvalent carboxylic acid component) and a divalent or higher alcohol (a polyhydric alcohol component). The polyester resin may be amorphous or crystalline.

[0082] The valence of the polyvalent carboxylic acid component and the polyhydric alcohol component is preferably 2 to 3, and particularly preferably 2. Therefore, as a particularly preferred embodiment, the case where the valence is 2 (i.e., a dicarboxylic acid component and a diol component) will be described.

[0083] 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; and methylenesuccinic acid. unsaturated aliphatic dicarboxylic acids such as 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-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and anthracenedicarboxylic acid; and lower alkyl esters and acid anhydrides of these may also be used. The dicarboxylic acid component may be used alone or in combination of two or more.

[0084] In addition, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides of the above carboxylic acid compounds, or alkyl esters having 1 to 3 carbon atoms can also be used.

[0085] Examples of the diol component include 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 neopentanediol. Examples of the diol component include saturated aliphatic diols such as butyl 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; and aromatic diols such as bisphenols such as bisphenol A and bisphenol F, and alkylene oxide adducts of bisphenols such as ethylene oxide adducts and 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 kinds.

[0086] The method for producing the polyester resin is not particularly limited, and the polyester resin can be produced by polycondensing (esterifying) the polyvalent carboxylic acid component and the polyhydric alcohol component using a known esterification catalyst.

[0087] Examples of catalysts that can be used in the production of polyester resins include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; compounds of metals such as aluminum, zinc, manganese, antimony, titanium, tin, zirconium, and germanium; phosphorous compounds; phosphoric acid compounds; and amine compounds. Specifically, examples of tin compounds include dibutyltin oxide (dibutyltin oxide), tin octoate, tin dioctoate, and salts thereof. Examples of titanium compounds include titanium alkoxides such as tetra-normal-butyl titanate (Ti(On-Bu)4), tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as polyhydroxytitanium stearate; and titanium chelates such as titanium tetraacetylacetonate, titanium lactate, and titanium triethanolamine. Examples of germanium compounds include germanium dioxide. Examples of aluminum compounds include polyaluminum hydroxide, aluminum alkoxide, and tributylaluminate. These may be used alone or in combination of two or more.

[0088] The polymerization temperature is not particularly limited, but is preferably 70 to 250° C. The polymerization time is also not particularly limited, but is preferably 0.5 to 10 hours. During the polymerization, the reaction system may be decompressed as necessary.

[0089] An example of a resin having complementary multiple hydrogen bonding groups is a resin represented by the following structural formula: In the structural formula, the "-M-B1" portion is a side chain portion.

[0090] [ka]

[0091] In the above structural formula, M and B1 are defined as in general formula (1), and n and m represent the number of moles added. n and m correspond to the molar ratio of the above-mentioned "unit (S) not having a complementary multiple hydrogen-bonding group B" to the "unit (T) having a complementary multiple hydrogen-bonding group B." In the above styrene-acrylic resin, n=n1+n2+n3.

[0092] In the present invention, as long as the desired physical properties such as the fluidity / non-fluidity of the resin composition, the fixing rate of the toner, and the reproducibility of fine lines are exhibited, there is no particular limitation, but the number average molecular weight (Mn) of the resin is preferably 1000 to 500000, more preferably 2000 to 300000, and even more preferably 3000 to 100000. It is also known that the melting temperature range of the resin composition becomes sharper as the molecular weight distribution becomes narrower, and there is no particular limitation as long as the desired physical properties are exhibited, but the ratio of the mass average molecular weight to the number average molecular weight (Mw / Mn) is preferably 1.05 to 5.0, more preferably 1.10 to 3.0, and even more preferably 1.20 to 2.5.

[0093] The Mn and Mw / Mn of the resin can be measured by the method described in the Examples.

[0094] <Photoisomerizable compounds> Next, a photoisomerizable compound having a complementary multiple hydrogen bonding group will be described. The photoisomerizable compound may have a photoisomerizable site in the molecule that changes from a trans structure to a cis structure and / or from a cis structure to a trans structure by light, and may have a photoisomerizable site in the molecule such as a styryl structure (Ph-C=C-), an azo structure (-N=N-), an azomethine structure (-C=N-), a propenimine structure (-C=CC=N-), etc. In a preferred embodiment, the photoisomerizable compound is represented by the following general formula (2):

[0095] [ka]

[0096] In general formula (2), L1 and L2 each independently represent a linking group. A1 and A2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group; Z1 and Z2 each independently represent N or CH; B2 represents a second group capable of forming at least two hydrogen bonds complementary to the first group; n is an integer from 1 to 10, When n is 1, G represents a second group capable of forming at least two hydrogen bonds complementary to the first group, and when n is 2 to 10, G represents an n-valent substituent or an n-valent third group capable of forming at least two hydrogen bonds complementary to the first group. It is a compound represented by the formula:

[0097] In general formula (2), examples of the linking group that may constitute L1 and L2 include a single bond, an alkylene group (e.g., methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, cyclohexane-1,4-diyl, etc.), an alkenylene group (e.g., ethene-1,2-diyl, butadiene-1,4-diyl, etc.), an alkynylene group (e.g., ethyne-1,2-diyl, butane-1,3-diyne-1,4-diyl, etc.), a linking group derived from a compound containing at least one aromatic group (e.g., substituted or unsubstituted benzene, condensed polycyclic hydrocarbons, aromatic heterocycles, aromatic hydrocarbon ring assemblies, aromatic heterocycle assemblies, etc.), and a heteroatom-containing linking group (a group containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a phosphorus atom, etc.), or a group that combines one or more types selected from the group. Among these, L1 and L2 are preferably a group selected from the group consisting of a single bond, an alkylene group (preferably an alkyl group having 1 to 12 carbon atoms), a linking group derived from a compound containing at least one aromatic group (preferably benzene), and a heteroatom-containing linking group (preferably an oxygen atom or a nitrogen atom), or a group combining one or more types selected from the group. These linking groups may be further substituted with the above-mentioned substituents, and may be combined to form a composite group.

[0098] Here, examples of the heteroatom-containing linking group include -NH-, -NHCO-, -CO-, -COO-, -NHCOO-, -O-, -S-, etc. Among these, -NH-, -NHCO-, -CO-, and -COO- are preferred.

[0099] In a preferred embodiment, L1 and L2 are each independently -(NHCO-R) n - (wherein R is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n is an integer of 1 to 6). R is preferably an alkyl group having 1 to 3 carbon atoms, or a phenyl group or a naphthyl group, and n is preferably an integer of 1 to 3. Specifically, L1 and L2 are -NHCO-CH2CH2-; -NHCO-CH2CH2-NHCO-CH2CH2-; NHCO-(CH2CH2)2-NHCO-CH2CH2-; -NHCO-CH(CH3)CH2-NHCO-CH2CH2-; -NHCO-Ph-NHCO-CH2CH2- (wherein Ph=C6H4); and the like.

[0100] In the general formula (2), A1 and A2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group. The aromatic hydrocarbon group that can constitute A1 and A2 in the general formula (2) is not particularly limited, but is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and examples thereof include groups derived from a hydrocarbon (aromatic hydrocarbon) ring containing one or more aromatic rings having 6 to 30 carbon atoms. In addition, when the aromatic hydrocarbon ring group contains two or more rings, the two or more rings may be bonded to each other by a single bond or condensed. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a benzene ring, a pentalene ring, an indene ring, a naphthalene ring, an anthracene ring, an azulene ring, a heptalene ring, an acenaphthalene ring, a phenalene ring, a fluorene ring, a phenanthrene ring, a biphenyl ring, a terphenyl ring, a triphenylene ring, a pyrene ring, a chrysene ring, a picene ring, a perylene ring, a pentaphene ring, a pentacene ring, a tetraphene ring, a hexaphene ring, a hexacene ring, a rubicene ring, a trinaphthylene ring, a heptaphene ring, and a pyranthrene ring. That is, examples of the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups derived from these rings or groups derived from a combination of these rings. In this specification, the terms "group derived from a ring" and "group derived from a combination of rings" refer to a group obtained by removing hydrogen atoms directly bonded to ring constituent elements from the ring structure by the amount of valence, resulting in a free valence.

[0101] The aromatic heterocyclic group that can constitute A1 and A2 in the general formula (2) is not particularly limited, but is a divalent aromatic heterocyclic group having 5 to 30 ring atoms, for example, a group derived from a ring (aromatic heterocycle) having 5 to 60 ring atoms including one or more aromatic rings having one or more heteroatoms (e.g., nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S)) and the remaining ring atoms being carbon atoms (C). In addition, when the aromatic heterocyclic group contains two or more rings, the two or more rings may be bonded to each other by a single bond or condensed. The aromatic heterocycle that constitutes the divalent aromatic heterocyclic group is not particularly limited, but examples thereof include a π-electron deficient aromatic heterocycle, a π-electron rich aromatic heterocycle, and a π-electron deficient-π-electron rich mixed aromatic heterocycle obtained by mixing a π-electron deficient aromatic heterocycle and a π-electron rich aromatic heterocycle. Specific examples of the π-electron deficient aromatic heterocycle include a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a naphthyridine ring, an acridine ring, a phenazine ring, a benzoquinoline ring, a benzoisoquinoline ring, a phenanthridine ring, a phenanthroline ring, a benzoquinone ring, a coumarin ring, an anthraquinone ring, a fluorenone ring, etc. Specific examples of the π-electron rich aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyrrole ring, an indole ring, a carbazole ring, an indolocarbazole ring, etc. Specific examples of the π-electron deficient-π-electron rich mixed aromatic heterocycle include an imidazole ring, a benzimidazole ring, a pyrazole ring, an indazole ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, a thiazole ring, an isothiazole ring, a benzothiazole ring, a benzisothiazole ring, an imidazolinone ring, a benzimidazolinone ring, an imidazopyridine ring, an imidazopyrimidine ring, an imidazophenanthridine ring, a benzimidazophenanthridine ring, an azadibenzofuran ring, an azacarbazole ring, an azadibenzothiophene ring, a diazadibenzofuran ring, a diazacarbazole ring, a diazadibenzothiophene ring, a xanthone ring, and a thioxanthone ring.That is, examples of the divalent aromatic heterocyclic group having 5 to 30 ring atoms include groups derived from these rings and groups derived from a combination of these rings.

[0102] In the general formula (2), Z1 and Z2 each independently represent N or CH. In a preferred embodiment, Z1 and Z2 each independently represent N or CH, and Z1≠Z2. Z1 and Z2 are each the same as an aromatic heterocyclic group, and may be a monovalent group.

[0103] In general formula (2), B2 is a second group which is a complementary multiple hydrogen bonding group and forms two or more hydrogen bonds complementary to the first group B1. The complementary multiple hydrogen bonding group has been described above and will not be described here.

[0104] In formula (2), n is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and further preferably an integer of 1 to 4.

[0105] In general formula (2), when n is 1, G is the second group of the complementary multiple hydrogen bonding group, and forms two or more hydrogen bonds complementary to the first group B1. The complementary multiple hydrogen bonding group has been described above and will not be described here.

[0106] In general formula (2), G, when n is 2 to 10, represents an n-valent substituent or an n-valent third group capable of forming at least two hydrogen bonds complementary to the first group. Here, the n-valent third group is the above-mentioned complementary multiple hydrogen bonding group having n bonds capable of forming two or more hydrogen bonds with the first group. Thus, the n-valent third group is an n-valent group derived from the compound described in the above-mentioned complementary multiple hydrogen bonding group.

[0107] In addition, the n-valent substituent that can constitute G in general formula (2) can be various and is not particularly limited, for example, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group. The n-valent substituent may be a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic heterocyclic group, bonded to each other by a single bond. In addition, one or more groups selected from the group consisting of -O-, -NHCO-, -CO-, and -COO- may be incorporated between the aliphatic hydrocarbon group, aromatic hydrocarbon group, or aromatic heterocyclic group that is an n-valent substituent that can constitute G.

[0108] The aliphatic hydrocarbon group which is an n-valent substituent that may constitute G is not particularly limited, but is an n-valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include an n-valent saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and an n-valent unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms. Examples of the n-valent aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups and alicyclic hydrocarbon groups having 3 to 30 carbon atoms.

[0109] Examples of the n-valent aliphatic hydrocarbon group include, for example, when n=1, an alkyl group having 1 to 20 carbon atoms; when n=2, an alkylene group having 1 to 20 carbon atoms; when n=3, an alkanetriyl group having 2 to 20 carbon atoms; and when n=4, an alkanetetrayl group having 3 to 20 carbon atoms.

[0110] The aromatic hydrocarbon group which is an n-valent substituent that may constitute G is not particularly limited, but is an n-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. For example, an n-valent group derived from an aromatic hydrocarbon ring which constitutes a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may constitute A1 and A2 can be similarly applied.

[0111] The aromatic heterocyclic group which is an n-valent substituent that can constitute G is not particularly limited, and is an n-valent aromatic heterocyclic group having 5 to 30 ring atoms, and for example, an n-valent group derived from an aromatic heterocycle which constitutes a divalent aromatic heterocyclic group having 6 to 30 carbon atoms that can constitute A1 and A2 can be similarly applied. Among them, the aromatic heterocyclic group which is an n-valent substituent that can constitute G is preferably a group derived from a triazine ring.

[0112] Examples of the n-valent substituent that can constitute G in general formula (2) include n-valent groups (residues) derived from thiol compounds obtained by esterifying polyhydric alcohols such as pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, triazine, 1,3,5-benzenetricarboxylic acid, pentaerythritol, dipentaerythritol, trimethylolpropane, and ditrimethylolpropane with mercaptoacetic acid and 3-mercaptopropionic acid.

[0113] In a preferred embodiment, the n-valent substituent is represented by the following structural formulas (x-1) to (x-13). In the following structures, the site marked with "*" represents a bond to L2 in general formula (2). In the following structural formulas (x-1) and (x-2), R is an alkyl group having 1 to 10 carbon atoms.

[0114] [ka]

[0115] Examples of the photoisomerizable compound represented by general formula (2) include compounds 1 to 154 shown below.

[0116] [ka]

[0117] [ka]

[0118]

change

[0119]

change

[0120]

change

[0121]

change

[0122]

change

[0123]

change

[0124]

change

[0125]

change

[0126]

change

[0127]

change

[0128]

change

[0129] In the resin composition of the present invention, the molar ratio of the complementary multiple hydrogen bonding groups of the photoisomerizable compound to the complementary multiple hydrogen bonding groups of the resin (molar number of complementary multiple hydrogen bonding groups of the photoisomerizable compound / molar number of complementary multiple hydrogen bonding groups of the resin) is preferably 0.05 to 7.0, more preferably 0.1 to 5.0, even more preferably 0.2 to 3.0, particularly preferably 0.3 to 2.5, and most preferably 0.5 to 2.0. When the molar ratio of the complementary multiple hydrogen bonding groups of the resin and the photoisomerizable compound is within the above range, the effects of the present invention are more pronounced.

[0130] <Method for preparing photoisomerizable compound> The method for preparing the photoisomerizable compound represented by the general formula (2) (a photoisomerizable compound having a complementary multiple hydrogen-bonding group) is not particularly limited. For example, the photoisomerizable compound can be prepared by first preparing a desired photoisomerizable compound and then introducing a complementary multiple hydrogen-bonding group into the obtained photoisomerizable compound.

[0131] [Synthesis Example 1: Synthesis of photoisomerizable compound 1] <Synthesis of Azomethine-2NO2> A 2000 ml four-neck flask equipped with a cooling tube, nitrogen inlet tube, and thermometer was charged with 4-nitroaniline (Tokyo Chemical Industry Co., Ltd.) (80.0 g, 0.58 mol), 5-nitro-2-furaldehyde (Kanto Chemical Co., Ltd.) (81.7 g, 0.58 mol), and 1000 ml of ethanol, and the reaction solution was heated and stirred at 50°C. The reaction solution was then suction filtered, and the resulting powder was washed with cooled ethanol. Further, recrystallization was carried out in a mixed solvent of methanol / ethanol, yielding 128.6 g (yield 85%) of azomethine-2NO2. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0132] <Synthesis of azomethine-2NH2> The synthesis was carried out with reference to Chemistry of Heterocyclic Compounds, 2004,40(6), 701.

[0133] A 1000ml four-neck flask was equipped with two three-way stopcocks, a thermometer, a dropping funnel and a ball stopper, and the pressure in the container was reduced, followed by nitrogen replacement. This operation was repeated three times. While nitrogen was flowing, 400ml of ethyl acetate, azomethine-2NO2 (100.0g, 0.38mol) and allylpalladium(II) chloride dimer (2.8g, 8mmol) were added to the four-neck flask and stirred at room temperature for 30 minutes. Then, while keeping the temperature of the solution in the four-neck flask at 10℃ or less in an ice bath, triethylsilane (53.4g, 0.46mol) added to the dropping funnel was dropped into the solution in the four-neck flask over 30 minutes. After dropping, the ice bath was replaced with an oil bath, and the reaction solution was stirred at 65℃ for 17 hours. The reaction solution was concentrated using an evaporator, and the obtained solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 50.1 g (65% yield) of azomethine-2NH2 was obtained. The structure is: 1 The results were confirmed by H-NMR and IR.

[0134] <Synthesis of Thymine-COOH> 1-(2-carboxyethyl)adenine was synthesized using thymine and β-propiolactone in a similar manner to Chem. Lett., 1973, 967. The structure is: 1 The results were confirmed by H-NMR and IR.

