WO2016111380A1 - Ultraviolet curable liquid composition, ultraviolet curing inkjet ink, ultraviolet curing wet electrophotographic liquid developer, ultraviolet curing electrostatic inkjet ink, and image forming method using thereof - Google Patents

Ultraviolet curable liquid composition, ultraviolet curing inkjet ink, ultraviolet curing wet electrophotographic liquid developer, ultraviolet curing electrostatic inkjet ink, and image forming method using thereof Download PDF

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Publication number
WO2016111380A1
WO2016111380A1 PCT/JP2016/051058 JP2016051058W WO2016111380A1 WO 2016111380 A1 WO2016111380 A1 WO 2016111380A1 JP 2016051058 W JP2016051058 W JP 2016051058W WO 2016111380 A1 WO2016111380 A1 WO 2016111380A1
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group
general formula
bis
compound represented
liquid composition
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PCT/JP2016/051058
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French (fr)
Inventor
Junji Ito
Naotake Sato
Yasuhiro Aichi
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Canon Kabushiki Kaisha
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Priority claimed from JP2015257003A external-priority patent/JP6646443B2/en
Application filed by Canon Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Priority to CN201680005328.XA priority Critical patent/CN107108774A/en
Priority to KR1020177021551A priority patent/KR20170102325A/en
Priority to US15/533,808 priority patent/US20170336728A1/en
Priority to EP16735118.8A priority patent/EP3242897A1/en
Publication of WO2016111380A1 publication Critical patent/WO2016111380A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/125—Developers with toner particles in liquid developer mixtures characterised by the liquid

Definitions

  • the present invention relates to an ultraviolet curing wet electrophotographic liquid developer that can be used in an image forming apparatus utilizing an electrophotographic system such as an
  • the present invention also relates to an image forming method by using of the ultraviolet curable liquid composition, the ultraviolet curing inkjet ink, the ultraviolet curable liquid composition, and the
  • an electrophotographic printing machine using a liquid developer and an inkjet printer capable of high-speed and high-image quality printing have been expected.
  • the liquid developer in which an electrically
  • the liquid developer has the following characteristics: reproducibility of a fine line image is good, gradation reproducibility is good, color reproducibility is excellent, and
  • a high- image quality and high-speed digital printing apparatus that utilizes such excellent characteristics and that utilizes an electrophotographic technique using the liquid developer is increasingly actively developed.
  • the photocuring liquid developer can be prepared by using a monomer or oligomer having a reactive functional group as an electrically insulating liquid, and further adding and dissolving a
  • the photocuring liquid developer can be cured by a polymerization reaction due to irradiation with light such as ultraviolet ray, and thus address a high-speed developing treatment.
  • a radical polymerization type and a cationic polymerization type are widely known.
  • an ionic photo-acid generator is known as described in Examples in PTL 1 and in NPL 1.
  • an electrostatic inkjet system is known.
  • the electrostatic inkjet system is a system which an ink including a charged particle dispersed in an electrically insulating liquid is used and the charged particle is electrophoresed by
  • the ultraviolet curing ink includes an ultraviolet curable liquid, and a colorant such as a dye and a pigment. Also as the ultraviolet curing ink, a radical polymerization type ink and a cationic polymerization type ink are widely known.
  • PTL 2 describes the following: a combination of a plurality of vinyl ether compounds as ultraviolet curable liquid components allow a cationic
  • Cited Literature 3 discloses the following: a cationic polymerization type ink has the problem of insufficient storage stability due to a reaction based on an acid generated over time, and the instability is a large obstacle to practical use.
  • PTL 3 describes an active radiation-curing inkjet ink composition to which a basic compound including a tertiary hindered amine structure in the molecule is added in order to suppress deterioration in storage stability due to generation of the acid.
  • Such a technique is an attempt where the basic compound including a photodecomposable tertiary hindered amine structure is contained in the ink and the compound is decomposed during exposure to allow storage stability of the ink during storage and
  • PTL 4 describes use of a thioxanthone derivative and a naphthalene derivative as a sensitizer for a cationically polymerizable composition to thereby allow an excellent sensitization effect to be exerted.
  • PTL 5 describes a cationic polymerization type
  • ultraviolet curable composition in which an ionic aromatic onium salt is used as a photopolymerization initiator, and an anthracene derivative and a
  • naphthalene derivative or a benzene derivative are used in combination as a photopolymerization sensitizer composition .
  • NPL 1 Koji ARIMITSU, Fine Chemical Vo. 139
  • a radical polymerization type photocuring liquid developer including an acrylic monomer may be inhibited by oxygen from being cured, and is required to be used in combination with an acrylic monomer or oligomer having a relatively high molecular weight. As a result, the viscosity of the liquid developer may be increased to result in a reduction in the
  • electrophoretic velocity of a toner charged namely, a reduction in the rate of production in image formation.
  • cationic polymerization is a polymerization system less affected by oxygen and suitable for a photocuring liquid developer.
