JP2018070836A - Composite resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin that can be processed at lower temperature and has excellent durability after processed.SOLUTION: The present invention provides a composite resin in which: a hydrogen bond is formed between a polymer including a carboxy group, and a compound including a functional group to form the hydrogen bond with the carboxy group and having liquid crystallinity. The hydrogen bond can be cut by light irradiation.SELECTED DRAWING: None

Description

  The present invention relates to a composite resin.

  Resin products are indispensable in modern life, and in 2012, 280 million tons of resin products were produced worldwide. Resin products are often melted using thermal energy during processing, but the amount of heat used is enormous. From the viewpoint of energy saving, it is desired to reduce the amount of heat used during processing. For this reason, various low-temperature processing technologies that reduce the softening temperature and glass transition temperature of the resin and reduce the amount of heat during processing have been studied. ing.

  When the softening temperature or glass transition temperature of the resin is lowered, the temperature can be lowered to some extent, but there is a problem that the thermal stability and the like are lowered with time. Thus, studies have been made on techniques for reducing the softening temperature and glass transition temperature of the resin and lowering the processing temperature by adding a functional material to the resin. For example, Patent Document 1 discloses a developer containing a binder resin, a colorant, and an additive, and the additive includes a compound that undergoes a cis-trans isomerization reaction by light absorption and undergoes a phase transition. ing.

JP 2014-191078 A

  However, in the technique described in Patent Document 1, although the softening temperature and the glass transition temperature of the resin are lowered, when a physical force is applied by pressing or friction after processing, the additive oozes out. There was a problem that the phenomenon was observed and the durability after processing was insufficient.

  Therefore, an object of the present invention is to provide a composite resin that can be processed at a lower temperature and has excellent durability after processing.

  The inventors of the present invention have made extensive studies. As a result, a composite resin formed by forming a hydrogen bond between a polymer having a carboxy group and a compound having a functional group that forms a hydrogen bond with the carboxy group and having liquid crystallinity, the hydrogen bond Has found that the above problems can be solved by a composite resin that is a bond that can be cleaved by light irradiation.

  According to the present invention, processing at a lower temperature is possible, and a composite resin excellent in durability after processing is provided.

It is a schematic diagram which shows the mechanism of the effect expression of the composite resin by one form of this invention. 1 is a schematic configuration diagram illustrating an image forming apparatus used in an image forming method according to an embodiment of the present invention. It is a schematic block diagram of the irradiation part in an image forming apparatus.

  The present invention is a composite resin formed by forming a hydrogen bond between a polymer having a carboxy group and a compound having a functional group that forms a hydrogen bond with the carboxy group and having liquid crystallinity. The bond is a composite resin that can be cleaved by light irradiation. The composite resin of the present invention having such a configuration can be processed at a lower temperature and has excellent durability even after processing.

  The details of why the above effect can be obtained by the composite resin of the present invention are unknown, but the following mechanism is conceivable. Note that the following mechanism is based on speculation, and the present invention is not limited to the following mechanism. Further, in the present specification, a polymer having a carboxy group is also simply referred to as “carboxy group-containing polymer” or “polymer”, and has a functional group that forms a hydrogen bond with the carboxy group and has liquid crystallinity. Is also simply referred to as “liquid crystalline compound”.

  FIG. 1 is a schematic diagram illustrating a mechanism of effect expression of a composite resin according to an embodiment of the present invention.

  When a carboxy group-containing polymer and a liquid crystal compound are mixed, a carboxy group in the carboxy group-containing polymer (black portion in FIG. 1) and a functional group that forms a hydrogen bond with the carboxy group in the liquid crystal compound. A hydrogen bond with (gray-coated portion in FIG. 1) is formed, and a composite resin partially formed with a crosslinked structure is formed by the liquid crystalline compound. At this time, there is a liquid crystal compound that does not form a hydrogen bond with the carboxy group-containing polymer, and the liquid crystal compound tends to gather together due to intermolecular interaction and has a crystal structure. Therefore, the composite resin as a whole behaves as a crystalline resin (1 in FIG. 1). When the liquid crystal compound is irradiated with light having an absorption wavelength of the liquid crystal compound (for example, ultraviolet light), the structure of the liquid crystal compound is changed to a mixture of geometric isomers. The hydrogen bond formed with the functional group in the compound is broken, and the degree of freedom of molecular motion of the composite resin is increased. In this way, the portion that has become a mixture of geometric isomers has decreased anisotropy (crystallinity) and exhibits liquid crystallinity (liquidity), so to speak, it acts as a plasticizer for the composite resin. Softening temperature and glass transition temperature decrease (2 in FIG. 1). Therefore, the composite resin of the present invention can be processed at a lower temperature. When the composite resin of the present invention is used for toner, the toner is fixed on the recording medium by pressurizing the composite resin after softening (3 in FIG. 1).

  Furthermore, when the softened composite resin is irradiated with visible light, the liquid crystalline compound, which was in the state of a mixture of geometric isomers, changes its structure again to the compound having the original geometric isomerism, and the hydrogen bonds that have been broken are also regenerated. Since it is formed, the strength of the composite resin is restored (4 in FIG. 1). Even when a physical force such as pressure or friction is applied to the composite resin of the present invention whose strength has been recovered, a phenomenon such as the liquid crystal compound exuding is not observed. That is, the composite resin of the present invention is excellent in durability after processing.

  Hereinafter, preferred embodiments of the present invention will be described. In this specification, “X to Y” indicating a range means “X or more and Y or less”. In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

[Composition of composite resin]
<Polymer having carboxy group (carboxy group-containing polymer)>
Examples of the carboxy group-containing polymer include addition polymers of monomers having a carboxy group and an ethylenically unsaturated group. Containing a carboxy group in the form of a copolymer by appropriately combining a monomer having a carboxy group and an ethylenically unsaturated group with another monomer copolymerizable with the monomer A polymer can be obtained. Moreover, the homopolymer of the monomer which has a carboxy group and an ethylenically unsaturated group can also be used.

  Examples of monomers having a carboxy group and an ethylenically unsaturated group include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid A monoester etc. are mentioned.

  Examples of other copolymerizable monomers include, for example, α-olefins such as ethylene and propylene, styrene monomers such as styrene, α-methylstyrene and vinyltoluene, vinylcyclohexane, vinylnaphthalene and vinylnaphthalene derivatives. Acrylic acid alkyl ester, acrylic acid aryl ester, methacrylic acid alkyl ester, methacrylic acid aryl ester, crotonic acid alkyl ester, itaconic acid dialkyl ester, maleic acid dialkyl ester and the like.

  Examples of the copolymer used as the carboxy group-containing polymer include ethylene-acrylic acid copolymer, styrene-maleic acid copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, vinyl naphthalene- Maleic acid copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-methacrylic acid copolymer, acrylic acid alkyl ester-acrylic acid copolymer, methacrylic acid alkyl ester-methacrylic acid copolymer, styrene-methacrylic acid Examples thereof include an alkyl ester-methacrylic acid copolymer, a styrene-acrylic acid alkyl ester-acrylic acid copolymer, and a styrene-methacrylic acid aryl ester-methacrylic acid copolymer. Among these, ethylene-acrylic acid copolymer, styrene-maleic acid copolymer, and styrene-acrylic acid copolymer are preferable from the viewpoint of easily forming a hydrogen bond with the liquid crystalline compound. A copolymer containing a structural unit derived from ethylene is considered to have little steric hindrance and easily form a hydrogen bond with a liquid crystalline compound, and a copolymer containing a structural unit derived from styrene is a π- This is because it is considered that a hydrogen bond with the liquid crystalline compound is easily formed by the π interaction. These copolymers may further contain a monomer having a polyoxyethylene group or a hydroxy group as a copolymerization component as appropriate. These copolymers may be in any form such as a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer.