[0135] <Synthesis of thymine-COOPhCl5 (active ester)> In a 2L four-neck flask, 1000ml of DMF, 28.1g (0.28mol) of triethylamine, and pentachlorophenyl trichloroacetate (114.3g, 0.28mol) were added, and the mixture was stirred at room temperature to completely dissolve the mixture. 1-(2-carboxyethyl)thymine (50.0g, 0.25mol) was added to the solution, and the mixture was reacted at room temperature for 20h. Then, DMF, triethylamine, etc. were distilled off under reduced pressure until the solution solidified, and the resulting solid was taken out of the flask and washed with cold water on a Nutsche. The solid was dried in a reduced pressure oven at 50°C, and then recrystallized with CHCl3 / MeOH=1 / 1 (v / v), to obtain 40.6g of pentachlorophenyl 3-(2,4-dihydroxy-5-methylpyrimidin-1-yl)propionate (yield 36%). The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0136] <Synthesis of photoisomerizable compound 1> Pentachlorophenyl 3-(2,4-dihydroxy-5-methylpyrimidin-1-yl)propionate (24.4 g, 54.7 mmol) synthesized in <Synthesis of thymine-COOPhCl5 (active ester)>, azomethine-2NH2 (5.0 g, 24.8 mmol) synthesized in <Synthesis of azomethine-2NH2> in Synthesis Example 1, and 300 ml of DMF were added to a 1000 ml recovery flask and dissolved by stirring at room temperature. After reacting for 12 hours at room temperature, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain a solid. The obtained solid was washed with water and then with acetone. The washed solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 7.2 g (yield 51%) of photoisomerized compound 1 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0137] [Synthesis Example 2: Synthesis of photoisomerizable compound 4] Photoisomerizable compound 4 was synthesized in the same manner as in Synthesis Example 1, except that 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Ltd.) in Synthesis Example 1 was replaced with 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.). The structure is: 1 The results were confirmed by H-NMR and IR.

[0138] Synthesis Example 3: Synthesis of Photoisomerizable Compound 16 Synthesis of Azomethine-2NH2(2) Azomethine-2NH2(2) was synthesized in the same manner as in Synthesis Example 1, except that 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Inc.) in Synthesis Example 1 was replaced with 1-methyl-5-nitro-1H-pyrrole-2-amine (manufactured by Aurora Fine Chemicals LLC).

[0139] Synthesis of Azomethine-2NH2(3) Azomethine-2NH2(2) (100.0 g, 0.47 mol) was dissolved in 500 ml of toluene, and after adding triethylamine (114.3 g, 1.13 mol), the solution temperature was maintained at 10 °C or lower in an ice bath. 3-Aminopropanoyl chloride (manufactured by Aurora Fine Chemicals LLC) (110.4 g, 1.03 mol) was added dropwise to this solution over 30 minutes, and then the reaction was carried out at 50 °C for 5 hours. After adding methanol for quenching, it was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The obtained solid was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 86.5 g of Azomethine-2NH2(3) was obtained (yield 52%). The structure was 1 confirmed by 1H-NMR and IR.

[0140] Synthesis of Photoisomerizable Compound 16 Thereafter, the reaction of Azomethine-2NH2(3) with thymine-COOPhCl5 (active ester) was carried out in the same manner as in Synthesis Example 1 to synthesize Photoisomerizable Compound 16. The structure was 1 confirmed by 1H-NMR and IR.

[0141] Synthesis Example 4: Synthesis of Photoisomerizable Compound 18 Synthesis of Ph-3NO2 Two three-way cocks, a thermometer, a dropping funnel, and a stopper were installed in a 2000 ml four-necked flask. After evacuating the inside of the container, nitrogen substitution was performed. This operation was carried out three times. While flowing nitrogen, 800 ml of dehydrated toluene, 1-methyl-5-nitro-1H-pyrrole-2-amine (manufactured by Aurora Fine Chemicals LLC) (159.2 g, 1.24 mol), and dehydrated triethylamine (138.4 g, 1.37 mol) were charged into the four-necked flask and stirred at room temperature for 30 minutes. Then, while maintaining the liquid temperature of the solution in the four-necked flask at 10 °C or lower with an ice bath, 1,3,5-benzenetricarbonyl trichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (100.0 g, 0.38 mol) charged into the dropping funnel was added dropwise into the solution in the four-necked flask over 30 minutes. After the dropwise addition, the ice bath was removed, and the reaction solution was stirred at room temperature for 6 hours. Then, the reaction solution was concentrated using an evaporator, and the obtained solid was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 77.3 g (yield 38%) of Ph-3NO2 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0142] <Synthesis of Ph-3NH2> Into a 1000 ml Erlenmeyer flask, Ph-3NO2 (70.0 g, 0.13 mol) and palladium carbon (0.90 g, 1.94 mol) were placed, and then 200 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Then, palladium carbon was removed from the reaction solution, the obtained solution was concentrated, and recrystallization was performed with ethanol to obtain 51.3 g (yield 88%) of Ph-3NH2. The structure was 1 confirmed by 1H-NMR and IR.

[0143] <Synthesis of azomethine-3NO2> Into a 1000 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, Ph-3NH2 (50.0 g, 0.11 g) obtained from <Synthesis of Ph-3NH2>, 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) (55.4 g, 0.37 mol), 200 ml of ethanol, and 200 ml of tetrahydrofuran were added, and the mixture was heated and stirred at 50 °C for 3 hours. Next, the reaction solution was cooled to room temperature, suction filtered, and the obtained powder was washed with cooled ethanol. Furthermore, recrystallization was performed in a mixed solvent of methanol / ethanol to obtain 55.5 g (yield 61%) of azomethine-3NO2. The structure was 1 confirmed by 1H-NMR and IR.

[0144] <Synthesis of azomethine-3NH2> Synthesis was carried out with reference to Chemistry of Heterocyclic Compounds, 2004, 40(6), 701.

[0145] Two three-way cocks, a thermometer, a dropping funnel, and a stopper were installed in a 500 ml four-necked flask. After reducing the pressure inside the container, nitrogen substitution was performed. This operation was carried out 3 times. While flowing nitrogen, 300 ml of ethyl acetate, azomethine-3NO2 (50.0 g, 0.06 mol) obtained from <Synthesis of azomethine-3NO2>, and allylpalladium(II) chloride dimer (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.7 g, 2 mmol) were added, and the mixture was stirred at room temperature for 30 minutes. Then, while maintaining the liquid temperature of the solution in the four-necked flask at 10 °C or lower with an ice bath, triethylsilane (12.8 g, 0.11 mol) added to the dropping funnel was dropped into the solution in the four-necked flask over 30 minutes. After dropping, the ice bath was replaced with an oil bath, and the mixture was stirred at 65 °C for 17 hours. The reaction solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 33.8 g (yield 73%) of azomethine-3NH2 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0146] <Synthesis of photo-isomerization compound 18> Pentachlorophenyl 3-(2,4-dihydroxy-5-methylpyrimidin-1-yl)propionate (38.8 g, 86.9 mmol) synthesized in [Synthesis Example 1] <Synthesis of thymine-COOPhCl5 (active ester)>, azomethine-3NH2 (20.0 g, 26.3 mmol) synthesized in <Synthesis of azomethine-3NH2>, and 300 ml of DMF were added to a 1000 ml recovery flask and dissolved by stirring at room temperature. After reacting for 12 hours at room temperature, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain a solid. The obtained solid was washed with water and then with acetone. The washed solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 13.3 g (yield 39%) of photoisomerized compound 18 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0147] [Synthesis Example 5: Synthesis of photoisomerizable compound 22] <Synthesis of azobenzene-2NO2> A 2000 ml four-neck flask was equipped with two three-way stopcocks, a thermometer, a dropping funnel and a ball stopper, and the inside of the vessel was reduced in pressure and then replaced with nitrogen. This operation was performed three times. While flowing nitrogen, 4,4'-azoaniline (manufactured by Aurora Fine Chemicals LLC) (100.0 g, 0.47 mol), 500 ml of toluene and triethylamine (115.4 g, 1.14 mol) were added to the four-neck flask, and the solution temperature in the four-neck flask was kept below 10°C in an ice bath. 3-Nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (115.4 g, 1.04 mol) was added in portions to this solution while flowing nitrogen, and after the chloride was added, the reaction was carried out at 50°C for 5 hours. After adding methanol to quench the reaction, the reaction solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The obtained solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 153.9 g of azobenzene-2NO2 was obtained (yield 64%). The structure is: 1 The results were confirmed by H-NMR and IR.

[0148] <Synthesis of azobenzene-2NH2> Using the above azobenzene-2NO2, azobenzene-2NH2 was obtained in the same manner as <azomethine-3NH2> in Synthesis Example 4. The structure was 1 confirmed by 1H-NMR and IR.

[0149] <Synthesis of Photoisomerization Compound 22> The reaction of the above azobenzene-2NO2 with thymine-COOPhCl5 (active ester) was carried out in the same manner as in Synthesis Example 1 to synthesize photoisomerization compound 22. The structure was 1 confirmed by 1H-NMR and IR.

[0150] [Synthesis Example 6: Synthesis of Photoisomerization Compound 23] Using 4,4'-(1,2-ethylenediyl)dianiline (manufactured by Aurora Fine Chemicals LLC) and thymine-COOPhCl5 (active ester), photoisomerization compound 23 was synthesized in the same manner as in Synthesis Example 1. The structure was 1 confirmed by 1H-NMR and IR.

[0151] [Synthesis Example 7: Synthesis of Photoisomerization Compound 26] <Synthesis of TMP-3NH2> In the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, TMP-3NH2 was synthesized in the same manner as in the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, except that azomethine-2NH2 was replaced with trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.). The structure was 1 confirmed by 1H-NMR and IR.

[0152] <Synthesis of TMP-3NO2> In the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, TMP-3NO2 was synthesized in the same manner as in the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, except that azomethine-2NH2 and 3-aminopropanoyl chloride (manufactured by Aurora Fine Chemicals LLC) were replaced with TMP-3NH2 and 4-(4-nitrophenylazo)benzoyl chloride (manufactured by Chemieliva Pharmaceutical). The structure was 1 confirmed by 1H-NMR and IR.

[0153] <Synthesis of TMP-3NH2(2)> Using the above TMP-3NO2, TMP-3NH2(2) was obtained in the same manner as <Azomethine-3NH2> in Synthesis Example 4. The structure was 1 confirmed by 1H-NMR and IR.

[0154] <Synthesis of Photoisomerization Compound 26> Using the above TMP-3NH2(2) and thymine-COOPhCl5 (active ester), Photoisomerization Compound 26 was synthesized in the same manner as in Synthesis Example 1. The structure was 1 confirmed by 1H-NMR and IR [Synthesis Example 8: Synthesis of Photoisomerization Compound 29] <Synthesis of TAZ-3NO2> In the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, azomethine-2NH2 and 3-aminopropanoyl chloride (manufactured by Aurora Fine Chemicals LLC) were replaced with 4-[2-(nitrophenyl)ethenyl]aniline (manufactured by Chemieliva Pharmaceutical) and cyanuric chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and TAP-3NO2 was synthesized in the same manner as in the <Synthesis of Azomethine-2NH2(2)> of Synthesis Example 3, except that heating under reflux was carried out for 6 hours. The structure was 1 confirmed by 1H-NMR and IR.

[0155] <Synthesis of TAZ-3NH2> Using the above TAZ-3NO2, TAZ-3NH2 was obtained in the same manner as <Azomethine-3NH2> in Synthesis Example 4. The structure was 1 confirmed by 1H-NMR and IR.

[0156] <Synthesis of Photoisomerization Compound 29> Using the above TAZ-3NH2 and thymine-COOPhCl5 (active ester), Photoisomerization Compound 29 was synthesized in the same manner as in Synthesis Example 1. The structure was 1 confirmed by 1H-NMR and IR.

[0157] [Synthesis Example 9: Synthesis of photoisomerizable compound 36] <Synthesis of Azomethine-2NO2(2)> 4-Nitroaniline (Tokyo Chemical Industry Co., Ltd.) (80.0 g, 0.58 mol), 1-methyl-5-nitro-1H-pyrrole-2-carboxaldehyde (Accel Pharmtec Co., Ltd.) (89.3 g, 0.58 mol), and 300 ml of ethanol were added to a 500 ml four-neck flask equipped with a cooling tube, nitrogen inlet tube, and thermometer, and the mixture was heated and stirred at 50°C. The reaction solution was then suction filtered, and the resulting powder was washed with cooled ethanol. The mixture was then recrystallized in a mixed solvent of methanol / ethanol to obtain 136.6 g of azomethine-2NO2(2) (yield 86%). The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0158] <Synthesis of azomethine-2NH2(4)> A 1000 ml four-neck flask was equipped with two three-way stopcocks, a thermometer, a dropping funnel and a ball stopper, and the inside of the vessel was decompressed and replaced with nitrogen. This operation was repeated three times. While nitrogen was flowing, 250 ml of tetrahydrofuran, 250 ml of ethanol, azomethine-2NO2(2) (100.0 g, 0.36 mol) and allylpalladium(II) chloride dimer (2.7 g, 7 mmol) were added to the four-neck flask and stirred at room temperature for 30 minutes. Then, while keeping the temperature of the solution in the four-neck flask below 10°C in an ice bath, triethylsilane (50.9 g, 0.44 mol) added to the dropping funnel was dropped into the solution in the four-neck flask over 30 minutes. After dropping, the ice bath was replaced with an oil bath and the mixture was stirred at 65°C for 17 hours. The reaction solution was concentrated using an evaporator, and the obtained solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 64.1 g (yield 82%) of azomethine-2NH2 (4) was obtained. The structure is 1 The results were confirmed by H-NMR and IR.

[0159] <Synthesis of azomethine-2NH2(5)> A 1000 ml four-head flask was equipped with two three-way cocks, a thermometer, a dropping funnel and a ball stopper, and the inside of the container was decompressed and then replaced with nitrogen. This operation was performed three times. While flowing nitrogen, azomethine-2NH2 (4) (100.0 g, 0.47 mol) and 500 ml of toluene were added to the four-head flask to dissolve azomethine-2NH2, and then triethylamine (114.3 g, 1.13 mol) was added, and the solution temperature in the four-head flask was kept below 10 ° C. in an ice bath. 3-amino-2-methylpropanoyl chloride (manufactured by Aurora Fine Chemicals LLC) (114.3 g, 1.0 mol) was added dropwise to this solution over 30 minutes, and the reaction was carried out at 50 ° C. for 5 hours. The resulting reaction solution was quenched by adding methanol, and then concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The obtained solid was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 105.9 g of azomethine-2NH2 (5) was obtained (yield 59%). The structure is 1 The results were confirmed by H-NMR and IR.

[0160] <Synthesis of Adenine-COOH> 9-(2-carboxyethyl)adenine was synthesized using adenine and β-propiolactone in a similar manner to that described in Chem. Lett., 1973, 967. The structure is: 1 The results were confirmed by H-NMR and IR.

[0161] <Synthesis of adenine CF3-COOPhNO2 (active ester)> Into a 5 L four-necked flask, 2000 ml of pyridine, 9-(2-carboxyethyl)adenine (40.0 g, 0.19 mol), 4-nitrophenol (30.0 g, 0.22 mol), and 4-nitrophenyl trifluoroacetate (200.0 g, 0.85 mol) were added, and the mixture was stirred at 50 °C for 2 hours. Then, the reaction solution was concentrated with a rotary evaporator until the solution solidified, and the obtained solid was dissolved in CHCl3. Diethyl ether was added to this solution, and the precipitated solid was filtered with a Buchner funnel. This solid was redissolved in CHCl3 and slowly dropped into the same amount of diethyl ether as that of CHCl3 with vigorous stirring for reprecipitation purification. This solid was filtered with a Buchner funnel and dried in a vacuum oven at 50 °C to obtain 63.0 g of 4-nitrophenyl-3-(6-trifluoroacetamidopurin-9-yl)propionate (yield 77%). The structure was 1 confirmed by 1H-NMR and IR.

[0162] <Synthesis of the CF3CO-Protected Photoisomerization Compound 36> Into a 500 ml eggplant-shaped flask, 4-nitrophenyl-3-(6-trifluoroacetamidopurin-9-yl)propionate (66.2 g, 0.16 mol), azomethine-2NH2(4) (50.0 g, 0.13 mol) synthesized in the above <Synthesis of Azomethine-2NH2(4)>, and 200 ml of dimethyl sulfoxide were charged and dissolved by stirring at room temperature. Then, after reacting at room temperature for 3 days, it was concentrated under reduced pressure with a rotary evaporator to obtain a solid. The obtained solid was washed with water and then washed with diethyl ether. The washed solid was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 88.2 g (yield 71%) of the CF3CO-protected photoisomerization compound 36 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0163] <Synthesis of the Photoisomerization Compound 36 (Deprotection of CF3CO)> To a 100 ml eggplant flask, potassium carbonate (2.9 g, 20.9 mmol) and 20 ml of water were added and dissolved by stirring at room temperature. Then, into the solution obtained by adding 20 ml of methanol to this solution, the CF3CO-protected photo-isomerization compound 36 (10.0 g, 10.5 mmol) synthesized in the above <Synthesis of CF3CO-Protected Photo-Isomerization Compound 36> was added, and the mixture was stirred at room temperature for 12 hours. The resulting reaction solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid content was washed with water. The obtained solid was redissolved in ethanol and reprecipitated and purified by slowly dropping it into vigorously stirred water. By drying this solid content in a vacuum oven at 50 °C, 6.6 g of the photo-isomerization compound 36 was obtained (yield 83%). The structure was 1 confirmed by 1H-NMR and IR.