  • a vinyl ether monomer can be used as an electrically insulating liquid to thereby easily provide a liquid developer having a high volume
  • the vinyl ether monomer is suitable as an electrically insulating liquid for use in a photocuring liquid developer by cationic polymerization.
  • an ionic photo-acid generator is generally used.
  • the ionic photo-acid generator may cause the volume resistivity of the liquid developer to be significantly reduced, and thus the potential of an electrostatic latent image in a . developing step may be easily dropped, a high optical density may be difficult to achieve in the developing step, or image blurring may be caused.
  • the polymerization type photocuring liquid developer is again problematic in an inkjet photocuring ink in terms of a reduction in ink ejection performance, and a cationic polymerization type photocuring ink that can address a reduction in viscosity of the ink is suitable [0017]As described above, however, PTL 3 describes the following: the cationic polymerization type ink has the problem of being not sufficient in stability during storage due to a reaction based on an acid generated over time, and has a large obstacle to practical use. Then, in PTL 3, the basic compound including a tertiary hindered amine structure in the molecule is added to the active radiation-curing inkjet ink composition for the purpose of suppressing the action of an acid generated during storage. Such a technique is an attempt where the basic compound including a
  • photodecomposable tertiary hindered amine structure is decomposed during exposure to allow storage stability of the ink during storage and sensitivity thereof during exposure to be simultaneously satisfied.
  • the aromatic onium salt is used as a
  • An object of the present invention is to provide an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after ultraviolet curing, as well as a liquid developer and an inkjet ink using the ultraviolet curing liquid composition.
  • the ultraviolet curable liquid composition of the present invention is an ultraviolet curable liquid composition containing a cationically polymerizable liquid monomer, a photopolymerization initiator and a photopolymerization sensitizer, wherein the
  • cationically polymerizable liquid monomer is a vinyl ether compound
  • the photopolymerization initiator includes a compound represented by the following
  • sensitizer includes (A) at least one compound selected from the group consisting of a compound represented by the following general formula (2) and a compound
  • x represents an integer of 1 to 8
  • y represents an integer of 3 to 17
  • R 1 and R 2 are bound to each other to form a cyclic structure .
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
  • R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R
  • R and R each independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom
  • q and r each independently represent an integer of 0 to 4
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, or a glycidyl group
  • s represents an integer of 1 to 3
  • each R 11 is independently defined as above when a plurality of R u (s) are present
  • each R 12 is independently defined as above when a plurality of R 12 (s) are present
  • each R 13 is independently defined as above when a plurality of R 13 (s) are present.
  • R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom
  • u represents an integer of 0 to 4
  • R 15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, or a glycidyl group
  • t represents an integer of 1 or 2
  • each R 14 is independently defined as above when a plurality of R 14 (s) are present, and each R 15 is
  • the image forming method of the present invention is an image forming method to fix an image formed on a recording medium with the ultraviolet curable liquid composition and a colorant to the recording medium by an ultraviolet light irradiation.
  • a vinyl ether compound can be combined with the combination of the specific compounds as the photopolymerization initiator and the photopolymerization sensitizer, thereby
  • the ultraviolet curable liquid composition of the present invention includes the following components:
  • At least one vinyl ether compound as a cationically polymerizable liquid monomer
  • the ultraviolet curable liquid composition of the present invention contains a photopolymerization initiator, a photopolymerization sensitizer and a vinyl ether compound as a cationically polymerizable liquid monomer .
  • the photopolymerization initiator in the present invention is represented by the following general formula ( 1 ) .
  • x represents an integer of 1 to 8
  • y represents an integer of 3 to 17
  • R 1 and R 2 are bound to each other to form a cyclic structure in which the cyclic backbone is partially formed from an imide structure.
  • photopolymerization initiator represented by the general formula (1) can be contained to thereby provide an ultraviolet curable liquid composition that is high in resistivity unlike an ionic photo-acid generator while having sufficient fixability, and can be combined with a photopolymerization sensitizer described later to thereby realize an excellent storage stability.
  • the photopolymerization initiator in the present invention is photo-decomposed by irradiation with ultraviolet ray to generate sulfonic acid that is a strong acid.
  • the photopolymerization initiator is used in combination with a
  • C x Fy in the general formula (1) can be CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 or C 6 F 5 .
  • Examples of C x F y in the general formula (1) include the following respective groups.
  • the RF1 group, the RF2 group and the RF4 group are preferable, and the RF1 group and the RF4 group are further preferable in terms of availability and a decomposition property of the sulfonic acid ester moiety.
  • photopolymerization initiator that can be used in the present invention, in which the cyclic backbone is partially formed from an imide structure, can be selected from the group consisting of structures utilized for absorption of ultraviolet ray among a nitrogen-containing monocyclic structure, a nitrogen- containing bicyclic structure, a nitrogen-containing tricyclic structure and a nitrogen-containing
  • tetracyclic structure each having a cyclic imide structure.
  • the cyclic structure selected, in which the cyclic backbone is partially formed from an imide structure can be utilized in combination with various moieties for sulfonic acid release.