  Examples of the homopolymer used as the carboxy group-containing polymer include polyacrylic acid, polymethacrylic acid, polyalginic acid and the like, which are preferable from the viewpoint of forming a hydrogen bond with a liquid crystal compound with little steric hindrance. Is polyacrylic acid. In addition, cellulose derivatives such as carboxymethyl cellulose and carboxyethyl cellulose can also be used as the polymer.

  As the carboxy group-containing polymer, a commercially available product or a synthetic product may be used. In the case of synthesis, a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization can be appropriately employed.

  The weight average molecular weight of the carboxy group-containing polymer is preferably 1000 to 100,000, and more preferably 3000 to 10,000. Within this range, the polymer having a carboxy group and the compound having a functional group that forms a hydrogen bond with the carboxy group and having liquid crystallinity can efficiently form a hydrogen bond.

  The weight average molecular weight of the carboxy group-containing polymer can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. More specifically, using an apparatus “HLC-8120GPC” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZ-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran ( THF) at a flow rate of 0.2 mL / min. A measurement sample (polymer) is dissolved in tetrahydrofuran so as to have a concentration of 1 mg / ml under dissolution conditions in which treatment is performed for 5 minutes using an ultrasonic disperser at room temperature. Next, a sample solution is obtained by processing with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution is injected into the apparatus together with the above carrier solvent, and is detected using a refractive index detector (RI detector) and measured. The molecular weight distribution of the sample is calculated using a calibration curve measured using monodisperse polystyrene standard particles. Ten polystyrenes are used for calibration curve measurement.

<Liquid crystal compound>
The liquid crystal compound is a compound having a liquid crystallinity and a functional group that forms a hydrogen bond with the carboxy group of the polymer. Further, this hydrogen bond is a relatively weak bond that can be broken by light irradiation. The liquid crystalline compound has a structure in which a rigid π-conjugated skeleton and a flexible long-chain alkyl group are combined.

  Specifically, the liquid crystal compound is preferably a compound represented by the following chemical formula (1).

In the above chemical formula (1),
X is CH or a nitrogen atom,
Y ₁ and Y ₂ are each independently a group capable of forming a hydrogen bond with a carboxy group in a polymer having a carboxy group,
Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group or a divalent heterocyclic group,
R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a thiol group, a cyano group, or a substituted or unsubstituted alkyl group, alkenyl group, alkoxy group, amino group, aryl group or heterocyclic ring. A group that may be linked together to form a ring structure,
n and m are each independently an integer of 3 or more and 10 or less.

  The geometric isomerism of the double bond between X in the compound represented by the chemical formula (1) is E type, but a Z type liquid crystalline compound may be used.

  X in the chemical formula (1) is CH or a nitrogen atom. When X is CH, the compound represented by the chemical formula (1) is a stilbene derivative, and when X is a nitrogen atom, the compound represented by the chemical formula (1) is an azobenzene derivative. Here, X is preferably a nitrogen atom. That is, the compound represented by the chemical formula (1) is preferably an azobenzene derivative. If it is an azobenzene derivative, the sensitivity to light is improved, the structural change to the geometric isomer mixture occurs at a faster rate, and the temperature during processing tends to decrease.

Specific examples of the group capable of forming a hydrogen bond with the carboxy group represented by Y ₁ and Y ₂ in the chemical formula (1) include a carboxy group, a heterocyclic group containing a nitrogen atom, a hydroxy group, a carbonyl group, A halogen group etc. are mentioned. Among these, a heterocyclic group containing a nitrogen atom is preferable. This is because the nitrogen atom contained in the heterocyclic group is weak in nucleophilicity and forms a hydrogen bond with a moderate strength with the carboxy group in the polymer.

  Specific examples of the heterocyclic group containing a nitrogen atom include pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, pyranyl group, thiopyranyl group, thioxanthenyl group, imidazolyl group, pyrazolinyl group, benzopyrazolinyl group, pyrazolidinyl group, Thiazolyl, isothiazolyl, triazolyl, tetrazolyl, oxathiazolyl, oxathiazinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, thianaphthel, thiadiazolyl, triazinyl, oxazolyl, isoxazolyl, benzoxazolyl, benzo Isoxazolyl group, benzoisothiazolyl group, furazanyl group, pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, indolyl group, isoindolyl group , Indazolyl group, purinyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group, naphthidinyl group, phthalazinyl group, quinoxalinyl group, cinnolinyl group, benzoxazinyl group, pteridinyl group, carbazolyl group, phenanthridinyl group, acridinyl group, perimidinyl group, Nantrolinyl group, phenazinyl group, phenotelazinyl group, phenotherazinyl group, phenothiazinyl group, phenoxazinyl group, antiridinyl group, quinazolinyl group, azetidinyl group, pyrrolidinyl group, pyrrolinyl group, piperidinyl group, piperazinyl group, morpholinyl group Thiomorpholinyl group, purinyl group, naphthyridinyl group, pyridopyrimidinyl group and the like.

One or more hydrogen atoms of the heterocyclic group containing a nitrogen atom are a halogen atom, a hydroxy group, a nitro group, a cyano group, a —NH ₂ group, a —NH (R) group (where R is a carbon number of 1 to 10). A straight-chain or branched alkyl group), a —N (R ′) (R ″) group, (R ′ and R ″ are each independently a linear or branched group having 1 to 10 carbon atoms; Amidino group, hydrazine group, hydrazone group, carboxy group, sulfonic acid group, phosphoric acid group, linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Linear or branched alkyl halide group, linear or branched alkenyl group having 2 to 20 carbon atoms, linear or branched alkynyl group having 2 to 20 carbon atoms, carbon number 6 ~ 20 aryl group, C7-20 arylalkyl group, nitrogen atom, A heteroaryl group having 5 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of an elementary atom, a phosphorus atom and a sulfur atom, or a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom It can be substituted with a substituent such as a heteroarylalkyl group having 6 to 20 carbon atoms containing at least one selected heteroatom.

  Among the above heterocyclic groups containing a nitrogen atom, an imidazolyl group or a pyridyl group is preferable, and an imidazolyl group is more preferable from the viewpoint that the bond strength of a hydrogen bond becomes more appropriate.

  Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group or a divalent heterocyclic group. Examples of the divalent heterocyclic group include a pyridinediyl group, a diazaphenylene group, a quinolinediyl group, a quinoxalinediyl group, an acridinediyl group, and a bipyridyldiyl group. The alkyl group, alkenyl group, alkoxy group, amino group, aryl group or heterocyclic group may be substituted. The phenylene group or divalent heterocyclic group that may be used for Ar and Ar ′ may be substituted. Examples of the substituent include the same substituents as those described for the heterocyclic group containing a nitrogen atom, and thus the description thereof is omitted here.