[0164] [Synthesis Example 10: Synthesis of Photo-Isomerization Compound 39] In the <Synthesis of Azomethine-2NO2(2)> of [Synthesis Example 9], 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-methyl-5-nitro-1H-pyrrole-2-carboxaldehyde (manufactured by Accel Pharmtec) were replaced with 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-thiophenamine (manufactured by Chemieliva Pharmaceutica), and the photo-isomerization compound 39 was synthesized in the same manner as [Synthesis Example 9]. The structure was 1 confirmed by 1H-NMR and IR.

[0165] [Synthesis Example 11: Synthesis of Photo-Isomerization Compound 49] In <Synthesis of CF3CO-Protected Photo-Isomerization Compound 36> of [Synthesis Example 9], azomethine-2NH2(4) was replaced with 4,4'-azodianiline (manufactured by Sigma-Aldrich), and then the photo-isomerization compound 49 was synthesized in the same manner as <Synthesis of Photo-Isomerization Compound 36 (Deprotection of CF3CO)>. The structure was 1 confirmed by 1H-NMR and IR.

[0166] [Synthesis Example 12: Synthesis of Photo-Isomerization Compound 57] [Synthesis of STB-COCl] 50 ml of CH2Cl2, 4-carboxy-4'-nitrostilbene (10.0 g, 37.1 mmol) and a few drops of DMF were added to a 100 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel and a thermometer, and stirred at room temperature to dissolve. The solution was cooled in an ice bath and the liquid temperature was maintained at 10°C or less. Then, oxalyl chloride (Tokyo Chemical Industry Co., Ltd.) (5.2 g, 40.9 mmol) was added dropwise to the solution over 30 minutes, and then the ice bath was removed to return the liquid temperature to room temperature and stirred for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and 50 ml of CH2Cl2 was added again, followed by concentration under reduced pressure using a rotary evaporator. This operation was repeated three times. As a result, 10.5 g of STB-COCl was obtained (yield 98%).

[0167] <Synthesis of photoisomerizable compound 57> Photoisomerizable compound 57 was synthesized in the same manner as in <Synthesis of photoisomerizable compound 36 (deprotection of CF3CO)> in [Synthesis Example 7] and [Synthesis Example 9], except that trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(4-nitrophenylazo)benzoyl chloride (manufactured by Chemieliva Pharmaceutical Co., Ltd.) and thymine-COOPhCl5 (active ester) in [Synthesis Example 7] were replaced with pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.), STB-COCl synthesized above, and adenine CF3-COOPhNO2 (active ester). The structure is: 1 The results were confirmed by H-NMR and IR.

[0168] [Synthesis Example 13: Synthesis of photoisomerizable compound 62] <Synthesis of Uracil-NO2> In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, 6-(hydroxymethyl)-1-methyl-2,4-pyrimidinedione (manufactured by Aurora Fine Chemicals) (5.0 g, 32.0 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.8 g, 57.6 mmol) were added and dissolved at room temperature by stirring. The solution was cooled in an ice bath and the liquid temperature was maintained at 10°C or less. Then, 4-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (7.1 g, 38.4 mmol) was added dropwise to the solution over 30 minutes and stirred at room temperature for 5 hours. Then, the solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 7.2 g of uracil-NO2 (74% yield) was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0169] <Synthesis of Uracil-NH2> Uracil-NO2 (7.0 g, 22.9 mmol) and palladium carbon (0.11 g, 229 mmol) were placed in a 200 ml Erlenmeyer flask, and 30 ml each of ethanol and tetrahydrofuran were added. The mixture was stirred while hydrogen was sealed in. Palladium carbon was removed from the reaction solution, and the resulting solution was concentrated and then recrystallized from ethanol to obtain 5.4 g of uracil-NH2 (yield 86%). The structure is: 1 The results were confirmed by H-NMR and IR.

[0170] <Synthesis of Uracil-CHO> In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, 6-(hydroxymethyl)-1-methyl-2,4-pyrimidinedione (manufactured by Aurora Fine Chemicals) (5.0 g, 32.0 mmol) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.8 g, 57.6 mmol) were added and stirred at room temperature to dissolve. The solution was cooled in an ice bath and the liquid temperature was maintained at 10°C or less. Then, 4-formylbenzoyl chloride (manufactured by Aurora Fine Chemicals) (6.5 g, 38.4 mmol) synthesized above was added dropwise to this solution over 30 minutes and stirred at room temperature for 5 hours. Then, the solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 7.8 g of uracil-CHO was obtained (yield 84%). The structure was confirmed by 1H-NMR and IR. 1 The results were confirmed by H-NMR and IR.

[0171] <Synthesis of photoisomerizable compound 62> The uracil-NH2 (7.0 g, 25.4 mmol) and uracil-CHO (7.3 g, 25.4 mmol) synthesized above and 30 ml of ethanol were placed in a 100 ml four-neck flask equipped with a cooling tube, a nitrogen inlet tube, and a thermometer, and heated and stirred at 50°C. The reaction liquid was suction filtered, and the resulting powder was washed with cooled ethanol. It was further purified by column chromatography using a methylene chloride / methanol solvent. As a result, 9.0 g (yield 65%) of photoisomerized compound 62 was obtained. The structure is: 1 The results were confirmed by H-NMR and IR.

[0172] [Synthesis Example 14: Synthesis of photoisomerizable compound 63] Photoisomerizable compound 63 was synthesized in the same manner as in Synthesis Example 13, except that 4-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6-hydroxymethyl-1-methyl-2,4-pyrimidinedione (manufactured by Aurora Fine Chemicals) in Synthesis Example 13 were replaced with 5-nitro-2-fluoroyl chloride (manufactured by Sigma-Aldrich Co., Ltd.) and 6-(2-aminoethyl)-1-methyl-2,4-pyrimidinedione (manufactured by Aurora Fine Chemicals Co., Ltd.), respectively. The structure is: 1 The results were confirmed by H-NMR and IR.

[0173] [Synthesis Example 15: Synthesis of photoisomerizable compound 70] <Synthesis of uracil-COOPhCl5 (active ester)> Uracil-COOPhCl5 (active ester) was synthesized in the same manner as in <Synthesis of thymine-COOPhCl5 (active ester)> in [Synthesis Example 1], except that 1-(2-carboxyethyl)thymine was replaced with 2-(1-methylpyrimidine 2,4-dione-4-yl)acetic acid. The structure is: 1 The results were confirmed by H-NMR and IR.

[0174] <Synthesis of photoisomerizable compound 70> Photoisomerized compound 70 was synthesized in the same manner as in <Synthesis of thymine-COOPhCl5 (active ester)> in [Synthesis Example 6], except that pentachlorophenyl 3-(2,4-dihydro-5-methylpyrimidin-1-yl)propionate in [Synthesis Example 6] was replaced with the synthesis of uracil-COOPhCl5 (active ester) synthesized above. The structure is: 1 The results were confirmed by H-NMR and IR.

[0175] [Synthesis Example 16: Synthesis of photoisomerizable compound 75] <Synthesis of photoisomerizable compound 75> Photoisomerized compound 75 was synthesized in the same manner as in Synthesis Example 7, except that thymine-COOPhCl5 (active ester) in Synthesis Example 7 was replaced with <Synthesis of uracil-COOPhCl5 (active ester)> in Synthesis Example 15 above. The structure is:1 The results were confirmed by H-NMR and IR.

[0176] [Synthesis Example 17: Synthesis of photoisomerizable compound 79] <Synthesis of photoisomerizable compound 79> Photoisomerizable compound 79 was synthesized in the same manner as in Synthesis Example 13, except that 4-nitrobenzoyl chloride (Tokyo Chemical Industry Co., Ltd.) and 6-hydroxymethyl-1-methyl-2,4-pyrimidinedione (Aurora Fine Chemicals) in Synthesis Example 13 were replaced with 5-nitro-1H-pyrrole-2-carbonyl chloride (Chemiliva Pharmaceutical Co., Ltd.) and 2,6-diacetamido-4-hydroxymethylpyridine (Hong Kong Cemphre Co., Ltd.), respectively. The structure is: 1 The results were confirmed by H-NMR and IR.

[0177] [Synthesis Example 18: Synthesis of photoisomerizable compound 87] <Synthesis of 2,6-diacetamidopyridine-NO2> In a 200 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, 2,6-diacetamido-4-hydroxymethylpyridine (Apichemical) (10.0 g, 44.8 mmol), and triethylamine (Tokyo Chemical Industry) (8.2 g, 80.6 mmol) were added and stirred at room temperature to dissolve. The solution was cooled in an ice bath to maintain the liquid temperature at 10°C or less. Then, 4-nitrobenzoyl chloride (Sigma-Aldrich) (10.0 g, 53.8 mmol) was added dropwise to the solution over 30 minutes, and the solution was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 12.3 g (74% yield) of 2,6-diacetamidopyridine-NO2 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0178] <Synthesis of 2,6-diacetamidopyridine-NH2> Into a 200 ml Erlenmeyer flask, 2,6-diacetamidopyridine-NO2 (10.0 g, 26.9 mmol) and palladium carbon (0.12 g, 269 mmol) were added. Then, 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Palladium carbon was removed from the reaction solution, and the obtained solution was concentrated and then recrystallized with ethanol to obtain 8.4 g (yield 91%) of 2,6-diacetamidopyridine-NH2.

[0179] <Synthesis of Photoisomerization Compound 87> Into a 200 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, 2,6-diacetamidopyridine-NH2 (12.3 g, 35.8 mmol) synthesized above, and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.4 g, 53.7 mmol) were charged and stirred at room temperature until dissolved. The solution was cooled in an ice bath to maintain the liquid temperature at 10°C or lower. Then, a CH2Cl2 solution of 4,4'-azodibenzoyldichloride (manufactured by Sigma-Aldrich) (5.0, 16.3 mmol) was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 10.0 g (yield 67%) of the photoisomerization compound 87 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0180] [Synthesis Example 19: Synthesis of Photoisomerization Compound 88] Using 2,6-diacetamido-4-hydroxymethylpyridine (manufactured by Apichemical) and 4,4'-stilbenedicarbonyl chloride (manufactured by Sigma-Aldrich), the photoisomerization compound 88 was synthesized in the same manner as in [Synthesis Example 18] <Synthesis of Photoisomerization Compound 87>. The structure was 1 confirmed by 1H-NMR and IR.

[0181] [Synthesis Example 20: Synthesis of Photoisomerization Compound 91] <Synthesis of TMP-NO2(2)> Into a 200 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.0 g, 37.3 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (18.7 g, 184.5 mmol) were added, and the mixture was stirred and dissolved at room temperature. The solution was cooled in an ice bath to maintain the liquid temperature below 10°C. Then, a CH2Cl2 solution of 4-nitrobenzoyl dichloride (manufactured by Sigma-Aldrich) (22.8 g, 123.0 mmol) was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 16.9 g (yield 78%) of TMP-NO2(2) was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0182] <Synthesis of TMP-NH2(2)> Into a 200 ml Erlenmeyer flask, TMP-NO2(2) (15.0 g, 25.8 mmol) and palladium carbon (0.18 g, 387 mmol) were placed, 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Palladium carbon was removed from the reaction solution, the resulting solution was concentrated, and then recrystallized from ethanol to obtain 11.0 g (yield 87%) of TMP-NH2(2).

[0183] <Synthesis of 2,6-diacetamidopyridine-CHO(2)> In a 200 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CHCl, 2,6-diacetamido-4-hydroxymethylpyridine (Apichemical) (10.0 g, 36.6 mmol), and triethylamine (Tokyo Chemical Industry) (6.7 g, 65.9 mmol) were added and stirred at room temperature to dissolve. The solution was cooled in an ice bath to maintain the liquid temperature at 10°C or less. Then, a solution of 5-formyl-2-furancarbonyl chloride (Aurora Fine Chemicals) (7.0 g, 43.9 mmol) in CHCl was added dropwise to the solution over 30 minutes, and the solution was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 10.7 g (85% yield) of 2,6-diacetamidopyridine-CHO (2) was obtained. The structure is 1 The results were confirmed by H-NMR and IR.

[0184] <Synthesis of photoisomerizable compound 91> The above synthesized TMP-NH2 (2) (10.0 g, 20.3 mmol), 2,6-diacetamidopyridine-CHO (2) (7.0 g, 20.3 mmol), and 30 ml of DMF were placed in a 100 ml four-neck flask equipped with a condenser, nitrogen inlet, and thermometer, and the mixture was heated and stirred at 50°C. The reaction solution was suction filtered, and the resulting powder was washed with cooled ethanol. The mixture was further purified by column chromatography using a methylene chloride / methanol solvent. As a result, 15.6 g (yield 52%) of photoisomerized compound 91 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0185] [Synthesis Example 21: Synthesis of photoisomerizable compound 101] <Synthesis of photoisomerizable compound 101> [Synthesis Example 3: Synthesis of Azomethine-2NH2(2)] Using Azomethine-2NH2(2) synthesized in <Synthesis of Azomethine-2NH2(2)> and Carbonyldiisocyanate (manufactured by Chemiliva Pharmaceutical), Photoisomerization Compound 101 was synthesized with reference to Chemische Berichte, 1986, 119(3), 83. The structure was 1 confirmed by 1H-NMR and IR.

[0186] [Synthesis Example 22: Synthesis of Photoisomerization Compound 102] [Synthesis of Photoisomerization Compound 102] Using 4,4'-Azodianiline and Carbonyldiisocyanate (manufactured by Chemiliva Pharmaceutical), Photoisomerization Compound 102 was synthesized with reference to Chemische Berichte, 1986, 119(3), 83. The structure was 1 confirmed by 1H-NMR and IR.

[0187] [Synthesis Example 23: Synthesis of Photoisomerization Compound 105] [Synthesis of STB-NO2(2)] Into a 200 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 50 ml of CH2Cl2, 4,4'-(1,2-ethenediyl)-bisaniline (manufactured by Aurora Fine Chemicals LLC) (10.0 g, 47.6 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (15.9 g, 156.9 mmol) were charged and stirred at room temperature until dissolved. The solution was cooled in an ice bath to maintain the liquid temperature at 10 °C or lower. Then, a solution of 3-nitrobenzoyl chloride (manufactured by Sigma-Aldrich) (19.4 g, 104.6 mmol) in CH2Cl2 was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol solvent system. As a result, 17.9 g (yield 74%) of STB-NO2(2) was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0188] <Synthesis of STB-NH2(2)> Into a 200 ml Erlenmeyer flask, STB-NO2(2) (15.0 g, 29.5 mmol) and palladium carbon (0.14 g, 295 mmol) were added. Then, 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Palladium carbon was removed from the reaction solution, and the resulting solution was concentrated. After recrystallization with ethanol, 10.8 g (yield 82%) of STB-NH2(2) was obtained.

[0189] <Synthesis of Photoisomerization Compound 105> Using STB-NH2(2) and carbonyldiisocyanate (manufactured by Chemiliva Pharmaceutical), photoisomerization compound 105 was synthesized with reference to Chemische Berichte, 1986, 119(3), 83. The structure was 1 confirmed by 1H-NMR and IR.

[0190] 〔Synthesis Example 24: Synthesis of Photoisomerization Compound 106〕 <Synthesis of DTMP-CHO> Into a 500 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 200 ml of CH2Cl2, di(trimethylolpropane) (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.0 g, 39.9 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (26.7 g, 263.6 mmol) were charged and stirred at room temperature until dissolved. The solution was cooled in an ice bath to maintain the liquid temperature at 10 °C or lower. Then, a CH2Cl2 solution of 4-formylbenzoyl chloride (manufactured by Sigma-Aldrich) (29.6 g, 175.8 mmol) was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 19.0 g (yield 61%) of DTMP-CHO was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0191] <Synthesis of DTMP-NO2> Into a 100 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, the DTMP-CHO (15.0 g, 19.3 mmol) synthesized above, 5-nitro-2-furanamine (10.9 g, 84.7 mmol), and 30 ml of CH2Cl2 were added, and the mixture was heated and stirred at 50 °C. The reaction solution was suction filtered, and the obtained powder was washed with cooled ethanol. Further, purification was performed by column chromatography using a methylene chloride / methanol-based solvent. As a result, 13.4 g (yield 56%) of DTMP-NO2 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0192] <Synthesis of DTMP-NH2> Into a 200 ml Erlenmeyer flask, DTMP-NO2 (12.0 g, 9.7 mmol) and palladium carbon (0.09 g, 193.1 mmol) were placed, then 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Palladium carbon was removed from this reaction solution, and after the obtained solution was concentrated, recrystallization was performed with ethanol to obtain 9.9 g (yield 91%) of DTMP-NH2.

[0193] <Synthesis of Photoisomerization Compound 106> Using DTMP-NH2 and carbonyldiisocyanate (manufactured by Chemiliva Pharmaceutical), photoisomerization compound 106 was synthesized with reference to Chemische Berichte, 1986, 119(3), 83. The structure was 1 confirmed by 1H-NMR and IR.

[0194] [Synthesis Example 25: Synthesis of Photoisomerization Compound 113] <Synthesis of Azomethine-2NH2(6)> Azomethine-2NH2(6) was synthesized in the same manner as in Synthesis Example 1 <Synthesis of Azomethine-2NH2>, except that 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Inc.). The structure was 1 confirmed by 1H-NMR and IR.

[0195] <Synthesis of photoisomerized compound 113> In a 500 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 300 ml of DMF, the above synthesized azomethine-NH2 (6) (12.0 g, 56.8 mmol), and sodium hydrogen carbonate (Kanto Chemical Co., Ltd.) (15.7 g, 187.4 mmol) were added, and the mixture was stirred at room temperature to dissolve. The solution was cooled in an ice bath, and the liquid temperature was maintained at 10°C or less. Then, 2-chloro-4,6-diamino-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.) (18.2 g, 125.0 mmol) was added dropwise to the solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. After the solution was poured into water, the water-insoluble solid was filtered, and the obtained solid was washed with water. After drying the solid after washing with water, it was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 11.4 g (yield 49%) of the photoisomerized compound 113 was obtained. The structure is: 1 The results were confirmed by H-NMR and IR.

[0196] [Synthesis Example 26: Synthesis of photoisomerizable compound 115] <Synthesis of photoisomerizable compound 115> Photoisomerizable compound 115 was synthesized in the same manner as in Synthesis Example 25, except that 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 5-nitrothiophene-2-carboxaldehyde (manufactured by Aurora Fine Chemicals LLC). The structure is: 1 The results were confirmed by H-NMR and IR.

[0197] [Synthesis Example 27: Synthesis of photoisomerizable compound 117] <Synthesis of photoisomerizable compound 117> Photoisomerization compound 117 was synthesized in the same manner as in Synthesis Example 25, except that azomethine-NH2 (6) in Synthesis Example 25 <Synthesis of photoisomerization compound 113> was replaced with 4,4'-(1,2-ethylenediyl)dianiline (manufactured by Aurora Fine Chemicals LLC). The structure is: 1 The results were confirmed by H-NMR and IR.

[0198] [Synthesis Example 28: Synthesis of photoisomerizable compound 124] <Synthesis of TMP-NO2(2)> Into a 500 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 300 ml of CH2Cl2, trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.0 g, 37.3 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (18.7 g, 184.5 mmol) were added and stirred at room temperature until dissolved. The solution was cooled in an ice bath to maintain the liquid temperature at 10 °C or lower. Then, a CH2Cl2 solution of STB-COCl (35.4 g, 123.0 mmol) synthesized in <Synthesis of STB-COCl> of [Synthesis Example 12] was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 17.9 g (yield 54%) of TMP-NO2(2) was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0199] <Synthesis of TMP-NH2(2)> Into a 300 ml Erlenmeyer flask, TMP-NO2(2) (15.0 g, 16.9 mmol) and palladium carbon (0.12 g, 253.4 mmol) were added. Then, 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Then, palladium carbon was removed from the reaction solution, the resulting solution was concentrated, and recrystallization was performed with ethanol to obtain 11.3 g (yield 84%) of TMP-NH2(2).

[0200] <Synthesis of Photoisomerization Compound 124> In a 500 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 150 ml of DMF, the TMP-NH2 (2) (11.0 g, 13.8 mmol) synthesized above, and sodium hydrogen carbonate (Kanto Chemical Co., Ltd.) (5.7 g, 68.2 mmol) were added and stirred at room temperature to dissolve. The solution was cooled in an ice bath to maintain the liquid temperature at 10°C or less. Then, 2-chloro-4,6-diamino-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.) (6.6 g, 45.5 mmol) was added dropwise to this solution over 30 minutes, and the solution was stirred at room temperature for 5 hours. After the solution was poured into water, the water-insoluble solid was filtered, and the obtained solid was washed with water. After drying the solid after washing with water, it was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 6.4 g (41% yield) of photoisomerized compound 124 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0201] [Synthesis Example 29: Synthesis of photoisomerizable compound 129] <Synthesis of azomethine-2CN> [Synthesis Example 1] Azomethine-2CN was synthesized in the same manner as in Synthesis Example 1, except that in <Synthesis of azomethine-2NO2>, 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Ltd.) were replaced with 4-aminobenzonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-formylfuran-2-carbonitrile (manufactured by Aurora Fine Chemicals LLC). The structure is: 1 The results were confirmed by H-NMR and IR.

[0202] <Synthesis of photoisomerizable compound 129> Into a 100 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 150 ml of DMF, the azomethine-2CN (10.0 g, 45.2 mmol) synthesized above, and potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) (2.8 g, 49.7 mmol) were added. Then, dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd.) (8.4 g, 99.4 mmol) was added to the reaction solution in the four-necked flask, and the mixture was heated under reflux for 6 hours. After the solution was poured into water, the solid insoluble in water was filtered, and the obtained solid content was washed with water. After drying the solid content after washing with water, it was purified by column chromatography using a methylene chloride / methanol solvent system. As a result, 18.9 g (yield 47%) of the photo-isomerization compound 129 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0203] [Synthesis Example 30: Synthesis of Photo-Isomerization Compound 132] [Synthesis of Photo-Isomerization Compound 132] [Synthesis Example 29] The photo-isomerization compound 132 was synthesized in the same manner as [Synthesis Example 29] <Synthesis of Photo-Isomerization Compound 129>, except that azomethine-2CN was replaced with 4,4'-(1E)-1,2-ethenediyldibenzonitrile (manufactured by Chemiliva Pharaceutical). The structure was 1 confirmed by 1H-NMR and IR.

[0204] [Synthesis Example 31: Synthesis of Photo-Isomerization Compound 135] [Synthesis of AZB-2CN] Into a 500 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 300 ml of CH2Cl2, 4,4'-azodianiline (manufactured by Sigma-Aldrich) (12.0 g, 56.5 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (18.9 g, 186.6 mmol) were added, and the mixture was stirred and dissolved at room temperature. The solution was cooled in an ice bath to maintain the liquid temperature below 10°C. Then, a CH2Cl2 solution of [Synthesis Example 12] 3-cyanobenzoyl chloride (20.6 g, 124.4 mmol) was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol-based solvent. As a result, 20.7 g (yield 78%) of AZB-2CN was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0205] <Synthesis of Photoisomerization Compound 135> [Synthesis Example 29: Synthesis of Photoisomerization Compound 135] Photoisomerization Compound 135 was synthesized in the same manner as [Synthesis Example 29: Synthesis of Photoisomerization Compound 129], except that azomethine-2CN was replaced with AZB-2CN. The structure was 1 confirmed by 1H-NMR and IR.

[0206] [Synthesis Example 32: Synthesis of Photoisomerization Compound 137] <Synthesis of DPE-2CN> DPE-2CN was synthesized in the same manner as Synthesis Example 24, except that di(trimethylolpropane) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-furanamine (manufactured by Aurora Fine Chemicals LLC) were replaced with di(pentaerythritol) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4-cyanoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) in [Synthesis Example 24: Synthesis of DTMP-CHO] and [Synthesis Example 24: Synthesis of DTMP-NO2]. The structure was 1 confirmed by 1H-NMR and IR.

[0207] <Synthesis of Photoisomerization Compound 137> [Synthesis Example 29: Synthesis of Photoisomerization Compound 129] Photoisomerization Compound 137 was synthesized in the same manner as [Synthesis Example 29: Synthesis of Photoisomerization Compound 129], except that azomethine-2CN was replaced with DPE-2CN. The structure was confirmed by 1 1H-NMR and IR.

[0208] [Synthesis Example 33: Synthesis of Photoisomerization Compound 140] [Synthesis of Azomethine-2NH2(7)] [Synthesis Example 1: Synthesis of Azomethine-2NO2] Azomethine-2NH2(7) was synthesized in the same manner as [Synthesis Example 1: Synthesis of Azomethine-2NO2] and [Synthesis of Azomethine-2NH2], except that 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Inc.) were replaced with 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-furanamine (manufactured by Aurora Fine Chemicals LLC). The structure was confirmed by 1 1H-NMR and IR.

[0209] [Synthesis of Photoisomerization Compound 140] Using the azomethine-NH2(7) synthesized above and 1,3-dioxoisoindole-5-carbonyl chloride (manufactured by Aurora Fine Chemicals LLC), Photoisomerization Compound 140 was synthesized in the same manner as [Synthesis Example 31: Synthesis of AZB-2CN]. The structure was confirmed by 1 1H-NMR and IR.

[0210] [Synthesis Example 34: Synthesis of Photoisomerization Compound 145] [Synthesis of Azomethine-2NH2(8)] [Synthesis Example 1] <Synthesis of Azomethine-2NO2> Azomethine-2NH2 (8) was synthesized in the same manner as in [Synthesis Example 1] <Synthesis of Azomethine-2NO2> and <Synthesis of Azomethine-2NH2>, except that 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitro-2-furaldehyde (manufactured by Kanto Chemical Co., Inc.) were replaced with 4-nitrobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5-nitrothiophene-2-carboxaldehyde (manufactured by Aurora Fine Chemicals LLC). The structure was 1 confirmed by 1H-NMR and IR.

[0211] [Synthesis of Photoisomerization Compound 145] Using the azomethine-NH2 (5) synthesized above and 1,3-dioxoisoindole-5-carbonyl chloride (manufactured by Aurora Fine Chemicals LLC), photoisomerization compound 140 was synthesized in the same manner as in [Synthesis Example 31] <Synthesis of AZB-2CN>. The structure was 1 confirmed by 1H-NMR and IR.

[0212] [Synthesis Example 35: Synthesis of Photoisomerization Compound 149] [Synthesis of Photoisomerization Compound 149] Using 4,4’-(1,2-ethenediyl)-bisaniline (manufactured by Aurora Fine Chemicals LLC) and 1,3-dioxoisoindole-5-carbonyl chloride (manufactured by Aurora Fine Chemicals LLC), photoisomerization compound 140 was synthesized in the same manner as in [Synthesis Example 31] <Synthesis of AZB-2CN>. The structure was 1 confirmed by 1H-NMR and IR.

[0213] [Synthesis Example 36: Synthesis of Photoisomerization Compound 153] [Synthesis of TMP-3NO2] Into a 500 ml four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 200 ml of CH2Cl2, trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.0 g, 37.3 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (18.7 g, 184.5 mmol) were added and stirred at room temperature until dissolved. The solution was cooled in an ice bath to maintain the liquid temperature below 10°C. Then, a CH2Cl2 solution of 4-(4-nitrophenylazo)benzoyl chloride (manufactured by Chemimiva Pharmaceutical) (35.6 g, 123.0 mmol) was added dropwise to this solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the resulting solid was washed with water. The solid after washing with water was purified by column chromatography using a methylene chloride / methanol solvent system. As a result, 21.3 g (yield 64%) of TMP-3NO2 was obtained. The structure was 1 confirmed by 1H-NMR and IR.

[0214] <Synthesis of TMP-3NH2> Into a 300 ml Erlenmeyer flask, TMP-NO2 (2) (15.0 g, 16.8 mmol) and palladium carbon (0.12 g, 251.7 mmol) were added. Then, 50 ml each of ethanol and tetrahydrofuran were added, and the mixture was stirred while enclosing hydrogen. Palladium carbon was removed from the reaction solution, and the resulting solution was concentrated and then recrystallized from ethanol to obtain 11.9 g (yield 88%) of TMP-NH2 (2).

[0215] <Synthesis of Photoisomerization Compound 153> In a 200 ml 4-neck flask equipped with a nitrogen inlet tube, a dropping funnel, and a thermometer, 100 ml of CHCl, TMP-3NH (10.0 g, 12.4 mmol), and triethylamine (Tokyo Chemical Industry Co., Ltd.) (6.2 g, 61.6 mmol) were added, and the mixture was stirred at room temperature to dissolve. The solution was cooled in an ice bath, and the liquid temperature was maintained at 10°C or less. Then, a solution of 1,3-dioxoisoindole-5-carbonyl chloride (Aurora Fine Chemicals LLC) (8.6 g, 41.1 mmol) in CHCl was added dropwise to the solution over 30 minutes, and the mixture was stirred at room temperature for 5 hours. The solution was concentrated under reduced pressure using a rotary evaporator, and the obtained solid was washed with water. The solid after washing was purified by column chromatography using a methylene chloride / methanol solvent. As a result, 11.5 g (70% yield) of photoisomerized compound 153 was obtained. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0216] Although some methods for synthesizing the photoisomerizable compounds have been exemplified above, the method for synthesizing the photoisomerizable compounds used in the present invention is not limited to these.

[0217] <Other Additives for Resin Composition> In addition to the resins described above, various additives can be used in the resin composition of the present invention as long as they do not impair the effects of the present invention. Examples of applicable additives are shown below.

[0218] (Plasticizer) In the present invention, the addition of a compound known as a plasticizer is preferable from the viewpoint of modifying the resin composition, such as improving mechanical properties, imparting flexibility, imparting water absorption resistance, and reducing moisture permeability.

[0219] Plasticizers applicable to the present invention include phosphate ester plasticizers, ethylene glycol ester plasticizers, glycerin ester plasticizers, diglycerin ester plasticizers (fatty acid esters), polyhydric alcohol ester plasticizers, dicarboxylate ester plasticizers, polycarboxylate ester plasticizers, and polymer plasticizers.

[0220] Among these, it is preferable to use either a polyhydric alcohol ester plasticizer (an ester plasticizer made of a polyhydric alcohol and a monovalent carboxylic acid), a polycarboxylic acid ester plasticizer (an ester plasticizer made of a polyvalent carboxylic acid and a monovalent alcohol), or both.

[0221] As for details of the plasticizer applicable to the resin composition of the present invention, for example, the compounds described in paragraphs

[0102] to

[0162] of Japanese Patent No. 5380840 can be mentioned.

[0222] The amount of the plasticizer added is preferably within the range of 0.001 to 50 parts by mass, more preferably 0.01 to 30 parts by mass, and even more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the resin composition of the present invention.

[0223] (Antioxidants) An antioxidant may be added to the resin composition of the present invention in order to prevent the resin from being decomposed by heat or light.

[0224] Examples of antioxidants applicable to the present invention include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, heat-resistant processing stabilizers, light stabilizers, oxygen scavengers, etc. Among these, phenol-based antioxidants, particularly hindered phenol-based antioxidants having a bulky branched alkyl at the ortho position relative to the hydroxy group of the phenol compound, 2,2,6,6-tetraalkylpiperidine derivatives, and combinations thereof are preferred.

[0225] As for details of the antioxidant applicable to the resin composition of the present invention, for example, the compounds described in paragraphs

[0163] to

[0186] of Japanese Patent No. 5380840 can be mentioned.

[0226] The amount of antioxidant added is appropriately selected within a range that does not impair the object of the present invention, but is preferably within the range of 0.001 to 5 parts by mass, more preferably 0.01 to 3.0 parts by mass, and even more preferably 0.1 to 1.0 part by mass, per 100 parts by mass of the resin composition of the present invention.

[0227] (acid scavenger, UV absorber) Examples of additives that can be used in the three-dimensional laminate using the resin composition of the present invention include acid scavengers described in paragraphs

[0187] to

[0192] of Japanese Patent No. 5380840, and ultraviolet absorbers described in paragraphs

[0193] to

[0197] of the same.

[0228] (Other additives) In addition, various resin additives that can be used in combination with the resin composition of the present invention include fine particles, release agents, dyes and pigments, flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, dispersants, and antibacterial agents. In addition, various fillers can be blended. There are no particular limitations on the fillers to be blended as long as they do not reduce the functionality of the composition, and powdery, fibrous, granular, and plate-shaped inorganic fillers, as well as resin-based fillers and natural fillers, can be preferably used. Two or more of these may be used in combination.

[0229] The wavelength of the light irradiated to fluidize the resin composition is preferably 250 nm to 480 nm, more preferably 260 to 450 nm, and even more preferably 270 to 420 nm. Within this range, the resin composition is well absorbed, so that the light melting property is improved and the fixability is improved. In addition, by irradiating the resin composition with the above wavelength, the resin composition can be fluidized without applying heat or pressure. In addition, by introducing a resin composition containing a resin having a complementary multiple hydrogen bonding group and a photoisomerization compound having a complementary multiple hydrogen bonding group into a toner described later, it is possible to obtain a toner that can be fixed at the above wavelength and has high thin line reproducibility. The above wavelength range is the ultraviolet region, but also includes the visible light region close to ultraviolet. This is because the resin composition of the present invention can be fluidized under the following irradiation conditions even with irradiation light in the visible light region close to ultraviolet.

[0230] In order to make the resin composition non-fluid, heat or light energy is applied to the fluidized resin composition. Although the type of energy varies depending on the partial structure of the photoisomerization compound, the wavelength of light when irradiating light is preferably 330 nm to 700 nm, more preferably 340 to 680 nm, and even more preferably 350 to 650 nm. Within this range, light is absorbed well, so that non-fluidization can be achieved without applying heat or pressure. Therefore, by introducing a resin composition containing a resin having a complementary multiple hydrogen bonding group and a photoisomerization compound having a complementary multiple hydrogen bonding group into a toner described later, fixation at the above wavelength is possible, and a toner with high thin line reproducibility can be obtained. The above wavelength range is the ultraviolet region, but also includes the visible light region close to ultraviolet. This is because the resin composition of the present invention can be non-fluidized even with irradiation light in the visible light region close to ultraviolet under the following irradiation conditions.