Examples of the alkyl group that can be used for R _{1 to} R ₈ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n- Examples thereof include alkyl groups having 1 to 10 carbon atoms such as a pentylo group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

Examples of alkenyl groups that can be used for R _{1 to} R ₈ include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and 1,3-butenyl group. Alkenyl groups having 2 to 10 carbon atoms such as 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group and 1-decenyl group.

Examples of alkoxy groups that can be used for R _{1 to} R ₈ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n -Pentyloxy group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. An alkoxy group is mentioned.

Examples of aryl groups that can be used for R _{1 to} R ₈ include phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group. Aryl groups having 6 to 20 carbon atoms such as naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group and pyrenyl group.

Examples of the heterocyclic group that can be used for R _{1 to} R ₈ include heterocyclic groups containing an oxygen atom such as a furanyl group, a pyranyl group, a tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, and a dioxanyl group.

The alkyl group, alkenyl group, alkoxy group, amino group, aryl group or heterocyclic group that can be used for R _{1 to} R ₈ may be substituted. Examples of the substituent include the same substituents as those described for the heterocyclic group containing a nitrogen atom, and thus the description thereof is omitted here. These groups are not substituted with the same substituent. For example, the alkyl group used in R _{1 to} R ₈ is not substituted with an alkyl group.

R _{1 to} R ₄ in the chemical formula (1) are preferably hydrogen atoms. When R _{1 to} R ₄ are hydrogen atoms, hydrophobic interaction between the molecules of the liquid crystal compound occurs, and the molecules of the liquid crystal compound are easily stacked, thereby making it easier to exhibit liquid crystallinity (liquidity). It becomes easier to obtain the function as a plasticizer. Therefore, the glass transition temperature of the composite resin is likely to decrease, and processing at a lower temperature is possible.

Z ₁ and Z ₂ in the chemical formula (1) are preferably an oxygen atom or a group in which R _{5 to} R ₈ are hydrogen atoms, that is, a methylene group, from the viewpoint of compatibility with a carboxy group-containing polymer, Is more preferable.

  m and n are each independently an integer of 3 to 10, but an integer of 4 to 8 is preferable, and an integer of 5 to 7 is more preferable. If it is this range, it will become easier to show liquid crystallinity (liquidity), and it will become easier to obtain the function as a plasticizer. Therefore, the glass transition temperature of the composite resin tends to be lowered, and processing at a good low temperature is possible.

  More specific examples of the liquid crystal compound include the following compounds.

  The liquid crystal compounds can be used alone or in combination of two or more. Moreover, a commercial item may be used for a liquid crystalline compound, and a synthetic item may be used. In the case of synthesis, a known synthesis method can be appropriately employed.

  As the liquid crystalline compound having an azobenzene structure (compound in which X in the general formula (1) is a nitrogen atom), for example, a compound having a group capable of forming a hydrogen bond with a polymer, an alkyl dihalide, and dihydroxyazobenzene are appropriately selected. It can synthesize | combine by making it react (refer following Reaction formula (1)).

  In addition, a liquid crystal compound having a stilbene structure (a compound in which X in the general formula (1) is CH) has, for example, a group capable of forming a hydrogen bond with a polymer after obtaining stilbene from 4-hydroxybenzaldehyde. It can synthesize | combine by making the compound which has (refer following Reaction formula (2)).

  The content of the liquid crystalline compound in the composite resin is preferably 1 to 50% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the entire composite resin.

[Production method of composite resin]
The method for producing the composite resin of the present invention is not particularly limited. For example, a composite resin can be obtained by mixing a carboxy group-containing polymer and a liquid crystal compound in a solvent and then removing the solvent by drying or the like. When the solution is applied onto a substrate such as a glass substrate and dried to remove the solvent, a film-like composite resin can be obtained.

  Examples of the solvent used include, for example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, and carbon tetrachloride; hydrocarbons such as n-hexane and n-heptane; methyl acetate, ethyl acetate, and the like. Esters: Aprotic polar solvents such as acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMA), sulfolane; diethyl ether, t-butyl methyl ether, 1,4-dioxane , Ethers such as tetrahydrofuran (THF) and 1,2-dimethoxyethane. These solvents may be used alone or in combination of two or more.

  As described above, when the composite resin of the present invention is irradiated with light (preferably ultraviolet light), the glass transition temperature is lowered, and processing at a lower temperature becomes possible. In the composite resin of the present invention, the decrease width of the glass transition temperature after the ultraviolet light irradiation with respect to the glass transition temperature before the ultraviolet light irradiation is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, more preferably 15 ° C. More preferably, it is super. The upper limit of the glass transition temperature drop is not particularly limited, but is preferably 50 ° C. or lower.

  The composite resin of the present invention can be solidified (cured) by irradiation with visible light after being softened by irradiation with ultraviolet light. The glass transition temperature of the composite resin thus obtained after irradiation with visible light (after curing) is preferably in the range of 40 to 200 ° C, and more preferably in the range of 60 to 150 ° C. If it is such a range, it will become a composite resin excellent in the durability after a process.

  The glass transition temperature of the composite resin can be measured by differential scanning calorimetry (DSC), and more specifically can be measured by the method described in the examples.

In the case where the hydrogen bond of the composite resin is cut and softened (melted), ultraviolet light having a wavelength within a range of 300 nm or more and less than 400 nm, and more preferably within a range of 330 nm or more and less than 390 nm is irradiated. At this time, the irradiation amount of ultraviolet light, preferably in the range of 0.1~200J / cm ^2, more preferably in the range of 0.5~100J / cm ^2, more preferably 1.0～70J / Within the range of cm ² . If the wavelength of light and the amount of light irradiation are in the above ranges, the structural change to the mixture of geometric isomers can proceed efficiently, and hydrogen bonds can be broken efficiently.

When the composite resin is softened (melted) and then solidified (cured), it is preferably irradiated with visible light having a wavelength in the range of 400 nm to 800 nm, more preferably in the range of 450 nm to 650 nm. At this time, the irradiation amount of visible light is preferably in the range of 0.1 to 200 J / cm ² , more preferably in the range of 0.5 to 100 J / cm ² , and further preferably 1.0 to 70 J / cm ^2. Within the range of cm ² . If the wavelength of light and the amount of light irradiation are in the above ranges, the structural change from the mixture of geometric isomers to the compound having the original geometric isomerism proceeds efficiently, and hydrogen bonds can also be efficiently re-formed.

[Usage]
The composite resin of the present invention can be suitably used for an electrophotographic toner, a light control adhesive that repeats liquefaction and solidification by light irradiation, and the like. Among these, it is preferable to use the toner for electrophotography because merits such as energy saving at the time of image formation and improvement in operability can be obtained. That is, the present invention also provides an electrophotographic toner containing the composite resin.

  Hereinafter, an electrophotographic toner containing the composite resin of the present invention (hereinafter also simply referred to as “the toner according to the present invention” or “toner”) will be described.

  The toner according to the present invention preferably contains 10% by mass or more, more preferably 20% by mass or more, of the composite resin of the present invention with respect to the total mass of the toner. Since the composite resin of the present invention can be used alone as a toner, the upper limit of the preferable content of the composite resin in the toner is 100% by mass.

  In addition to the composite resin, the toner according to the present invention may contain other components such as a binder resin, a colorant, a release agent, a charge control agent, and an external additive. Hereinafter, these other components will be described.

<Binder resin>
The toner according to the present invention may contain a binder resin. As such a binder resin, a resin generally used as a binder resin constituting a toner can be used without limitation. Specific examples include styrene resins, acrylic resins, styrene acrylic resins, polyester resins, silicone resins, olefin resins, amide resins, and epoxy resins. These binder resins can be used singly or in combination of two or more.

  Among these, the binder resin is at least one selected from the group consisting of a styrene resin, an acrylic resin, a styrene acrylic resin, and a polyester resin from the viewpoint of low viscosity when melted and high sharp melt properties. It is preferable that at least 1 sort (s) selected from the group which consists of a styrene acrylic resin and a polyester resin is included.

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

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

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

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

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

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

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

  In addition to the copolymer formed only with the styrene monomer and (meth) acrylate monomer described above, the styrene acrylic copolymer includes these styrene monomer and (meth) acrylate ester. In addition to the monomers, some are formed using a common vinyl monomer. Although the vinyl monomer which can be used together when forming the styrene acrylic copolymer said by this invention is illustrated below, the vinyl monomer which can be used together is not limited to what is shown below.

(1) Olefins Ethylene, propylene, isobutylene, etc. (2) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (3) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (4) Vinyl ketones Vinyl methyl ketone, Vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. (6) Other vinyl compounds such as vinyl naphthalene, vinyl pyridine, acrylonitrile, methacrylo Acrylic acid or methacrylic acid derivatives such as nitrile and acrylamide.

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

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

  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. For example, a known chain transfer agent such as n-octyl mercaptan may be used as necessary.

  When forming the styrene acrylic resin used in the present invention, the contents of the styrene monomer and the acrylate monomer are not particularly limited, and the softening temperature and glass transition temperature of the binder resin are controlled. It is possible to adjust appropriately from the viewpoint. Specifically, the content of the styrene monomer is preferably 40 to 95% by mass and more preferably 50 to 80% by mass with respect to the whole monomer. Moreover, 5-60 mass% is preferable with respect to the whole monomer, and, as for content of an acrylic ester monomer, 10-50 mass% is more preferable.

  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 polymerization initiators and peroxide polymerization initiators.

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

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

  Moreover, when forming a styrene acrylic resin particle by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

  Although superposition | polymerization temperature changes also with the kind of monomer and polymerization initiator to be used, it is preferable that it is 50-100 degreeC, and it is more preferable that it is 55-90 degreeC. Moreover, although superposition | polymerization time changes also with the kind of monomer to be used or a polymerization initiator, it is preferable that it is 2 to 12 hours, for example.

  The styrene acrylic resin particles formed by the emulsion polymerization method can also have a structure of two or more layers made of resins having different compositions. As a production method in this case, a polymerization initiator and a polymerizable monomer are added to a dispersion of resin particles prepared by an emulsion polymerization process (first stage polymerization) according to a conventional method, and this system is polymerized. A multistage polymerization method in which the treatment (second stage polymerization) is performed can be employed.

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

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

  Examples of the dicarboxylic acid component include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. (Dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18 -Saturated aliphatic dicarboxylic acids such as octadecane dicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as methylene succinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, dodecenyl succinic acid; phthalic acid, Terephthalic acid, isophthalic acid, t-butylisophthalic acid, tetrachloro And unsaturated aromatic dicarboxylic acids such as taric acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, anthracene dicarboxylic acid; These lower alkyl esters and acid anhydrides can also be used. The dicarboxylic acid components may be used alone or in combination of two or more.

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

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

  The production method of the polyester resin is not particularly limited, and can be produced by polycondensation (esterification) of the polyvalent carboxylic acid component and the polyhydric alcohol component using a known esterification catalyst.

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

  The polymerization temperature is not particularly limited, but is preferably 70 to 250 ° C. Moreover, although superposition | polymerization time is not specifically limited, It is preferable that it is 0.5 to 10 hours. During the polymerization, the pressure in the reaction system may be reduced as necessary.

  The content ratio when the toner of the present invention contains a binder resin is preferably in the range of composite resin: binder resin = 5: 95 to 80:20 (mass ratio). Within this range, the composite resin is likely to undergo a photophase transition, and the softening speed of the toner upon light irradiation is sufficient.

  The toner containing the composite resin and the binder resin of the present invention may have a single layer structure or a core-shell structure. The type of the binder resin used for the core particle and the shell part of the core-shell structure is not particularly limited.

<Colorant>
The toner according to the present invention may contain a colorant. As the colorant, generally known dyes and pigments can be used.

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

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

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

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

  The colorant for obtaining the toner of each color can be used alone or in combination of two or more for each color.

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

<Release agent>
The toner according to the present invention may contain a release agent. The release agent to be used is not particularly limited, and various known waxes can be used. Examples of the wax include low molecular weight polypropylene, polyethylene, or oxidized low molecular weight polypropylene, polyolefin such as polyethylene, paraffin, synthetic ester wax, and the like. In particular, a synthetic ester wax is used because of its low melting point and low viscosity. It is particularly preferable to use behenyl behenate, glycerine tribehenate, pentaerythritol tetrabehenate or the like as the synthetic ester wax.

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

<Charge control agent>
The toner according to the present invention may contain a charge control agent. The charge control agent to be used is not particularly limited as long as it is a substance that can give positive or negative charge by frictional charging and is colorless. Various known positively chargeable charge control agents and negative charge control agents can be used. A chargeable charge control agent can be used.

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

<External additive>
In order to improve the fluidity, charging property, cleaning property, etc. of the toner, the toner according to the present invention is constituted by adding external additives such as a so-called post-treatment agent such as a fluidizing agent and a cleaning aid to the toner particles. May be.

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

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

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

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

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

  Specifically, 0.02 g of a measurement sample (toner) is added to 20 mL of a surfactant solution (for example, a surfactant obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles). The solution was added to the solution and allowed to acclimate, and then ultrasonic dispersion was performed for 1 minute to prepare a toner dispersion. This toner dispersion was placed in “ISOTONII” (manufactured by Beckman Coulter, Inc.) in the sample stand. Pipette into beaker until display concentration of measuring device is 8%.

  Here, a reproducible measurement value can be obtained by setting the concentration range. In the measuring apparatus, the measurement particle count is 25000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integrated fraction is 50 % Particle size is the volume-based median diameter (D50).

[Toner Production Method]
The method for producing the toner according to the present invention is not particularly limited. For example, in the case of using only a composite resin as a toner, the composite resin obtained by the above production method is pulverized using an apparatus such as a hammer mill, a feather mill, a counter jet mill, etc., and then spin air sheave, crush seal, A production method including classification using a dry classifier such as a micron classifier to a desired particle size is preferred.

  When producing a toner that contains a composite resin and a colorant and does not contain a binder resin, a solvent that dissolves both the composite resin and the colorant is used to dissolve the composite resin and the colorant into a solution, and then the solvent is removed. Then, a production method including pulverization and classification by the same method as described above is preferable.

  In the case of producing a toner containing a composite resin, a colorant, and a binder resin, a production method using an emulsion aggregation method in which the particle size and shape can be easily controlled is preferable.