[0231] [Toner for developing electrostatic images] The toner for developing electrostatic images (hereinafter, also simply referred to as "toner") of the present invention is characterized by containing the resin composition of the present invention. The resin in the resin composition contained in the toner can be used as a binder resin. In the following description of the toner, "binder resin" is to be read as "resin having complementary multiple hydrogen bonding groups".

[0232] The content (content ratio) of the resin in the resin composition contained in the toner, i.e., the binder resin (resin having complementary multiple hydrogen bonding groups) and the photoisomerizable compound, depends on the type of compound and the type of resin, but from the viewpoint of fixability and fine line reproducibility, the molar ratio of the complementary multiple hydrogen bonding groups of the photoisomerizable compound to the complementary multiple hydrogen bonding groups of the resin (molar number of complementary multiple hydrogen bonding groups of the photoisomerizable compound / molar number of complementary multiple hydrogen bonding groups of the resin) is preferably 0.05 to 7.0, more preferably 0.1 to 5.0, even more preferably 0.2 to 3.0, particularly preferably 0.3 to 2.5, and most preferably 0.5 to 2.0. Within this range, the photo-phase transition of the photoisomerizable compound is easily caused, and the toner is softened at a sufficient speed by light irradiation.

[0233] The toner of the present invention includes toner particles having toner base particles and an external additive attached to the surface of the toner base particles.

[0234] In this specification, the term "toner base particles" refers to a particle that constitutes the base of a "toner particle." The "toner base particles" contain at least a resin composition, i.e., a binder resin (a resin having a complementary multiple hydrogen bonding group) and a photoisomerizable compound (a photoisomerizable compound having a complementary multiple hydrogen bonding group), and may contain other components such as a colorant, a release agent (wax), and a charge control agent, as necessary. The "toner base particles" are called "toner particles" when an external additive is added. And, "toner" refers to an aggregate of "toner particles."

[0235] <Binding resin> The toner base particles may contain, in addition to the resin having complementary multiple hydrogen bonding groups and the photoisomerizable compound having complementary multiple hydrogen bonding groups, another binder resin (hereinafter also referred to as "other resin") other than the resin having complementary multiple hydrogen bonding groups.

[0236] It is generally known that by utilizing an emulsion aggregation method, which will be described later, as a method for producing toner, toner particles having a substantially uniform particle size and shape can be produced.

[0237] By using a resin having complementary multiple hydrogen bonding groups in combination with another binder resin, it is possible to prepare toner particles having a substantially uniform particle size and shape by using salting out in an emulsion aggregation method. Therefore, a toner containing a resin having complementary multiple hydrogen bonding groups, a photoisomerizable compound having complementary multiple hydrogen bonding groups, and another binder resin can be more easily applied to electrophotographic toners.

[0238] Such other binder resins can be any resins that are generally used as binder resins constituting toners, without any restrictions.Specific examples include styrene resins, acrylic resins, styrene-acrylic resins, polyester resins, silicone resins, olefin resins, amide resins, and epoxy resins.These other binder resins can be used alone or in combination of two or more.

[0239] Among these, from the viewpoint of having a low viscosity when melted and having high sharp melting properties, the other binder resin preferably includes at least one selected from the group consisting of a styrene resin, an acrylic resin, a styrene-acrylic resin, and a polyester resin, and more preferably includes at least one selected from the group consisting of a styrene-acrylic resin and a polyester resin.

[0240] The styrene-acrylic resin and polyester resin, which are preferred forms of other binder resins, are similar to the styrene-acrylic resin and polyester resin contained in the resin composition of the present invention, and therefore description thereof will be omitted here.

[0241] The toner containing the resin having a complementary multiple hydrogen-bonding group, the photoisomerizable compound having a complementary multiple hydrogen-bonding group, and other binder resins may have a single-layer structure or a core-shell structure. The types of binder resins used for the core particles and shell of the core-shell structure are not particularly limited.

[0242] <Coloring agent> The toner base particles preferably further contain a colorant. It is believed that the photoisomerizable compound having a complementary multiple hydrogen bonding group is colorless, but can induce reversible fluidization and non-fluidization phenomena upon isomerization. Therefore, by introducing a desired colorant into the toner together with the photoisomerizable compound having a complementary multiple hydrogen bonding group, a toner can be obtained that is fixable by light irradiation and has high color reproducibility of the added colorant. Generally known dyes and pigments can be used as the colorant.

[0243] Examples of colorants for obtaining black toner include carbon black, magnetic materials, iron-titanium composite oxide black, etc. Examples of carbon black include channel black, furnace black, acetylene black, thermal black, lamp black, etc. Examples of magnetic materials include ferrite, magnetite, etc.

[0244] Colorants for obtaining yellow toners include dyes such as CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, and 162; and pigments such as CI Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, and 185.

[0245] Colorants for obtaining magenta toner include dyes such as CI Solvent Red 1, 49, 52, 58, 63, 111, and 122; and pigments such as CI Pigment Red 5, 48:1, 53:1, 57:1, 122, 139, 144, 149, 166, 177, 178, and 222.

[0246] Colorants for obtaining cyan toner include dyes such as CI Solvent Blue 25, 36, 60, 70, 93, and 95; and pigments such as CI Pigment Blue 1, 7, 15, 60, 62, 66, and 76.

[0247] The colorants for obtaining the toner of each color may be used alone or in combination of two or more kinds for each color.

[0248] The content of the colorant in the toner base particles is preferably within a range of 0.5 to 20% by mass, and more preferably within a range of 2 to 10% by mass.

[0249] <Release agent> The toner of the present invention preferably further contains a release agent. By introducing a release agent into the toner together with the resin composition of the present invention (resin and photoisomerizable compound), a toner having better fixing property can be obtained.

[0250] The release agent used is not particularly limited, and various known waxes can be used. Examples of waxes include polyolefins such as low molecular weight polypropylene, polyethylene, or oxidized low molecular weight polypropylene and polyethylene, paraffin, and synthetic ester waxes. In particular, it is preferable to use synthetic ester waxes because of their low melting point and low viscosity, and it is particularly preferable to use behenyl behenate, glycerin tribehenate, pentaerythritol tetrabehenate, etc. as the synthetic ester wax.

[0251] The content of the release agent in the toner base particles is preferably within a range of 1 to 30% by mass, and more preferably within a range of 3 to 15% by mass.

[0252] <Charge control agent> The toner of the present invention may further contain a charge control agent. The charge control agent used is a substance that can impart positive or negative charge by frictional charging and is colorless, and is not particularly limited. Various known positively and negatively chargeable charge control agents can be used.

[0253] The content of the charge control agent in the toner base particles is preferably within a range of 0.01 to 30% by mass, and more preferably within a range of 0.1 to 10% by mass.

[0254] <External additives> In order to improve the fluidity, chargeability, cleaning properties, etc. of the toner, external additives such as a fluidizing agent, a cleaning aid, etc., which are so-called post-treatment agents, may be added to the toner particles to form the toner of the present invention.

[0255] Examples of the external additive include inorganic particles such as inorganic oxide particles, such as silica particles, alumina particles, and titanium oxide particles, inorganic stearic acid compound particles, such as aluminum stearate particles and zinc stearate particles, and inorganic titanic acid compound particles, such as strontium titanate particles and zinc titanate particles. These may be used alone or in combination of two or more kinds.

[0256] These inorganic particles may be surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat resistance, storage stability, and environmental stability.

[0257] The amount of these external additives added is preferably within a range of 0.05 to 5% by mass, and more preferably within a range of 0.1 to 3% by mass, of the toner base particles.

[0258] <Average particle size of toner> The average particle size of the toner is the volume-based median diameter (D 50 ) is preferably in the range of 4 to 10 μm, and more preferably in the range of 6 to 9 μm. 50 ) in the above range, the transfer efficiency is increased, the image quality of halftones is improved, and the image quality of fine lines, dots, etc. is improved.

[0259] In the present invention, the volume-based median diameter (D 50 ) is measured and calculated using a measuring device consisting of a "Coulter Counter 3" (manufactured by Beckman Coulter, Inc.) connected to a computer system (manufactured by Beckman Coulter, Inc.) equipped with the data processing software "Software V3.51."

[0260] Specifically, 0.02 g of the measurement sample (toner) was added to 20 mL of surfactant solution (for example, a neutral detergent containing a surfactant component diluted 10 times with pure water for the purpose of dispersing toner particles). After adding the toner to a surfactant solution and mixing, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is then poured with a pipette into a beaker containing an "ISOTON II" (manufactured by Beckman Coulter, Inc.) in the sample stand until the concentration indicated on the measuring device reaches 8%.

[0261] By setting the concentration range in this way, it is possible to obtain reproducible measured values. In the measurement device, the number of measured particles is set to 25,000, the aperture diameter is set to 50 μm, the measurement range of 1 to 30 μm is divided into 256 parts, and the frequency value is calculated. The particle diameters of 50% from the largest volume cumulative fraction are determined to be the volume-based median diameter (D 50 ) is said to be

[0262] [Toner manufacturing method] The method for producing the toner of the present invention is not particularly limited.

[0263] When a toner containing the compound represented by the general formula (1), a binder resin, and additives such as a colorant is produced, a production method utilizing an emulsion aggregation method, which allows easy control of particle size and shape, is preferable.

[0264] Such a manufacturing method is (1A) Binder resin particle dispersion preparation step of preparing a binder resin particle dispersion (1B) A colorant particle dispersion liquid preparation step for preparing a colorant particle dispersion liquid (1C) A photoisomerizable compound solution preparation step of preparing a solution of the photoisomerizable compound (2) An association step in which a flocculant is added to an aqueous medium in which binder resin particles, colorant particles, and a photoisomerizable compound are present, and salting out is promoted while simultaneously flocculation and fusion are carried out to form associated particles. (3) Aging process to form toner base particles by controlling the shape of aggregated particles (4) A filtering and washing process for filtering the toner particles from the aqueous medium and removing surfactants and the like from the toner base particles. (5) A drying process for drying the washed toner base particles. (6) Additive addition step of adding additives to the dried toner base particles It is preferable that the method includes the steps of: Steps (1A) to (1C) are described below.

[0265] (1A) Binder resin particle dispersion preparation process In this process, resin particles are formed by a conventional emulsion polymerization or the like, and the resin particles are aggregated and fused to form binder resin particles. As an example, polymerizable monomers constituting the binder resin are introduced into an aqueous medium, dispersed therein, and polymerized by a polymerization initiator to prepare a dispersion of binder resin particles.

[0266] As a method for obtaining a binder resin particle dispersion, in addition to the above-mentioned method of polymerizing a polymerizable monomer in an aqueous medium by a polymerization initiator, for example, a method of performing a dispersion treatment in an aqueous medium without using a solvent, or a method of dissolving a binder resin (such as a crystalline resin) in a solvent such as ethyl acetate to prepare a solution, emulsifying and dispersing the solution in an aqueous medium using a disperser, and then performing a solvent removal treatment can be mentioned.

[0267] In this case, if necessary, a release agent (wax) may be incorporated in advance into the binder resin. For dispersion, it is also preferable to carry out polymerization in the presence of a known surfactant (e.g., an anionic surfactant such as polyoxyethylene (2) sodium dodecyl ether sulfate, sodium dodecyl sulfate, or dodecylbenzenesulfonic acid). A release agent particle dispersion may be prepared separately from the binder resin particle dispersion in the same manner as in the colorant particle dispersion preparation step, and may be present in the aqueous medium in the association step (2) above.

[0268] The volume-based median diameter of the binder resin particles in the dispersion is preferably within a range of 50 to 300 nm. The volume-based median diameter of the binder resin particles in the dispersion can be measured by a dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

[0269] (1B) Colorant particle dispersion preparation process The colorant particle dispersion preparation step is a step of dispersing a colorant in the form of fine particles in an aqueous medium to prepare a colorant particle dispersion.

[0270] The colorant can be dispersed by utilizing mechanical energy. The median diameter based on the number of colorant particles in the dispersion is preferably within a range of 10 to 300 nm, and more preferably within a range of 50 to 200 nm. The median diameter based on the number of colorant particles can be measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).

[0271] (1C) Photoisomerizable compound solution preparation process The photoisomerizable compound solution preparation step is a step of dissolving a photoisomerizable compound having a complementary multiple hydrogen bonding group in an organic solvent to prepare a photoisomerizable compound solution. The amount of the organic solvent used is not particularly limited as long as it is sufficient to dissolve the photoisomerizable compound, but it is preferable to use as little as possible from the viewpoint of efficiently carrying out the subsequent association step and aging step.

[0272] <Organic solvent> The organic solvent used in this step is not particularly limited as long as it can dissolve the photoisomerizable compound of the present invention. Specific examples 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.

[0273] Such organic solvents can be used alone or in combination of two or more kinds. Among these organic solvents, ketones and halogenated hydrocarbons are preferred, and acetone, methyl ethyl ketone and dichloromethane are more preferred.

[0274] <Aqueous medium> The aqueous medium used in steps (1A) and (1B) may be water, or an aqueous medium containing water as the main component and water-soluble solvents such as alcohols and glycols, and optional components such as surfactants and dispersants. The aqueous medium used is preferably a mixture of water and a surfactant.

[0275] Examples of the surfactant include cationic surfactants, anionic surfactants, and nonionic surfactants. Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, and hexadecyl trimethyl ammonium bromide. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl benzene sulfonate, and sodium dodecyl sulfate. Examples of the nonionic surfactant include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, and monodecanoyl sucrose.

[0276] Such surfactants can be used alone or in combination of two or more. Among the surfactants, anionic surfactants are preferred, and sodium dodecylbenzenesulfonate is more preferred.

[0277] The amount of the surfactant added is preferably within a range of 0.01 to 10 parts by mass, and more preferably within a range of 0.04 to 1 part by mass, relative to 100 parts by mass of the aqueous medium.

[0278] The steps from (2) association step to (6) external additive addition step can be carried out according to various conventionally known methods.

[0279] The flocculant used in the (2) association step is not particularly limited, but is preferably selected from metal salts. Examples of metal salts include monovalent metal salts such as salts of alkali metals such as sodium, potassium, and lithium; divalent metal salts such as calcium, magnesium, manganese, and copper; and trivalent metal salts such as iron and aluminum. Specific examples of metal salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Among these, it is particularly preferable to use divalent metal salts because they can promote flocculation with a smaller amount. These can be used alone or in combination of two or more.

[0280] [Developer] The toner of the present invention may be used, for example, as a one-component magnetic toner by incorporating a magnetic material, as a two-component developer by mixing with a so-called carrier, or as a non-magnetic toner alone, and any of these may be suitably used.

[0281] As the magnetic material, for example, magnetite, γ-hematite, or various ferrites can be used.

[0282] As the carrier constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, steel, nickel, cobalt, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used.

[0283] As the carrier, it is preferable to use a coated carrier in which the surface of magnetic particles is coated with a coating agent such as resin, or a so-called resin dispersion type carrier in which magnetic powder is dispersed in a binder resin. The resin for coating is not particularly limited, but for example, olefin resin, styrene resin, styrene acrylic resin, silicone resin, polyester resin, or fluororesin is used. In addition, the resin for constituting the resin dispersion type carrier is not particularly limited, and a known one can be used, for example, acrylic resin, styrene acrylic resin, polyester resin, fluororesin, phenol resin, etc. can be used.

[0284] The volume-based median diameter of the carrier is preferably within a range of 20 to 100 μm, and more preferably 25 to 80 μm. The volume-based median diameter of the carrier can be measured typically by a laser diffraction particle size distribution measuring device "HELOS" (manufactured by SYMPATEC) equipped with a wet disperser.

[0285] The mixed amount of the toner to the carrier is preferably within a range of 2 to 10% by mass, with the total mass of the toner and carrier being 100% by mass.

[0286] [Image forming method] The toner of the present invention can be used in various known electrophotographic image forming methods. For example, it can be used in monochrome image forming methods and full-color image forming methods. In the full-color image forming method, it can be applied to any image forming method, such as a four-cycle image forming method consisting of four types of color developing devices for yellow, magenta, cyan, and black, and one photoconductor, and a tandem image forming method in which image forming units having color developing devices and photoconductors for each color are installed for each color.

[0287] An image forming method according to one embodiment of the present invention includes the steps of forming a toner image made of a toner containing the resin composition of the present invention on a recording medium, and irradiating the toner image with light to soften the toner image.

[0288] In order to sufficiently fluidize the photoisomerizable compound in the toner and quickly soften the toner image, it is preferable that the wavelength of the light used when irradiating the toner image is within the range of 280 nm to 480 nm.

[0289] From the viewpoint of obtaining a better fixing property, it is preferable to further include a step of pressurizing the toner image. Furthermore, from the viewpoint of obtaining a better fixing property, it is preferable to further heat the toner image in the pressurizing step.

[0290] Fig. 1 is a schematic 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 form and illustrated example. Fig. 1 shows an example of a monochrome image forming apparatus 100, but the present invention can also be applied to a color image forming apparatus.

[0291] The image forming apparatus 100 is an apparatus for forming an image on a recording paper S as a recording medium, and is equipped with an image reading device 71 and an automatic document feeder 72, and performs image formation on the recording paper S transported by a paper transport system 7 using an image forming unit 10, an irradiation unit 40, and a pressing unit 9.