Such a manufacturing method is
(1A) Binder resin particle dispersion preparation step for preparing a dispersion of binder resin particles (1B) Colorant particle dispersion preparation step for preparing a dispersion of colorant particles (1C) A dispersion of composite resin particles Step of preparing composite resin particle dispersion to be prepared (2) Addition of a flocculant to an aqueous medium in which binder resin particles, colorant particles and composite resin particles are present, and at the same time agglomeration / melting is performed. (3) Maturation step for forming toner particles by controlling the shape of the associated particles (4) Separating the toner particles from the aqueous medium, and the surfactant from the toner particles (5) A drying step for drying the washed toner particles (6) Each step of an external additive adding step for adding an external additive to the dried toner particles is included. preferable. Hereinafter, the steps (1A) to (1C) will be described.

(1A) Binder Resin Particle Dispersion Preparation Step In this step, resin particles are formed by conventionally known emulsion polymerization, and the resin particles are aggregated and fused to form binder resin particles. As an example, a dispersion of binder resin particles is prepared by charging and dispersing polymerizable monomers constituting the binder resin in an aqueous medium, and polymerizing these polymerizable monomers with a polymerization initiator. .

  Further, as a method of obtaining a binder resin particle dispersion, in addition to the method of polymerizing a polymerizable monomer with a polymerization initiator in the above aqueous medium, for example, a dispersion treatment in an aqueous medium without using a solvent. Or a method in which a crystalline resin is dissolved in a solvent such as ethyl acetate to form a solution, the solution is emulsified and dispersed in an aqueous medium using a disperser, and then a solvent removal treatment is performed.

  At this time, if necessary, the binder resin may contain a release agent in advance. In addition, for dispersion, polymerization is suitably performed in the presence of a known surfactant (for example, an anionic surfactant such as sodium polyoxyethylene (2) dodecyl ether sulfate, sodium dodecyl sulfate, dodecylbenzene sulfonic acid). Is also preferable.

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

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

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

(1C) Composite resin particle dispersion preparation step This composite resin particle dispersion preparation step is a step of preparing a dispersion of composite resin particles by dispersing the composite resin in the form of fine particles in an aqueous medium. In preparing the composite resin particle dispersion, first, a composite resin emulsion is prepared. Examples of the method for preparing the composite resin emulsion include a method of obtaining a composite resin solution in which the composite resin is dissolved in an organic solvent and then emulsifying the composite resin solution in an aqueous medium.

  The method for dissolving the composite resin in the organic solvent is not particularly limited. For example, there is a method of adding the composite resin to the organic solvent and stirring and mixing so that the composite resin is dissolved. The addition ratio of the composite resin is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the organic solvent.

  Next, the composite resin liquid and the aqueous medium are mixed and stirred using a known disperser such as a homogenizer. As a result, the composite resin becomes droplets and is emulsified in the aqueous medium to prepare a composite resin emulsion.

  The addition ratio of the composite resin liquid is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the aqueous medium.

  Further, the temperature of each of the composite resin liquid and the aqueous medium at the time of mixing the composite resin liquid and the aqueous medium is a temperature range that is less than the boiling point of the organic solvent, preferably 20 ° C. or higher and 80 ° C. or lower, more preferably. Is 30 ° C. or higher and 75 ° C. or lower. During mixing of the composite resin liquid and the aqueous medium, the temperature of the composite resin liquid and the temperature of the aqueous medium may be the same as or different from each other, and preferably the same.

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

  The composite resin particle dispersion is prepared by removing the organic solvent from the composite resin emulsion. Examples of the method for removing the organic solvent from the composite resin emulsion include known methods such as air blowing, heating, decompression, or a combination thereof.

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

  The mass average particle diameter of the composite resin particles in the composite resin particle dispersion is preferably 90 nm or more and 1200 nm or less. The mass average particle diameter of the composite resin particles is determined appropriately by the viscosity when the composite resin particles are blended in an organic solvent, the blending ratio of the composite resin liquid and water, the stirring speed of the disperser when preparing the composite resin emulsion, etc. By adjusting, it can set in the said range. The mass average particle diameter of the composite resin particles in the composite resin particle dispersion can be measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).

<Organic solvent>
The organic solvent used in this step is not particularly limited and can be used as long as it can dissolve the composite resin of the present invention. Specifically, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, saturated hydrocarbons such as hexane and heptane, dichloromethane, dichloroethane, four And halogenated hydrocarbons such as carbon chloride.

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

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

  Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl Examples include sucrose.

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

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

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

  In addition, although the coagulant | flocculant used in (2) an association process is not specifically limited, What is selected from a metal salt is used suitably. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum. Etc. Specific metal salts can include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. It is particularly preferable to use a divalent metal salt. These may be used alone or in combination of two or more.

[Developer]
The toner according to the present invention may be used, for example, as a one-component magnetic toner containing a magnetic material, when used as a two-component developer mixed with a so-called carrier, or when using a non-magnetic toner alone. Any of these can be suitably used.

  As said magnetic body, magnetite, (gamma) -hematite, or various ferrites can be used, for example.

  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 are used. Can be used.

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

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

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

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

  FIG. 2 is a schematic configuration diagram showing an image forming apparatus 100 used in the image forming method according to the embodiment of the present invention. However, the image forming apparatus used in the present invention is not limited to the following forms and illustrated examples. FIG. 2 shows an example of a monochrome image forming apparatus 100, but the present invention can also be applied to a color image forming apparatus.

  The image forming apparatus 100 is an apparatus that forms an image on a recording sheet S as a recording medium. The image forming apparatus 100 includes an image reading device 71 and an automatic document feeder 72, and the image is formed on the recording sheet S conveyed by the sheet conveying system 7. An image is formed by the forming unit 10, the first irradiation unit 40a, the pressure bonding unit 9, and the second irradiation unit 40b. Hereinafter, when the first irradiation unit 40a and the second irradiation unit 40b are collectively referred to, they are referred to as the irradiation unit 40.

  Further, although the recording sheet S is used as the recording medium in the image forming apparatus 100, the medium on which image formation is performed may be other than the sheet.

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

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

  In the image forming unit 10, a charger 2, an exposure unit 3, a developing unit 4, a transfer unit 5, a charge removing unit 6, and a cleaning unit 8 are arranged in this order around the photoconductor 1 along the rotation direction of the photoconductor 1. Arranged and configured.

  The photoconductor 1 as an image carrier is an image carrier having a photoconductive layer formed on the surface thereof, and is configured to be rotatable in the direction of the arrow in FIG. 2 by a driving device (not shown). A thermohygrometer 17 that detects the temperature and humidity in the image forming apparatus 100 is provided in the vicinity of the photoreceptor 1.

  The charger 2 uniformly charges the surface of the photoreceptor 1 and charges the surface of the photoreceptor 1 uniformly. The exposure device 3 includes a beam emission source such as a laser diode, and the charged surface of the photosensitive member 1 is irradiated with beam light so that the charge on the irradiated portion disappears. An electrostatic latent image is formed. The developing unit 4 supplies toner contained therein to the photoconductor 1 to form a toner image based on the electrostatic latent image on the surface of the photoconductor 1.

  The transfer unit 5 faces the photoconductor 1 through the recording paper S and transfers the toner image onto the recording paper S. The neutralization unit 6 performs neutralization on the photoreceptor 1 after the toner image is transferred. The cleaning unit 8 includes a blade 85. The surface of the photoreceptor 1 is cleaned by the blade 85 to remove the developer remaining on the surface of the photoreceptor 1.

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

  Further, the image forming apparatus 100 includes a sheet reversing unit 24, and the recording sheet S that has been heat-fixed is conveyed to the sheet reversing unit 24 before the paper discharge unit 14, and is discharged with the front and back reversed. Alternatively, the recording sheet S with the front and back reversed can be conveyed again to the image forming unit 10 to form images on both sides of the recording sheet S.

<Irradiation part>
FIG. 3 is a schematic configuration diagram of the irradiation unit 40 in the image forming apparatus 100.

  The image forming apparatus 100 according to an embodiment of the present invention includes an irradiation unit 40 including a first irradiation unit 40a and a second irradiation unit 40b. As an example of the apparatus which comprises the irradiation part 40, a light emitting diode (LED), a laser light source, etc. are mentioned.

The first irradiation part 40a melts a substance (a composite resin of the present invention) that undergoes phase transition by light absorption contained in the developer, and is preferably in the range of 300 nm to less than 400 nm, more preferably 330 nm to 390 nm. Irradiate with ultraviolet light having a wavelength within the range of less than. Dose of ultraviolet light in the first illumination portion 40a is preferably in the range of 0.1~200J / cm ^2, more preferably in the range of 0.5~100J / cm ^2, more preferably, 1.0 Within the range of 50 J / cm ² .

The second irradiation unit 40b cures the composite resin, and preferably irradiates visible light having a wavelength in the range of 400 nm to 800 nm, more preferably in the range of 450 nm to 650 nm. The irradiation amount of visible light in the second irradiation unit 40b is preferably 0.1 to 200 J / cm ² , more preferably 0.5 to 100 J / cm ² , and still more preferably 1.0 to 50 J / cm ² . .

  That is, an image forming method according to an embodiment of the present invention includes a step of forming a toner image made of the electrophotographic toner of the present invention on a recording medium, and a wavelength of 300 nm or more and less than 400 nm with respect to the toner image. Irradiating light to soften the toner image; irradiating the softened toner image with light having a wavelength of 400 nm to 800 nm to solidify the toner image and fix it on a recording medium; including.

  The first irradiation unit 40 a and the second irradiation unit 40 b irradiate light toward the first surface on the photosensitive member side of the recording paper S holding the toner image, and are nipped between the photosensitive member 1 and the transfer roller 50. It is arranged on the photoconductor side with respect to the recording paper S surface. Further, the first irradiation unit 40a and the second irradiation unit 40b are arranged in this order along the conveyance direction (paper conveyance direction) of the recording paper S.

  The first irradiation unit 40 a is disposed on the downstream side in the paper conveyance direction with respect to the nip position between the photoreceptor 1 and the transfer roller 40, and on the upstream side in the paper conveyance direction with respect to the pressure bonding unit 9.

  The second irradiation unit 40b is installed on the downstream side in the paper conveyance direction with respect to the first irradiation unit 40a and on the upstream side in the paper conveyance direction with respect to the paper discharge unit 14. The second irradiation unit 40b can be installed between the crimping unit 9 and the paper discharge unit 14 in the paper transport direction.

  According to the image forming method of one embodiment of the present invention, the charger 2 is charged by applying a uniform potential to the photoreceptor 1 and then charged with the light beam irradiated by the exposure device 3 based on the original image data. The body 1 is scanned to form an electrostatic latent image. Next, a developer containing a compound that undergoes phase transition by light absorption is supplied onto the photoreceptor 1 by the developing unit 4.

  When the recording paper S is conveyed from the tray 16 to the image forming unit 10 in accordance with the timing at which the toner image carried on the surface of the photoconductor 1 reaches the position of the transfer member 50 by the rotation of the photoconductor 1, The toner image on the photoreceptor 1 is transferred onto the recording sheet S nipped between the transfer member 50 and the photoreceptor 1 by the applied transfer bias.

  Further, the transfer member 50 also serves as a pressure member, and the composite resin contained in the toner image can be brought into intimate contact with the recording paper S while transferring the toner image from the photoreceptor 1 to the recording paper S.

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

  In the process in which the recording paper S to which the toner image has been transferred is transported to the pressure-bonding unit 9 by the transport belt 13, the first irradiation unit 40a is 300 nm or more and less than 400 nm with respect to the toner image transferred onto the recording paper S. Irradiate ultraviolet light having a wavelength. By irradiating the toner image on the first surface of the recording sheet S with the ultraviolet light by the first irradiation unit 40a, the toner image can be more reliably melted and the fixing property of the toner image to the recording sheet S can be improved. Can be improved.

  When the recording paper S on which the toner image is held reaches the pressure-bonding portion 9 by the conveying belt 13, the pressure members 91 and 92 press the toner image onto the first surface of the recording paper S. Since the toner image is softened by the ultraviolet light irradiation by the first irradiation unit 40a before the fixing process is performed by the pressing unit 9, energy saving of the image pressing to the recording paper S can be achieved. That is, in the image forming method of the present invention, the softened toner image is pressed before the step of solidifying (curing) the toner image and fixing it to the recording medium by irradiating visible light having a wavelength of 400 nm to 800 nm. It is preferable to further include a step of pressurizing with a member.

  Further, the pressure member 91 can heat the toner image on the recording paper S when the recording paper S passes between the pressure members 91 and 92. The toner image softened by the light irradiation is further softened by this heating, and as a result, the fixability of the toner image to the recording paper S is further improved. The temperature of the pressure member 91 when heating is preferably 30 ° C. or higher and 100 ° C. or lower, and preferably 40 ° C. or higher and 100 ° C. or lower.

  The recording paper S that has passed between the pressure members 91 and 92 is irradiated with visible light having a wavelength of 400 nm or more and 800 nm or less to the toner image on the recording paper S before reaching the paper discharge unit 14. A second irradiation unit 40b is provided. By irradiating visible light from the second irradiation unit 40b, the toner image on the recording paper S can be more reliably cured, and the fixing property of the toner image to the recording paper S can be further improved.

  When forming images on both sides of the recording paper S, the recording paper S subjected to the pressure-bonding process is transported to the paper reversing unit 24 before the paper discharge unit 14 and discharged with the front and back reversed or the front and back reversed. The recording sheet S is conveyed again to the image forming unit 10.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

  The weight average molecular weight of the carboxy group-containing polymer was measured as follows.

  Using an apparatus “HLC-8120GPC” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZ-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) was used as a carrier solvent at a flow rate of 0. Flowed at 2 mL / min. The measurement sample (polymer) was dissolved in tetrahydrofuran to a concentration of 1 mg / ml under dissolution conditions in which treatment was performed for 5 minutes using an ultrasonic disperser at room temperature. Next, a sample solution is obtained by processing with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution is injected into the apparatus together with the above carrier solvent, and is detected using a refractive index detector (RI detector) and measured. The molecular weight distribution of the sample was calculated using a calibration curve measured using monodisperse polystyrene standard particles. Ten polystyrenes were used for calibration curve measurement.

Example 1
<Preparation of polymer having carboxy group>
A polyacrylic acid (1) having a weight average molecular weight of 5000 (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared.