[0292] Furthermore, while image forming apparatus 100 uses recording paper S as a recording medium, the medium on which an image is formed may be something other than paper.

[0293] An original d placed on the platen of the automatic document feeder 72 is scanned and exposed by the optical system of the scanning exposure device of the image reading device 71 and read into the image sensor CCD. An analog signal photoelectrically converted by the image sensor CCD is subjected to analog processing, A / D conversion, shading correction, image compression processing, etc. in the image processing unit 20, and then input to the exposure device 3 of the image forming unit 10.

[0294] The paper transport system 7 includes a plurality of trays 16, a plurality of paper feed units 11, transport rollers 12, a transport belt 13, etc. The trays 16 each store recording paper S of a predetermined size, and operate the paper feed unit 11 of the specified tray 16 in response to an instruction from the control unit 90 to supply the recording paper S. The transport rollers 12 transport the recording paper S sent out from the tray 16 by the paper feed unit 11 or the recording paper S brought in from the manual paper feed unit 15 to the image forming unit 10.

[0295] The image forming unit 10 is configured with a charger 2, an exposure unit 3, a developing unit 4, a transfer unit 5, a charge removal unit (not shown), and a cleaning unit 8 arranged in this order around the photoreceptor 1 along the direction of rotation of the photoreceptor 1.

[0296] The photoconductor 1, which is an image carrier, is an image carrier having a photoconductive layer formed on its surface, and is configured to be rotatable in the direction of the 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.

[0297] The charger 2 uniformly charges the surface of the photoreceptor 1, thereby uniformly charging the surface of the photoreceptor 1. The exposure unit 3 is equipped with a beam emission source such as a laser diode, and irradiates the charged surface of the photoreceptor 1 with a beam of light, thereby dissipating the charge in the irradiated area and forming an electrostatic latent image on the photoreceptor 1 according to the image data. The development unit 4 supplies the toner contained therein to the photoreceptor 1, and creates a toner image on the surface of the photoreceptor 1 based on the electrostatic latent image.

[0298] The transfer unit 5 faces the photoreceptor 1 via the recording paper S, and transfers the toner image onto the recording paper S. The charge removing unit removes charge from the photoreceptor 1 after the toner image has been transferred. The cleaning unit 8 includes a blade 85. The blade 85 cleans the surface of the photoreceptor 1 to remove any developer remaining on the surface of the photoreceptor 1.

[0299] The recording paper S onto which the toner image has been transferred is transported by a transport belt 13 to a pressing unit 9. The pressing unit 9 may be installed arbitrarily, and performs a fixing process on the recording paper S onto which the toner image has been transferred by applying pressure alone or heat and pressure with pressure members 91 and 92, thereby fixing the image onto the recording paper S. The recording paper S onto which the image has been fixed is transported by transport rollers to a paper discharge unit 14, and is discharged from the paper discharge unit 14 to the outside of the machine.

[0300] In addition, the image forming apparatus 100 is equipped with a paper inversion section 24, so that the recording paper S that has been subjected to the heat fixing process is transported to the paper inversion section 24 just before the paper discharge section 14, and the recording paper S is either inverted and discharged, or the inverted recording paper S is transported again to the image forming section 10, so that images can be formed on both sides of the recording paper S.

[0301] <Irradiation unit> FIG. 2 is a schematic diagram of the irradiation unit 40 in the image forming apparatus 100. As shown in FIG.

[0302] The image forming apparatus 100 according to one embodiment of the present invention includes an irradiation unit 40. Examples of devices constituting the irradiation unit 40 include a light emitting diode (LED) and a laser light source.

[0303] The irradiation section 40 melts and fluidizes the photoisomerizable compound contained in the toner of the developer. The wavelength of the irradiated light may be sufficient to sufficiently fluidize the toner, and light having a wavelength preferably in the range of 280 to 480 nm, more preferably in the range of 300 to 420 nm, and even more preferably in the range of 330 to 420 nm is irradiated. The amount of light irradiated by the irradiation section 40 (accumulated amount of light) may also be sufficient to sufficiently fluidize the toner, and is preferably 0.1 to 200 J / cm. 2within the range of 0.1 to 100 J / cm 2 within the range of 0.1 to 50 J / cm 2 is within the range.

[0304] When the photoisomerizable compound is to be made non-fluid (re-solidified), it may be made non-fluid by leaving it as it is at room temperature (within the range of 25±15° C.).

[0305] That is, an image forming method according to one embodiment of the present invention includes the steps of forming a toner image made of the toner of the present invention on a recording medium, irradiating the toner image with light having a wavelength in the range of 280 to 480 nm to soften the toner image, and leaving the softened toner image at room temperature (within the range of 25±15° C.) to solidify the toner image and fix it to the recording medium. Note that the fixing step preferably further includes a step of pressurizing the softened toner image. In the pressurizing step, it is preferable to further heat the softened toner image. This is because heating the toner image can further soften it.

[0306] The heating temperature during the further heating in the pressurizing step is preferably within the range of 30 to 100°C, and more preferably within the range of 40 to 100°C.

[0307] Irradiation unit 40 irradiates light toward a first surface of recording paper S holding a toner image, which is on the photoreceptor side, and is disposed on the photoreceptor side with respect to the surface of recording paper S nipped between photoreceptor 1 and transfer roller 5, which is a transfer unit. Irradiation unit 40 is disposed along the transport direction of recording paper S (paper transport direction).

[0308] The irradiation unit 40 is disposed downstream of the nip position between the photoconductor 1 and the transfer roller 5 in the paper transport direction and upstream of the pressure bonding unit 9 in the paper transport direction.

[0309] According to an image forming method according to an embodiment of the present invention, the photoconductor 1 is charged by applying a uniform potential to it using the charger 2, and then the photoconductor 1 is scanned with a light beam irradiated by the exposure unit 3 based on original image data to form an electrostatic latent image. Next, the developing unit 4 supplies a developer having a toner containing a photoisomerizable compound onto the photoconductor 1.

[0310] When the recording paper S is transported from the tray 16 to the image forming unit 10 in time with the rotation of the photoconductor 1 causing the toner image carried on the surface of the photoconductor 1 to reach the position of the transfer roller 5, which is the transfer unit, the toner image on the photoconductor 1 is transferred onto the recording paper S, which is nipped between the transfer roller 5 and the photoconductor 1, by the transfer bias applied to the transfer roller 5.

[0311] In addition, the transfer member 5 also serves as a pressure member, and can transfer the toner image from the photoreceptor 1 to the recording paper S while reliably bringing the photoisomerizable compound contained in the toner image into close contact with the recording paper S.

[0312] After the toner image is transferred onto the recording paper S, the blade 85 of the cleaning unit 8 removes the developer remaining on the surface of the photoconductor 1 .

[0313] In the process in which the recording paper S onto which the toner image has been transferred is transported by the transport belt 13 to the pressing unit 9, the irradiation unit 40 irradiates the toner image transferred onto the recording paper S with light having a wavelength of 280 to 480 nm. By irradiating the toner image on the first surface of the recording paper S with ultraviolet light by the irradiation unit 40, the toner image can be melted more reliably, and the fixability of the toner image to the recording paper S can be improved.

[0314] When the recording paper S carrying the toner image reaches the pressing unit 9 by the conveyor belt 13, the pressure members 91 and 92 press the toner image onto the first side of the recording paper S. Before the toner image is fixed by the pressing unit 9, the toner image is softened by irradiation with ultraviolet light by the irradiation unit 40, so that energy saving can be achieved in pressing the image onto the recording paper S. It is preferable that the image forming method of the present invention further includes a step of pressing the toner image with the pressure members 91 and 92 while leaving it at room temperature (within a range of 25±15° C.) in the step of solidifying the toner image and fixing it onto the recording medium. By applying pressure with the pressure members 91 and 92, the fixability of the toner image onto the recording paper S is further improved.

[0315] The pressure when pressing the toner image on the recording medium is not particularly limited, but is preferably in the range of 0.01 to 5.0 MPa, and more preferably in the range of 0.05 to 1.0 MPa. By setting the pressure to 0.01 MPa or more, the deformation amount of the toner image can be increased, so that the contact area between the toner image and the recording paper S increases, and it is easy to further improve the fixability of the image. In addition, by setting the pressure to 5.0 MPa or less, shock noise during pressing can be suppressed.

[0316] In the pressurizing step, it is preferable to further heat the toner image. By applying pressure and heat by the pressure members 91 and 92, the fixability of the toner image to the recording paper S is further improved. Specifically, when the recording paper S passes between the pressure members 91 and 92, the toner image softened by light irradiation is pressurized by the pressure member 91 in a state further softened by heating, so that the fixability of the toner image to the recording paper S is further improved.

[0317] Thereafter, the toner image on the recording paper S is solidified in a natural environment (left at room temperature). Specifically, by leaving the recording paper S that has passed between the pressure members 91 and 92 in a natural environment (left at room temperature) until it reaches the paper discharge unit 14, the toner image on the recording paper S can be solidified more reliably, and the fixability of the toner image to the recording paper S can be further improved.

[0318] When forming images on both sides of the recording paper S, the recording paper S that has been subjected to the pressure bonding process is transported to the paper inversion section 24 just before the paper discharge section 14, and either inverted and discharged, or the inverted recording paper S is transported again to the image forming section 10.

[0319] (Photoswitching Materials) The resin composition of the present invention is fluidized by light irradiation and then non-fluidized, so that a light-switching material can be prepared using the resin composition of the present invention. For example, a light-switching material can be prepared by utilizing the change in color or polarity, mass transfer, change in orientation, change in viscosity, and change in surface tension associated with photoisomerization. The resin composition of the present invention can be applied to patterning drawing that can be repeatedly rewritten in response to the change in molecular orientation associated with photoisomerization, for example, in liquid crystal materials. In addition, for example, the change in surface tension associated with light irradiation and the resulting mass transfer can be used to perform microfabrication of the surface of a polymer film. That is, according to one embodiment of the present invention, a light-switching material containing the resin composition of the present invention is provided.

[0320] (Photosensitive adhesive) The resin composition of the present invention is fluidized by light irradiation and then becomes non-fluid, so that a photosensitive adhesive that can be used repeatedly can be produced using the resin composition of the present invention. For example, the resin composition of the present invention can be applied to various adhesion techniques as a photosensitive adhesive that can be repeatedly attached and detached by light in response to changes in viscosity (friction coefficient). That is, one embodiment of the present invention is a photosensitive adhesive that includes the resin composition of the present invention.

[0321] The photosensitive adhesive of the present invention can be used for temporary fixing that can be reused repeatedly, and is also suitable for recycling, but is not limited thereto.

[0322] When the resin composition of the present invention is used as a temporary bonding material for bonding two objects, if it is not made non-fluid after peeling from the object by light irradiation, it will adhere to various things in the working environment and pollute the working environment. In addition, since it may cause deterioration of the quality of the object, it is necessary for the resin composition of the present invention to be made fluid by light irradiation and then non-fluid. In a preferred embodiment, the resin composition of the present invention is reversibly made fluid / non-fluid by light irradiation.

[0323] In addition to the resin composition of the present invention, the photosensitive adhesive of the present invention may contain additives such as plasticizers, antioxidants, acid scavengers, and UV absorbers described in <Other additives to the resin composition>, but is not limited to these. EXAMPLES

[0324] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the operations were performed at room temperature (25°C). Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[0325] The photoisomerizable compounds shown in the following Tables 1 to 4 were synthesized by the above-mentioned synthesis methods, respectively. Furthermore, the comparative compounds A to D used in the comparative examples were synthesized by the following method.

[0326] [ka]

[0327] [Synthesis of Comparative Compound A (Azobenzene Compound A)] Azobenzene compound A was obtained by the same method as "(1-1-1) Synthesis of UV softening material A" described in paragraphs

[0217] to

[0224] of JP2014-191078A. The structure is 1 1 H-NMR and IR confirmed that the desired compound had been obtained.

[0328] [ka]

[0329] [Synthesis of Comparative Compound B (Azobenzene Compound B)] Azobenzene compound B was obtained in the same manner as "(1-2-1) Synthesis of UV softening material B" described in paragraphs

[0227] to

[0237] of JP2014-191078A. The structure is: 1 1 H-NMR and IR confirmed that the desired compound had been obtained.

[0330] [ka]

[0331] [Synthesis of Comparative Compound C (Stilbene Compound C)] The synthesis was based on Chemistry of Materials, 2015, 27(21), 7388-7394.

[0332] [ka]

[0333] [Synthesis of Comparative Compound D (Azomethine Compound D)] 4-Hydroxy-3-methylbenzaldehyde and 1-iodohexane (CH 13 I) was reacted with potassium carbonate (K2CO3) by heating under reflux, the reaction solution was washed with water, concentrated, and purified by column chromatography to obtain 4-hexyloxy-3-methylbenzaldehyde (see Scheme 1 below). 4-Hexyloxy-3-methylbenzaldehyde obtained in Scheme 1 and 5-hexylthiophene-2-amine were reacted in ethanol (EtOH) by heating and stirring, the reaction solution was filtered, the obtained powder was washed with cooled ethanol, and recrystallized from methanol / ethanol to obtain the target azomethine compound D (see Scheme 2 below). The structure is 11 H-NMR and IR confirmed that the desired compound had been obtained.

[0334] [ka]

[0335] The resins shown in Tables 1 to 4 below were each synthesized by the synthesis method described below.

[0336] In the following, the molar ratio of the unit (S) (unit S) not having a complementary multiple hydrogen bonding group B to the unit (T) (unit T) having a complementary multiple hydrogen bonding group B among all the units constituting the resin is, for example, in the case of PA1-1, MA / MA1=6 / 94 (mol / mol), so S / T=6 / 94. In addition, the content (molar ratio) of the complementary multiple hydrogen bonding group B, which is a side chain, in the resin composed of the unit S and the unit T is, for example, in the case of PA1-1, MA / MA1=6 / 94 (mol / mol), so B / (S+T)=6 / 100.

[0337] Compounds MA1 to MA8 represented below were synthesized by the following method. DC1 (5-(2-propen-1-yloxy)-1,3-benzenedicarboxylic acid), which is a polyvalent carboxylic acid component of the polyester resin, was purchased from Chemieliva Pharmaceutical.

[0338] [ka]

[0339] [Synthesis of (meth)acrylate monomers] <Synthesis example MA1> With reference to Organic & Biomolecular Chemistry, 2004, 2(22), 3374, 2-(6-amino-9H-purin-9-yl)ethanol (Sigma-Aldrich) and acryloyl chloride (Tokyo Chemical Industry Co., Ltd.) were used to obtain a monomer MA1 having an adenine moiety. The structure is:1 The results were confirmed by H-NMR and IR.

[0340] <Synthesis example MA2> With reference to Journal of Medicinal Chemistry, 2012, 55(20), 8712, a monomer MA2 having a thymine moiety was obtained using 2-bromoethyl acrylate (Sigma-Aldrich), 2,4-di-t-butyl-p-cresol (Tokyo Chemical Industry Co., Ltd.), and O,O'-bis(trimethylsilyl)thymine (Sigma-Aldrich). The structure is: 1 The results were confirmed by H-NMR and IR.

[0341] <Synthesis example MA3> A monomer MA3 having a 2,6-diacetamidopyridine moiety was obtained in the same manner as in Synthesis Example MA1, except that 2-(6-amino-9H-purin-9-yl)ethanol in Synthesis Example MA1 was replaced with 2,6-diacetamido-4-hydroxymethylpyridine (manufactured by Hong Kong Chemhere). The structure is: 1 The results were confirmed by H-NMR and IR.

[0342] <Synthesis example MA4> Monomer MA4 having a uracil moiety was obtained from Sigma-Aldrich.

[0343] <Synthesis example MA5> The monomer MA5 having a melamine moiety was obtained from Chemieliva Pharmaceutical.

[0344] <Synthesis example MA6> 1-(4-nitrophenyl)-1,3,5-triazine-2,4,6-trione (5.0 g, 20.0 mmol, manufactured by Chemieliva Pharmaceutical) and palladium carbon (0.09 g, 200 mmol) were placed in a 200 ml Erlenmeyer flask, and 30 ml each of ethanol and tetrahydrofuran were added. The mixture was stirred while hydrogen was sealed in. Palladium carbon was removed from the reaction solution, and the resulting solution was concentrated and then recrystallized from ethanol to obtain 4.2 g (yield 95%) of 1-(4-aminophenyl)-1,3,5-triazine-2,4,6-trione. Next, a monomer MA6 having a cyanuric acid moiety was obtained in the same manner as in <Synthesis Example MA1>, except that 2-(6-amino-9H-purin-9-yl)ethanol in <Synthesis Example MA1> was replaced with 1-(4-aminophenyl)-1,3,5-triazine-2,4,6-trione. The structure is as follows: 1 The results were confirmed by H-NMR and IR.

[0345] <Synthesis example MA7> The monomer MA7 having a diaminotriazine moiety was obtained from Chemieliva Pharmaceutical.

[0346] <Synthesis example MA8> A monomer MA8 having a naphthalimide moiety was obtained in the same manner as in Synthesis Example MA1, except that 2-(6-amino-9H-purin-9-yl)ethanol in Synthesis Example MA1 was replaced with 5-amino-1H-benzo[de]isoquinoline-1,3-dione (manufactured by Chemieliva Pharmaceutical). The structure is: 1 The results were confirmed by H-NMR and IR.

[0347] [Synthesis of acrylic resin] The acrylic resins PA1-1 to PA1-5 and PA2 to PA8 shown below were synthesized by the following method.

[0348] [ka]

[0349] <Synthesis Example PA1-1> 50 ml of tetrahydrofuran was added to a 100 ml three-neck flask equipped with a nitrogen line and a cooling tube, and heated to reflux for 10 minutes. The flask was cooled to room temperature while nitrogen was flowing, and 9.5 ml of degassed tetrahydrofuran was measured using a nitrogen-substituted syringe. This tetrahydrofuran was added to a 50 ml four-neck flask equipped with a nitrogen line, a cooling tube, and a thermometer, and already substituted with nitrogen using a vacuum pump and nitrogen. Then, under nitrogen flow, methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.05 g, 0.6 mmol), MA1 (2.57 g, 11.0 mmol) obtained in <Synthesis Example MA1>, and AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.10 g, 0.6 mmol) were added, and heated to reflux for 6 hours. After cooling to room temperature, the polymerization solution was slowly dropped into 50 ml of vigorously stirred ethanol, and reprecipitated. After the entire polymerization solution was dropped, the solution was stirred at room temperature for 30 minutes, and the solids were filtered. The obtained solid was dried using a vacuum pump to obtain 2.28 g of PA1-1 having an adenine moiety (yield 87%). The molar ratio of MA (methyl acrylate) to MA1 (MA / MA1) in PA1-1 was: 1 The ratio was calculated from the integral ratio of H-NMR and was found to be 6 / 94 (mol / mol).

[0350] In the case of PA1-1, among all the units constituting the resin, the molar ratio of the units (S) that do not have complementary multiple double hydrogen bonding groups B as side chains to the units (T) that have complementary multiple hydrogen bonding groups B as side chains was MA / MA1 = 6 / 94 (mol / mol), and therefore S / T = 6 / 94.

[0351] Furthermore, for a resin composed of units S and units T, the content of the complementary multiple hydrogen bonding group B, which is a side chain, is, for example, in the case of PA1-1, MA / MA1=6 / 94 (mol / mol), and therefore B / (S+T)=6 / 100.

[0352] The molecular weight of the resulting resin was measured by gel permeation chromatography (GPC) under the following conditions.

[0353] (GPC measurement conditions) Solvent: methylene chloride Column: Shodex K806, K805, K803 (three columns made by Showa Denko Co., Ltd. were connected and used) Column temperature: 25℃ Sample concentration: 0.1% by mass Detector: RI Model 504 (GL Sciences) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0mL / min.

[0354] The Mn of PA1-1 thus determined was 21,400, and the Mw / Mn was 2.33.

[0355] <Synthesis Example PA1-2> Except for using methyl acrylate (Tokyo Chemical Industry Co., Ltd.) (0.25 g, 2.9 mmol), MA1 (2.03 g, 8.7 mmol) obtained in <Synthesis Example MA1>, and AIBN (Tokyo Chemical Industry Co., Ltd.) (0.10 g, 0.6 mmol), the same procedure as in <Synthesis Example PA1-1> was followed to obtain 1.92 g of PA1-2 (yield 84%). The ratio of MA to MA2 in PA1-2 (MA / MA2), i.e., S / T, was 1 The Mn of PA1-2 was 26,800, and the Mw / Mn was 2.41.

[0356] <Synthesis Example PA1-3 (Feed Ratio: 50 / 50)> Except for using methyl acrylate (Tokyo Chemical Industry Co., Ltd.) (0.5 g, 5.8 mmol), MA1 (1.35 g, 5.8 mmol) obtained in <Synthesis Example MA1>, and AIBN (Tokyo Chemical Industry Co., Ltd.) (0.10 g, 0.6 mmol), the same procedure as in <Synthesis Example PA1-1> was followed to obtain 1.92 g of PA1-3 (yield 84%). The ratio of MA to MA3 in PA1-3 (MA / MA3), i.e., S / T, was 1 The ratio was calculated from the integral ratio of H-NMR and was 52 / 48 (mol / mol). In addition, Mn of PA1-3 was 29100, and Mw / Mn was 2.32.

[0357] <Synthesis Example PA1-4> Except for using methyl acrylate (Tokyo Chemical Industry Co., Ltd.) (1.0 g, 11.6 mmol), MA1 (0.9 g, 3.9 mmol) obtained in <Synthesis Example MA1>, and AIBN (Tokyo Chemical Industry Co., Ltd.) (0.13 g, 0.8 mmol), the same procedure as in <Synthesis Example PA1-1> was followed to obtain 1.56 g of PA1-4 (yield 82%). The ratio of MA to MA1 in PA1-1 (MA / MA1), i.e., S / T, was 1 The ratio was calculated from the integral ratio of H-NMR and was 77 / 23 (mol / mol). In addition, Mn of PA1-4 was 24,400, and Mw / Mn was 2.21.

[0358] <Synthesis Example PA1-5> Except for using methyl acrylate (Tokyo Chemical Industry Co., Ltd.) (2.0 g, 23.2 mmol), MA1 (0.29 g, 1.2 mmol) obtained in <Synthesis Example MA1>, and AIBN (Tokyo Chemical Industry Co., Ltd.) (0.20 g, 1.22 mmol), the same procedure as in <Synthesis Example PA1-1> was followed to obtain 1.97 g of PA1-5 (yield 86%). The ratio of MA to MA1 in PA1-5 (MA / MA1), i.e., S / T, was: 1 The molar ratio was calculated from the integral ratio of H-NMR and was 93 / 7 (mol / mol). In addition, Mn of PA1-5 was 25700, and Mw / Mn was 2.08.

[0359] <Synthesis example PA-A: Comparative example> Except for using methyl acrylate (Tokyo Chemical Industry Co., Ltd.) (2.0 g, 23.2 mmol) and AIBN (Tokyo Chemical Industry Co., Ltd.) (0.19 g, 1.16 mmol), the same procedure as in <Synthesis Example PA1-1> was followed to obtain 1.82 g of PA-A (yield 91%). The Mn of PA-A was 26300, and the Mw / Mn was 2.44.

[0360] <Synthesis examples PA2~PA8> PA2 to PA8 were synthesized in the same manner as in <Synthesis Example PA1-4>, except that MA1 in <Synthesis Example PA1-4> was replaced with MA2 to MA8.

[0361] [Synthesis of polyesters and polyesters with complementary multiple hydrogen-bonding groups] According to the method described below, polyesters PES1-1 to PES1-3 shown below were synthesized, and then complementary multiple hydrogen-bonding groups were introduced to synthesize polyesters PES1-1-1 to PES1-3-1. Also, according to the method described below, polyesters PES2-1-1 to PES2-3-1 shown below were synthesized, and then complementary multiple hydrogen-bonding groups were introduced to synthesize polyesters PES2-1 to PES2-3.

[0362] [ka]

[0363] [ka]

[0364] <Synthesis examples PES1-1 to PES1-3> PES1-1 to PES1-3 were synthesized using 5-(2-propen-1-yloxy)-1,3-benzenedicarboxylic acid (manufactured by Chemieliva Pharmaceutical) (DC1) with reference to Journal of Polymer Science, Polymer Physics Edition, 21, 7, 1091-1101 (1983). The introduction rate of allyloxy group units in the polymer was 1 The ratios calculated from the integral ratios of H-NMR were 5 / 95, 74 / 26, and 96 / 4 (mol / mol), respectively.

[0365] <Synthesis examples PES1-1-1~PES1-3-1> After PES1-1 to PES1-3 were completely dissolved in tetrahydrofuran, 1.5 times the molar amount of 6-amino-9H-purine-9-ethanethiol (manufactured by Aurora Fine Chemicals LLC) was added to the reaction solution relative to the allyl group contained in each polymer, and the reaction solution was irradiated with UV light (254 nm) while stirring in the same manner as in Green Chemistry, 2013, 15(4), 1016. Ethyl alcohol in an amount 30 times the amount of the reaction solution was placed in a flask, a mechanical stirrer and a Teflon (registered trademark) blade were installed, and the resulting reaction solution was dropped into the ethyl alcohol that was being vigorously stirred over 1 hour. After stirring for 2 hours, the mixture was filtered under reduced pressure using a Nutsche filter and filter paper. The resulting solid was dried under reduced pressure at 60°C to obtain PES1-1-1 to PES1-3-1. 1 The disappearance of the double bond of the allyl group was confirmed by the integral ratio of 1 H-NMR.

[0366] In addition, S / T in PES1-1-1 to PES1-3-1 is 1 The ratios were calculated based on the integral ratios of allyl groups in H-NMR and were 5 / 95, 74 / 26, and 96 / 4 (mol / mol), respectively. The Mn values ​​of PES1-1-1 to PES1-3-1 were 20,800, 21,700, and 19,600, respectively, and the Mw / Mn values ​​of PES1-1-1 to PES1-3-1 were 2.38, 2.27, and 2.41, respectively.

[0367] <Synthesis examples PES2-1~PES2-3> PES2-1 to PES2-3 were synthesized with reference to Macromolecules, 37, 7, 2532-2537 (2004). The introduction rate of allyloxy group units in the polymer was 1 The NMR integral ratios were calculated to be 7 / 93, 76 / 24, and 94 / 6 (mol / mol), respectively.

[0368] <Synthesis examples PES2-1-1~PES2-3-1> PES2-1-1 to PES2-3-1 were obtained in the same manner as in <Synthesis Examples PES1-1-1 to PES1-3-1>, except that PES2-1 to PES2-3 were used instead of PES1-1 to PES1-3. 1The disappearance of the double bond of the allyl group was confirmed by the integral ratio of 1 H-NMR.

[0369] In addition, S / T in PES2-1-1 to PES2-3-1 is 1 The ratios were calculated based on the integral ratios of allyl groups in H-NMR and were 7 / 93, 76 / 24, and 94 / 6 (mol / mol), respectively. The Mn values ​​of PES2-1-1 to PES2-3-1 were 22700, 24100, and 22200, respectively, and the Mw / Mn values ​​of PES2-1-1 to PES2-3-1 were 2.51, 2.35, and 2.27, respectively.

[0370] [Synthesis of polycarbonates and polycarbonates with complementary multiple hydrogen-bonding groups] According to the method described below, polycarbonates PC1-1 to PC1-3 shown below were synthesized, and then used to synthesize polycarbonates PC1-1-1 to PC1-3-1 each having complementary multiple hydrogen bonding groups.

[0371] [ka]

[0372] <Synthesis example PC1-1~PC1-3> PC1-1 to PC1-3 were synthesized with reference to Macromolecules, 25, 18, 4588-4596 (1992). The introduction rate of allyloxy group units in the polymer was 1 The ratios calculated from the integral ratios of H-NMR were 6 / 94, 76 / 24, and 93 / 7 (mol / mol), respectively.

[0373] <Synthesis example PC1-1-1~PC1-3-1> PC1-1-1 to PC1-3-1 were obtained in the same manner as in <Synthesis Examples PES1-1-1 to PES1-3-1>, except that PC1-1 to PC1-3 were used instead of PES1-1 to PES1-3. 1 The disappearance of the double bond of the allyl group was confirmed by the integral ratio of 1 H-NMR.

[0374] In addition, S / T in PC1-1-1 to PC1-3-1 is 1 The ratios were calculated based on the integral ratios of the allyl groups in H-NMR and were 6 / 94, 76 / 24, and 93 / 7 (mol / mol), respectively. The Mn values ​​of PC1-1-1 to PC1-3-1 were 17,400, 19,600, and 18,800, respectively, and the Mw / Mn values ​​of PC1-1-1 to PC1-3-1 were 2.02, 2.29, and 2.14, respectively.

[0375] (1) Example 1 [Preparation of resin composition] <Preparation of Resin Composition 1-1> 100 mg of PA1-1 and 235 mg of photoisomerizable compound 1 were placed in a petri dish, and 100 ml of CHCl3 was added. The dish was covered with aluminum foil and left in a fume hood until the CHCl3 had dried. The solvent was then removed by vacuum drying at room temperature using a reduced pressure dryer.

[0376] <Resin Compositions 1-2 to 1-53 and 1-A to 1-F> Compositions 1-2 to 1-53 and Comparative Examples 1-A to 1-F were prepared in the same manner as in <Preparation of Composition 1-1> using the resins and photoisomerization compounds shown in Tables 1 and 2, and using the resins and photoisomerization compounds in the ratios shown in Tables 1 and 2. In the case of compositions that were difficult to dissolve, the solution was heated to dissolve them.

[0377] [Photoresponsive adhesion test] The changes in adhesiveness of the resin compositions 1-1 to 1-53 and 1-A to 1-H prepared above due to light irradiation were evaluated by the following photoresponsive adhesion test using the device shown in FIG.

[0378] As shown in FIG. 3, 2 mg of compound was placed on an 18 mm square cover glass 1 within a 6 mm radius from the center of the glass, and a cover glass 2 of the same size was placed at a position shifted by about 4 mm in the parallel direction relative to the cover glass 1.

[0379] After each of resin compositions 1-1 to 1-53 and 1-A to 1-F was sandwiched between cover glasses, the cover glasses were heated to melt the resin composition and bond cover glass 1 and cover glass 2. Each of the obtained samples was subjected to the following fluidization test (non-fluidity to fluidity test), and then to the following non-fluidization test (fluidity to non-fluidity test).

[0380] <Fluidity test (test to change non-fluidity to fluidity)> Part (A) shown in Figure 3 was fixed to the stand with cellophane tape, and a 30 cm long vinyl string with a 100 g weight attached was fixed to part (C) with cellophane tape. Part (B) was irradiated with light of 365 nm wavelength at a dose of 30 J / cm. 2 It was then confirmed whether cover glass 2 peeled off from cover glass 1, and the result was judged according to the following evaluation criteria. In the following evaluation criteria, ○ and △ were considered to be acceptable. The obtained results are shown in Tables 1 and 2.

[0381] (Evaluation Criteria) ○: Cover glass 2 was completely peeled off from cover glass 1 △: Cover glass 2 is displaced ×: The cover glass 2 did not move.

[0382] <Defluidity test (fluidity to non-fluidity test)> Non-fluidity → 5 minutes after the start of the fluidity test (the 5 minutes were left in a natural environment, i.e., at room temperature (within the range of 25±15°C)), cover glass 3 (same size as cover glasses 1 and 2) was placed over the sample portion (part (B)) of cover glass 1 used in the above test, and it was confirmed whether cover glass 1 and cover glass 3 were adhered, and judged according to the evaluation criteria below. In the evaluation criteria below, ○ and △ were considered to be passing. The results are shown in Tables 1 and 2.

[0383] (Evaluation Criteria) 〇: Did not adhere (had become non-fluid) △: Partially adhered (partially maintained in a fluid state) ×: Adhered (fluid state was maintained) In addition, in the following Tables 1 to 4, "B in photoisomerizable compound / B in resin" represents "the number of moles of complementary multiple hydrogen bonding groups in the photoisomerizable compound / the number of moles of complementary multiple hydrogen bonding groups in the resin."

[0384] [Table 1]

[0385] [Table 2]

[0386] As shown by the above results, it was confirmed that the resin composition of the present invention induces reversible fluidization / non-fluidization phenomena in the fluidization and non-fluidization tests. In contrast, the resin composition of the comparative example did not induce both fluidization and non-fluidization phenomena. In addition, in the fluidization test for the comparative resin composition 1-A, the cover glass 2 was completely peeled off from the cover glass 1, but the coating film peeled off from the cover glass.

[0387] [Example 2-1: Preparation of Toner 1] (2) Example 2 [Production of Toner 2-1] <Preparation of styrene acrylic resin particle dispersion 1C-C> (First stage polymerization) A solution of 8 g of sodium dodecyl sulfate dissolved in 3000 g of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, and the internal temperature was raised to 80° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. After the temperature was raised, a solution of 15.0 g of potassium persulfate dissolved in 200 g of ion-exchanged water was added, and the liquid temperature was again raised to 80° C. Meanwhile, a polymerizable monomer solution consisting of styrene (475.2 g, 4.56 mol), n-butyl acrylate (247.5 g, 1.93 mol), methacrylic acid (67.3 g, 0.93 mol), the monomer MA1 (17.5 g, 0.08 mol) synthesized in <Synthesis Example MA1>, and 16.0 g of n-octyl-3-mercaptopropionate was mixed, and then a 5 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 8. After that, the monomer solution was dropped into the solution in which the surfactant and initiator were dissolved over the course of one hour. After the dropwise addition was completed, the mixture was heated and stirred at 80°C for two hours to polymerize, and a styrene-acrylic resin particle dispersion (1A) containing styrene-acrylic resin particles (1a) was prepared. This solution was heated to 60°C, and photoisomerization compound 1 (synthesized in <Synthesis Example 1>) (42.1 g, 0.08 mol) dissolved in a minimum amount of acetone was slowly added. After the addition, the mixture was stirred for 90 minutes, and the acetone was removed to prepare a styrene-acrylic resin particle dispersion (1A-A) crosslinked with photoisomerization compound 1.