  <Synthesis of Liquid Crystalline Compound 1>

  1 equivalent of sodium hydride with respect to imidazole was suspended in THF, and the suspension was cooled to 0 ° C., and then a THF solution of imidazole was added dropwise, followed by stirring at room temperature (25 ° C.) for 30 minutes. Subsequently, 1 equivalent of 1,6-dibromohexane in THF was added to the system and stirred at room temperature (25 ° C.) for 18 hours. After stirring, the solution was concentrated to dryness with a rotary evaporator and purified by silica gel column chromatography using a mixed solvent of chloroform: methanol = 20: 1 to 5: 1 (volume ratio) as a developing solution, and Compound A was 56%. The yield was obtained.

4,4′-dihydroxyazobenzene and 2.2 equivalents of Compound A to 4,4′-dihydroxyazobenzene are mixed in acetone, and 3 equivalents of potassium carbonate to 4,4′-dihydroxyazobenzene are added. In addition, the mixture was stirred at room temperature (25 ° C.) for 17 hours. Thereafter, the solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 3 (volume ratio) as a developing solution, and a liquid crystalline compound with a yield of 38%. 1 (compound 1) was obtained. The structure of Compound 1 was confirmed by ¹ H-NMR.

<Synthesis of composite resin>
500 mg of polyacrylic acid (1) and 10 mg of liquid crystal compound 1 are dissolved in 2 ml of chloroform, and the resulting solution is applied to a glass substrate by a spin coating method and then air-dried (drying time 6 hours) to form a film-like composite Resin 1 (thickness 20 μm) was obtained.

(Example 2)
Instead of polyacrylic acid (1), a styrene-acrylic acid copolymer (2) (manufactured by Seiko PMC Co., Ltd.) having a weight average molecular weight of 6500 was used in the same manner as in Example 1, A film-like composite resin 2 was obtained.

(Example 3)
Instead of polyacrylic acid (1), a styrene-acrylic acid copolymer (3) (manufactured by Seiko PMC Co., Ltd.) having a weight average molecular weight of 10,000 was used in the same manner as in Example 1, A film-like composite resin 3 was obtained.

Example 4
A film-like composite resin 4 was prepared in the same manner as in Example 1 except that an ethylene-acrylic acid copolymer (4) having a weight average molecular weight of 15000 was used instead of polyacrylic acid (1). Obtained.

(Example 5)
Instead of polyacrylic acid (1), a styrene-maleic acid copolymer (5) having a weight average molecular weight of 12000 (manufactured by Seiko PMC Co., Ltd.) was used. A film-like composite resin 5 was obtained.

(Example 6)
A film-like composite resin 6 was obtained in the same manner as in Example 3 except that the liquid crystal compound 2 synthesized by the following method was used instead of the liquid crystal compound 1.

  <Synthesis of Liquid Crystalline Compound 2>

  After stirring 1.2 equivalents of biscyclopentadienyl titanium chloride, 2.4 equivalents of manganese, and 2.4 equivalents of zinc with respect to 4-hydroxybenzaldehyde in THF at 0 ° C. for 1 hour, Hydroxybenzaldehyde in THF was added, and the mixture was stirred with heating under reflux for 4 hours. Then, t-butyl methyl ether was added, transferred to a separatory funnel, washed with 1N hydrochloric acid and saturated brine, the organic layer was concentrated to dryness, and a mixed solvent of ethyl acetate: heptane = 1: 2 (volume ratio). Was purified by silica gel column chromatography using as a developing solution to obtain Compound B.

The obtained compound B and 2.2 equivalents of compound A to compound B were mixed in acetone, 3 equivalents of potassium carbonate were added to compound B, and the mixture was stirred at room temperature (25 ° C.) for 17 hours. The solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 3 (volume ratio) as a developing solution, and a liquid crystalline compound was obtained in a yield of 62%. 2 (compound 2) was obtained. The structure of Compound 2 was confirmed by ¹ H-NMR.

(Example 7)
A liquid crystal compound 3 was synthesized in the same manner as in Example 1 <Synthesis of liquid crystal compound 1> except that 1,4-dibromobutane was used instead of 1,6-dibromohexane.

  A film-like composite resin 7 was obtained in the same manner as in Example 3, except that the obtained liquid crystal compound 3 was used instead of the liquid crystal compound 1.

(Example 8)
Liquid crystal compound 4 was synthesized in the same manner as in Example 1 <Synthesis of liquid crystal compound 1> except that 1,10-dibromodecane was used instead of 1,6-dibromohexane.

  A film-like composite resin 8 was obtained in the same manner as in Example 3, except that the obtained liquid crystal compound 4 was used instead of the liquid crystal compound 1.

Example 9
A film-like composite resin 9 was obtained in the same manner as in Example 3 except that the liquid crystal compound 5 synthesized by the following method was used instead of the liquid crystal compound 1.

  <Synthesis of Liquid Crystalline Compound 5>

  1 equivalent of sodium hydride with respect to imidazole was suspended in THF, and the suspension was cooled to 0 ° C., and then a THF solution of imidazole was added dropwise, followed by stirring at room temperature (25 ° C.) for 30 minutes. Next, 1 equivalent of a THF solution of 1,3-dibromopropane was added to the system and stirred at room temperature (25 ° C.) for 18 hours. After stirring, the solution was concentrated to dryness on a rotary evaporator and purified by silica gel column chromatography using a mixed solvent of chloroform: methanol = 10: 1 (volume ratio) as a developing solution, and Compound C was obtained in a yield of 68%. Obtained.

  1.1 equivalents of compound C in 4,4′-dihydroxyazobenzene and 4,4′-dihydroxyazobenzene are mixed in acetone, and then 1.5 equivalents of carbonic acid in 4,4′-dihydroxyazobenzene. Potassium was added and stirred at room temperature (25 ° C.) for 17 hours. The solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 2 (volume ratio) as a developing solution, and Compound D was obtained in a yield of 62%. Obtained.

The obtained compound D and 1.5 equivalents of compound C relative to compound D were mixed in acetone, 1.5 equivalents of potassium carbonate were added to compound D, and the mixture was stirred at room temperature (25 ° C.) for 17 hours. Thereafter, the solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 3 (volume ratio) as a developing solution, and a liquid crystalline compound was obtained in a yield of 65%. 5 (compound 5) was obtained. The structure of Compound 5 was confirmed by ¹ H-NMR.

(Example 10)
A film-like composite resin 10 was obtained in the same manner as in Example 3 except that the liquid crystal compound 6 synthesized by the following method was used instead of the liquid crystal compound 1.

  <Synthesis of Liquid Crystalline Compound 6>

  4,4′-dihydroxyazobenzene and 2.2 equivalents of ethyl 7-bromoheptanoate to 4,4′-dihydroxyazobenzene were mixed in acetone, and 3 equivalents to 4,4′-dihydroxyazobenzene. Of potassium carbonate was added and stirred at room temperature (25 ° C.) for 17 hours. The solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 5 (volume ratio) as a developing solution, and Compound E was obtained in a yield of 52%. Obtained.

To the DMF solution of Compound E, 10 equivalent of an aqueous sodium hydroxide solution (1N) was added and stirred for 6 hours. 1N hydrochloric acid was added until the reaction solution became acidic, and the mixture was partitioned with ethyl acetate. The obtained organic layer was concentrated and dried, and then recrystallized with a mixed solvent of ethyl acetate: heptane = 1: 1 (volume ratio) to obtain liquid crystal compound 6 (compound 6) in a yield of 40%. . The structure of Compound 6 was confirmed by ¹ H-NMR.