[0388] (Second stage polymerization) A solution of 7g of sodium polyoxyethylene-2-dodecyl ether sulfate dissolved in 800g of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, and heated to 98℃. Then, a polymerizable monomer solution of 260g of the above styrene acrylic resin particle dispersion (1A-A), styrene (242.6g, 2.33mol), n-butyl acrylate (118.8g, 0.93mol), the monomer MA1 (7.7g, 0.03mol) synthesized in <Synthesis Example MA1>, 1.5g of n-octyl-3-mercaptopropionate, and 67g of paraffin wax "HNP-11" (manufactured by Nippon Seiro Co., Ltd.) as a release agent was added at 90℃, and the mixture was mixed and dispersed for 1 hour using a mechanical disperser "CREARMIX" (manufactured by M Technique Co., Ltd.) with a circulation path to prepare a dispersion containing emulsified particles (oil droplets).

[0389] Next, an initiator solution in which 9.0 g of potassium persulfate was dissolved in 200 g of ion-exchanged water was added to this dispersion, and the system was heated and stirred at 82°C for 1 hour to polymerize, preparing a styrene-acrylic resin particle dispersion (1B) containing styrene-acrylic resin particles (1b). This solution was heated to 60°C, and photoisomerization compound 1 (synthesized in <Synthesis Example 1>) (18.5 g, 0.03 mol) dissolved in a minimum amount of acetone was slowly added. After the addition, the mixture was stirred for 90 minutes, and the acetone was removed to prepare a styrene-acrylic resin particle dispersion (1B-B) crosslinked with the photoisomerization compound 1.

[0390] (Third stage polymerization) A solution of 16.5g of potassium persulfate dissolved in 400g of ion-exchanged water was added to the above styrene-acrylic resin particle dispersion (1B-B), and a polymerizable monomer solution consisting of styrene (430.7g, 4.13mol), n-butyl acrylate (128.7g, 1.00mol), methacrylic acid (32.7g, 0.25mol), monomer MA1 (17.7g, 0.05mol) synthesized in <Synthesis Example MA1>, and 8g of n-octyl-3-mercaptopropionate was added dropwise over 1 hour under a temperature condition of 82°C. After the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, and then the mixture was cooled to 28°C to obtain styrene-acrylic resin particle dispersion 1 (1C) containing styrene-acrylic resin 1. This solution was heated to 60°C, and photoisomerization compound 1 (synthesized in <Synthesis Example 1>) (30.6g, 0.05mol) dissolved in a minimum amount of acetone was slowly added. After the addition, the mixture was stirred for 90 minutes and the acetone was removed to prepare a styrene-acrylic resin particle dispersion liquid (1C-C) crosslinked with the photoisomerizable compound 1.

[0391] (Preparation of Cyan Colorant Particle Dispersion) 11.5 g of sodium n-dodecyl sulfate was dissolved in 1600 g of pure water, 25 g of copper phthalocyanine (CI Pigment Blue 15:3) was gradually added, and then a cyan colorant particle dispersion was prepared using "Clearmix (registered trademark) W Motion CLM-0.8 (manufactured by M-Technique Co., Ltd.)". The median diameter of the cyan colorant particles in the dispersion, measured by number using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), was 151 nm.

[0392] (Agglomeration, fusion) The styrene-acrylic resin particle dispersion (1C-C) prepared above (504 g in solids), 900 g of ion-exchanged water, and 70 g of the cyan colorant particle dispersion (70 g in solids) were charged into a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling tube. The temperature inside the vessel was kept at 30°C, and a 5 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 10.

[0393] Next, an aqueous solution of 2 g of magnesium chloride hexahydrate dissolved in 1000 g of ion-exchanged water was added dropwise under stirring over a period of 10 minutes, and then the temperature was raised to 70°C over a period of 60 minutes. The particle growth reaction was continued while maintaining the temperature at 70°C. In this state, the particle size of the associated particles was measured using a Multisizer 3 (manufactured by Beckman Coulter, Inc.), and when the median diameter (D50) on a volume basis reached 6.5 μm, an aqueous solution of 190 g of sodium chloride dissolved in 760 g of ion-exchanged water was added to stop the particle growth. After stirring for 1 hour at 70°C, the temperature was raised again, and the particles were heated and stirred at 75°C to promote the fusion of the particles. The mixture was then cooled to 30°C to obtain a dispersion of toner particles.

[0394] The dispersion of the toner particles obtained above was subjected to solid-liquid separation using a centrifuge to form a wet cake of the toner particles. The wet cake was washed with ion-exchanged water at 35°C until the electrical conductivity of the filtrate from the centrifuge reached 5μS / cm, and then transferred to a "Flash Jet Dryer (manufactured by Seishin Enterprise Co., Ltd.)" and dried until the moisture content reached 0.5% by mass to produce Toner 2-1.

[0395] [Production of Toner 2-10] <Preparation of polyester resin particle dispersion 1D-D> In a 10-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2-mol adduct (518.8 g, 1.51 mol), terephthalic acid (104.0 g, 0.63 mol), fumaric acid (68.3 g, 0.59 mol), 5-(2-propen-1-yloxy)-1,3-benzenedicarboxylic acid (manufactured by Chemieliva Pharmaceutical Co., Ltd.) (6.1 g, 0.03 mol) and 2 g of tin octylate (esterification catalyst) were added, and a polycondensation reaction was carried out at a temperature of 230 ° C. for 8 hours. Further, the polycondensation reaction was continued for 0.5 hours at 8 kPa, and then cooled to 160 ° C. to obtain polyester resin (1d). After this polyester resin (1d) was completely dissolved in tetrahydrofuran, 1.5 times the molar amount of 6-amino-9H-purine-9-ethanethiol (manufactured by Aurora Fine Chemicals LLC) was added to the reaction solution relative to the allyl group contained in each polymer, and the reaction solution was irradiated with UV light (254 nm) while stirring in the same manner as in Green Chemistry, 2013, 15(4), 1016. Ethyl alcohol in an amount 30 times the amount of the reaction solution was placed in a flask, a mechanical stirrer and a Teflon (registered trademark) blade were installed, and the resulting reaction solution was dropped into the ethyl alcohol that was being vigorously stirred over 1 hour. After stirring for 2 hours, the mixture was filtered under reduced pressure using a Nutsche filter and filter paper. The resulting solid was dried under reduced pressure at 60°C to obtain polyester resin (1D). 1 The disappearance of the double bond of the allyl group was confirmed by the integral ratio of 1 H-NMR.

[0396] 100 g of polyester resin (1D) was pulverized using a "Random Mill, Model: RM" (manufactured by Tokuju Machine Works, Ltd.), mixed with 638 g of a previously prepared 0.26% by mass aqueous solution of sodium lauryl sulfate, and ultrasonically dispersed for 30 minutes at V-LEVEL and 300 μA using an ultrasonic homogenizer "US-150T" (manufactured by Nippon Seiki Co., Ltd.) while stirring, to obtain a polyester resin particle dispersion (1D-D).

[0397] (Agglomeration, fusion) Toner 2-10 was produced in the same manner as in [Production of Toner 2-1] (aggregation and fusion), except that the styrene acrylic resin particle dispersion (1C-C) used in the process was replaced with the polyester resin particle dispersion (1D-D) produced above.

[0398] [Preparation of Toners in Examples 2-2 to 2-68 and Comparative Examples 2-A to 2-F] Toner Examples 2-2 to 2-9, 2-12, 2-13, 2-16 to 1-50 and Comparative Examples 2-A to 2-F were produced in the same manner as in the production of Toner 2-1 in Example 2-1, with appropriate changes to the contents described in Tables 3 and 4. Toners 2-10, 2-11, 2-14, and 2-15 were produced with appropriate changes to the contents described in Table 2, with reference to [Production of Toner 2-10].

[0399] Among the units constituting the resins used in Examples 2-1 to 2-50 and Comparative Examples 2-A to 2-F, the units (T) having complementary multiple hydrogen bonding groups are represented by the following structures BU-1 to BU-9. In addition, in Tables 3 and 4, among the units constituting the resins, the compounds MA-1 to MA-8 and DC-1 used as monomers of the units having complementary multiple hydrogen bonding groups are the MA-1 to MA-8 and DC-1 whose structures are shown above.

[0400] [ka]

[0401] [Preparation of developer] For each of the toners prepared above, ferrite carrier particles with a volume average particle size of 30 μm coated with a copolymer resin of cyclohexane methacrylate and methyl methacrylate (monomer mass ratio 1:1) were mixed so that the toner particle concentration was 6 mass%, to obtain developers 2-1 to 2-50 and 2-A to 2-F. Mixing was performed for 30 minutes using a V-type mixer.

[0402] [Fixation test] Using each of the obtained developers, a toner image was formed on a recording medium, plain paper, to obtain a printed matter. 2 The developer was placed between a pair of parallel flat plate (aluminum) electrodes with a magnetic force, and the gap between the electrodes was 0.5 mm. The DC bias and AC bias were used to control the toner adhesion amount to 4 g / m. 2 The toner was developed under the above conditions to form a toner layer on the surface of the plain paper, which was then fixed by a fixing device to obtain a print.

[0403] <Evaluation> A 1 cm square image on this print was rubbed 10 times with a "JK Wiper (registered trademark)" (manufactured by Nippon Paper Crecia Co., Ltd.) at a pressure of 50 kPa, and the image fixation rate was evaluated. A fixation rate of 80% or more was considered a pass. The evaluation results (fixation rate) of the fixability test obtained are shown in Table 3 below. The image fixation rate is a numerical value obtained by measuring the density of the image after printing and after rubbing with a reflection densitometer "RD-918" (manufactured by Sakata Inx Engineering Co., Ltd.), and dividing the reflection density of the solid image after rubbing by the reflection density of the solid image after printing, expressed as a percentage.

[0404] The fixing devices used were the following three types of devices constructed by appropriately modifying the device shown in FIG.

[0405] Fixing device No. 1: There is no pressure bonding unit 9 in FIG. 2. The wavelength of the ultraviolet light emitted from the irradiation unit 40 is 365 nm (light source: LED light source with an emission wavelength of 365 nm±10 nm), and the irradiation amount is 10 J / cm 2 The toner softened by the ultraviolet light irradiation was left to solidify (make the compound non-fluid) and be fixed in the natural environment, i.e., at room temperature (20° C.), until it reached the paper discharge section 14 (see FIG. 1).

[0406] Fixing device No. 2: The fixing device No. 2 has the pressure bonding unit 9 in FIG. 2, the temperature of the pressure member 91 is 20° C., and the pressure when pressing is 0.2 MPa. The light source and the amount of irradiation of the irradiation unit are the same as those of No. 1. The toner softened by the ultraviolet light irradiation is fixed by pressure applied by the pressure member 91, and then solidified (the compound is made non-fluid) by leaving it at room temperature (20° C.) until it reaches the paper discharge unit 14 (see FIG. 1).

[0407] Fixing device No. 3: It has the pressure bonding unit 9 in FIG. 2, and the temperature of the pressure member 91 is 80° C. The light source and the amount of irradiation of the irradiation unit are the same as those of No. 1. The pressure when pressing by the pressure member 91 is the same as that of No. 2. The toner softened by the ultraviolet light irradiation is further softened and fixed by the pressure and heat of the pressure member 91. Thereafter, it is left at room temperature (20° C.) until it reaches the paper discharge unit 14 (see FIG. 1) and solidifies (the compound is made non-fluid).

[0408] [Thin line reproducibility test] <Image forming method> Using the obtained developer, a toner image was formed on a recording medium, plain paper, to obtain a printed matter. 2 The developer is placed between a pair of parallel flat plate (aluminum) electrodes with a magnetic force, and the gap between the electrodes is 0.5 mm. The DC bias and AC bias are used to control the toner adhesion amount to 4 g / m. 2 The toner was developed under the above conditions, a toner layer of each fine line of 6 lines / mm was formed on plain paper, and the print was fixed by a fixing device.

[0409] <Evaluation> The thin line image portion of the print was magnified with a digital microscope "VHX-600" (Keyence Corporation) and the line width of 6 lines / mm was measured with an indicator (W1) from the monitor image, and the thin line reproduction rate relative to the line width before fixing (W2) was calculated by {(W1 / W2) x 100}. In measuring the line width, the line width of the toner thin line differed depending on the measurement position, and both ends of the thin line in the line width direction had unevenness in the line width direction, so a straight line that averaged the unevenness was drawn at both ends, and the line width was determined as the distance between the straight lines.

[0410] [Table 3]

[0411] [Table 4]

[0412] As is clear from Tables 3 and 4, it was confirmed that the toners prepared in each Example had good fixability and excellent thin line reproducibility. In contrast, it was found that the toners prepared in Comparative Examples 2-A to 2-F were inferior in fixability and thin line reproducibility. Since the ultraviolet light source and ultraviolet light irradiation conditions used for evaluating fixability and thin line reproducibility were constant throughout Examples 2-1 to 2-9 and Comparative Examples 2-A to 2-F, it can be said that the toners of the Examples were reversibly fluidized / imfluidized more quickly than the toners of the Comparative Examples by light irradiation, and thus exhibited the effect of excellent fixability and thin line reproducibility.

[0413] As shown in each example, it has been found that when the toner contains a resin composition containing a resin having complementary multiple hydrogen bonding groups and a photoisomerizable compound having complementary multiple hydrogen bonding groups, the toner image shows an excellent fixing rate of 80% or more in a fixation test, and shows an excellent thin line reproduction rate of 110 or more in thin line reproduction. [Explanation of symbols]

[0414] 1 photoreceptor, 2 Charger, 3 Exposure device, 4 Development section, 5 Transfer section (transfer roller), 7 Paper transport system, 8 Cleaning section, 9 Crimping part, 10 Image forming unit, 11 Paper feed section, 12 Transport roller, 13 conveyor belt, 14 Paper ejection section, 15 Manual feed unit, 16 trays, 17 Thermohygrometer, 20 Image processing unit, 24 Paper reversing section, 40 Irradiation unit, 71 Image reading device, 72 Automatic document feeder, 85 blades, 90 control section, 91, 92 Pressurizing member, 100 Image forming apparatus, d manuscript, S Recording paper.

Claims

1. a resin having a first group capable of forming at least two hydrogen bonds; a photoisomerizable compound having a second group capable of forming at least two hydrogen bonds complementary to the first group and having a site that is reversibly isomerized by light; Including, The resin is represented by the following general formula (1): 【Chemistry 1】 In general formula (1), M represents a linking group; B 1 represents the first group; The structure includes The photoisomerizable compound is represented by the following general formula (2): 【Chemistry 2】 In general formula (2), L 1 and L 2 each independently represent a linking group; A 1 and A 2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group; Z 1 and Z 2 each independently represent N or CH; B 2 represents the second group; n is an integer from 1 to 10, When n is 1, G represents the second group, and when n is 2 to 10, G represents an n-valent substituent or an n-valent third group capable of forming at least two hydrogen bonds complementary to the first group. A compound represented by the formula: The resin composition, wherein the first group and the second group are a residue of any one compound selected from the group consisting of adenine, guanine, cytosine, thymine, uracil, urea, thiourea, melamine, cyanuric acid, barbituric acid, 2,6-diacylaminopyridine, 4,6-diamino-2-pyrimidinone, 2-amino-4,6-pyrimidinedinone, 2,4,6-triaminopyrimidine, phthalimide, 2,6-diamino-1,3,5-triazine, 2-ureido-4-amino-1,3,5-triazine, and 2-ureido-4-pyrimidinone, or a derivative thereof.

2. The resin composition according to claim 1, wherein the first group and the second group are each independently a residue of any one compound selected from the group consisting of adenine, thymine, 2,6-diacylaminopyridine, uracil, melamine, cyanuric acid, phthalimide, and 2,6-diamino-1,3,5-triazine.

3. 3. The resin composition according to claim 1, wherein the resin has at least one main chain selected from the group consisting of an acrylic resin, a styrene-acrylic resin, and a polyester resin.

4. In the general formula (2), the Z １ and Z ２ are each independently N or CH, and Z １ ≠Z ２ The resin composition according to any one of claims 1 to 3.

5. The resin composition according to any one of claims 1 to 4, wherein the first group and the second group are a pair of residues selected from adenine / thymine, 2,6-diacylaminopyridine / uracil, melamine / cyanuric acid, and 2,6-diamino-1,3,5-triazine / phthalimide.

6. The resin composition according to any one of claims 1 to 5, which is rendered fluid by light irradiation and then rendered non-fluid.

7. The resin composition according to claim 6, wherein the wavelength of the light irradiation is 250 nm to 480 nm.

8. A toner comprising the resin composition according to any one of claims 1 to 7.

9. The toner according to claim 8 , further comprising a binder resin.

10. The toner according to claim 9 , wherein the binder resin comprises at least one selected from the group consisting of a styrene-acrylic resin and a polyester resin.

11. The toner according to any one of claims 8 to 10, further comprising a colorant.

12. The toner according to any one of claims 8 to 11, further comprising a release agent.

13. forming a toner image on a recording medium, the toner image being made of the toner according to any one of claims 8 to 12; irradiating the toner image with light to soften the toner image; An image forming method comprising:

14. The image forming method according to claim 13, wherein the wavelength of the light is 280 nm or more and 480 nm or less.

15. 15. The image forming method according to claim 13, further comprising a step of pressing the toner image.

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

17. A photosensitive adhesive using the resin composition according to any one of claims 1 to 7.

18. A light switching material comprising the resin composition according to any one of claims 1 to 7.

Images