(Comparative Example 1)
A styrene-acrylic acid copolymer (3) was formed into a film by the same method as described above.

(Comparative Example 2)
A composite resin 11 was prepared in the same manner as in Example 1 except that polystyrene (6) (Scientific Polymer, Inc.) having a weight average molecular weight of 10,000 was used instead of polyacrylic acid (1). Obtained.

(Comparative Example 3)
A film-like composite resin 12 was obtained in the same manner as in Example 3 except that the liquid crystal compound 8 synthesized by the following method was used instead of the liquid crystal compound 1.

4,4′-dihydroxyazobenzene and 4 equivalents of 1-bromohexane to 4,4′-dihydroxyazobenzene were mixed in acetone, and 6 equivalents of potassium carbonate to 4,4′-dihydroxyazobenzene were added. The mixture was further stirred at room temperature (25 ° C.) for 17 hours. The solution was concentrated to dryness on a rotary evaporator and separated and purified using ethyl acetate and water. The obtained organic layer was concentrated and dried, and then purified by silica gel column chromatography using a mixed solvent of ethyl acetate: heptane = 1: 4 (volume ratio) as a developing solution, and a liquid crystalline compound with a yield of 58%. 8 (Compound 8) was obtained. The structure of Compound 8 was confirmed by ¹ H-NMR.

(Comparative Example 4)
In the same manner as in Example 1 except that polyethylene terephthalate (PET) (7) having no carboxy group having a weight average molecular weight of 7000 was used instead of polyacrylic acid (1), a film form was obtained. The composite resin 13 was obtained.

[Evaluation]
<Glass transition temperature (Tg)>
The glass transition temperature of the film-like composite resin or resin produced in the above Examples and Comparative Examples was measured using a differential scanning calorimeter as follows. As a measuring instrument, “Diamond DSC” (manufactured by PerkinElmer Japan Co., Ltd.) was used. Measurement of Tg (normal Tg) before irradiation with ultraviolet light at atmospheric pressure and room temperature (25 ° C.) is performed by cutting each film before irradiation with ultraviolet light into 2 mm squares and enclosing them in a measuring pan. Bread was used. The measurement conditions were a measurement temperature of 0 ° C. to 150 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Perform analysis based on the data in Heat, and draw an extension of the baseline before the rise of the first endothermic peak and a tangent line indicating the maximum slope between the rise of the first peak and the peak apex, The intersection was defined as the glass transition temperature (Tg).

Measurement of Tg after irradiation with ultraviolet light (Tg after irradiation with ultraviolet light) was performed by cutting each film into 2 mm squares and measuring the film irradiated with ultraviolet light (wavelength 369 nm, lamp illuminance 100 mW / cm ² ) for 10 minutes. And was performed under the same measurement conditions as described above.

Measurement of Tg after irradiation with visible light was performed by cutting each film into 2 mm squares, irradiating with ultraviolet light (wavelength 369 nm, lamp illuminance 100 mW / cm ² ) for 10 minutes, and then further visible light (wavelength 499 nm, lamp illuminance). A film irradiated with 100 mW / cm ² ) for 10 minutes was enclosed in a measurement pan and measured under the same measurement conditions as described above.

  The measurement results of the glass transition temperature are shown in Table 1 below. In addition, the “Tg reduction degree” in the following Table 1 is a reduction range of the glass transition temperature obtained by subtracting the Tg after irradiation with ultraviolet light from the normal Tg, and processing at a lower temperature is possible as the reduction range increases. This indicates that the resin is excellent in low temperature processability. In the column, ◎ indicates a decrease range of 20 ° C. or more, ○ indicates a decrease range of 10 ° C. or more and less than 20 ° C., Δ indicates a decrease range of 5 ° C. or more and less than 10 ° C., and x indicates a decrease range of less than 5 ° C. ◎ to △ indicate that it is practical.

<Pressure transfer evaluation>
After irradiation with ultraviolet light and visible light, each resin film was cut into 1 cm squares and placed on high-quality paper A (J paper manufactured by Konica Minolta, Inc.). While heating this sample at a temperature 10 ° C. higher than the normal Tg measured above, the sample was irradiated with ultraviolet light (wavelength 369 nm, lamp illuminance 100 mW) for 10 minutes, and then at room temperature (25 ° C.), visible light (wavelength 499 nm, (Illuminance of the lamp 100 mW) is irradiated for 10 minutes, and further, high-quality paper B (manufactured by Konica Minolta Co., Ltd., J paper) is stacked, the resin film part is pressurized at 0.5 MPa, and the added liquid crystalline compound is added to the high-quality paper B The presence or absence of movement was confirmed visually with a microscope. In Table 1 below, ◯ indicates that there was no movement of the liquid crystalline compound to the high quality paper B, and × indicates that there was movement of the liquid crystalline compound to the high quality paper B. It can be said that it has excellent durability.

  As is clear from Table 1 above, it was suggested that the composite resin of the example can be processed at a lower temperature after being irradiated with ultraviolet light, and is excellent in durability after processing.

  In addition, it was suggested that the composite resin of the present invention was excellent in durability when used as a toner because no seepage of the liquid crystal compound was observed even when pressurized after irradiation with visible light.

1 Photoconductor,
2 charger,
3 Exposure unit,
4 Development section,
5 Transcription part,
6 Static elimination part 7 Paper transport system,
8 Cleaning section,
9 Crimping part,
10 Image forming unit,
11 Paper feeder,
12 transport rollers,
13 Conveyor belt,
14 Paper discharge section,
15 Manual paper feeder
16 trays,
17 Thermohygrometer,
20 image processing unit,
24 Paper reversing section,
40 Irradiation part,
40a 1st irradiation part,
40b 2nd irradiation part,
50 transfer roller,
71 image reading device,
72 Automatic document feeder,
85 blades,
90 control unit,
91, 92 Pressurizing member,
100 image forming apparatus,
d Manuscript,
S Recording paper.

Claims (5)

  A composite resin in which a polymer having a carboxy group and a compound having a functional group that forms a hydrogen bond with the carboxy group and having liquid crystallinity form a hydrogen bond, wherein the hydrogen bond is irradiated with light. A composite resin that is a bond that can be cleaved by. The composite resin according to claim 1, wherein the liquid crystal compound is a compound represented by the following chemical formula (1):
In the above chemical formula (1),
X is CH or a nitrogen atom,
Y ₁ and Y ₂ are each independently a group capable of forming a hydrogen bond with a carboxy group in a polymer having a carboxy group,
Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group or a divalent heterocyclic group,
R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a thiol group, a cyano group, or a substituted or unsubstituted alkyl group, alkenyl group, alkoxy group, amino group, aryl group or heterocyclic ring. A group that may be linked together to form a ring structure,
n and m are each independently an integer of 3 or more and 10 or less. The composite resin according to claim 2, wherein Y ₁ and Y ₂ are each independently a heterocyclic group having a nitrogen atom.   An electrophotographic toner comprising the composite resin according to claim 1. Forming a toner image made of the electrophotographic toner according to claim 4 on a recording medium;
Irradiating the toner image with light having a wavelength of 300 nm or more and less than 400 nm to soften the toner image;
Irradiating the softened toner image with light having a wavelength of 400 nm to 800 nm to solidify the toner image and fix it on a recording medium;
An image forming method.