  • a cyclic structure included in a compound described later can be adopted, and can be used in combination with a sulfonic acid release moiety
  • Examples of the cyclic structure having an imide structure forming a light absorption moiety in the compound represented by the general formula (1) include the following respective groups.
  • R' in the formula (1-4) can be selected from the group consisting of a hydrogen atom, an alkylthio group having 1 to 6 carbon atoms, such as C 4 H 9 -S-, or an arylthio group having any structure represented below.
  • the photopolymerization initiator can be used singly or in combinations of two or more.
  • the content of the photopolymerization initiator in the ultraviolet curable liquid composition of the present invention is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass, further preferably 0.1 to 0.5 parts by mass based on 100 parts by mass of the cationically polymerizable liquid monomer. If two or more compounds represented by the general formula (1) are combined, the content of the photopolymerization initiator is the total content of such compounds.
  • a photopolymerization sensitizer is often used in combination with a photopolymerization
  • the photopolymerization initiator for the purposes of an enhancement in acid generation efficiency of a photo-acid generator and an increase in photosensitive wavelength.
  • the photopolymerization initiator for the purposes of an enhancement in acid generation efficiency of a photo-acid generator and an increase in photosensitive wavelength.
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
  • examples of the unsubstituted alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i- propyl group, an n-butyl group, an i-butyl group and a t-butyl group.
  • examples of the unsubstituted alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i- propyl group, an n-butyl group, an i-butyl group and a t-butyl group.
  • cycloalkyl group include a cyclohexyl group.
  • the unsubstituted alkoxy group include linear or branched alkylalkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i- butoxy group and a t-butoxy group.
  • Examples of the unsubstituted aryloxy group include a phenoxy group.
  • the unsubstituted alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group .
  • Examples of the aralkyl group include a benzyl group .
  • halogen atom examples include a chlorine atom, a bromine atom and an iodine atom.
  • substituted alkyl group, the substituted cycloalkyl group, the substituted alkoxy group, the substituted aryloxy group, the substituted aralkyl group and the substituted alkoxycarbonyl group may be any substituent that can allow the compound represented by the general formula (2) to function as the intended
  • substituents such as an
  • alkyloxy group having 1 to 4 carbon atoms a phenyl group and a morpholino group.
  • substituted alkoxycarbonyl group a group in which a carboxyl group is esterified by polyethylene glycol can also be utilized.
  • Examples of the compound represented by the general formula (2) include the following compounds, for example, thioxanthone, 2-isopropylthioxanthone, 2- dodecylthioxanthone, 2-cyclohexylthioxanthone, 2,4- diethylthioxanthone, 2 , 4-dimethylthioxanthone, 1- phenoxythioxanthone, 1-methoxycarbonylthioxanthone, 2- ethoxycarbonylthioxanthone, 3- (2- methoxyethoxycarbonyl ) -thioxanthone, 4- butoxycarbonylthioxanthone, 3-butoxycarbonyl-7- methylthioxanthone, 3, 4-di- [2- (2-methoxyethoxy) - ethoxycarbonyl ] -thioxanthone, 2-chlorothioxanthone, 1- ethoxycarbonyl-3-ethoxythio
  • 2-isopropylthioxanthone, 2- cyclohexylthioxanthone, 2 , 4-diethylthioxanthone, 2- chlorothioxanthone or l-chloro-4-n-propoxythioxanthone can be adopted because of being easily synthesized, having a high sensitization effect of the ultraviolet curable liquid composition, and exerting an excellent sensitization effect when used in combination with the compound represented by the general formula (4) or the compound represented by the general formula (5) .
  • R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R 9 and R
  • examples of the alkyl group in each of R 7 and R 8 include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t-butyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the alkoxy group include a methoxy group and an ethoxy group.
  • Examples of the aryloxy group include a phenoxy group.
  • Examples of the aralkyl group include a benzyl group.
  • halogen atom examples include a chlorine atom, a bromine atom and an iodine atom.
  • examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with a substituent having an oxygen atom, in R 9 and R 10 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom.
  • examples of the substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group.
  • Examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2- hydroxyethyl group, a 3-hydroxyethyl group, a 2- hydroxypropyl group, a 2-methoxyethyl group, a 2- ethoxyethyl group and a 2-phenoxyethyl group.
  • Examples of the glycidyl group include a glycidyl group and a 2- methylglycidyl group.
  • Examples of an anthracene-9, 10-dioxy compound represented by the general formula (3) include the following compounds:
  • examples of the anthracene-9, 10- dioxy compound of the general formula (3), having an alkyl group as a substituent on the anthracene ring include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
  • examples of the anthracene-9, 10- dioxy compound of the general formula (3), having a halogen atom as a substituent on the anthracene ring include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
  • examples of the anthracene-9 , 10- dioxy compound of the general formula (3), having an alkoxy group as a substituent on the anthracene ring include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
  • examples of the anthracene-9, 10- dioxy compound of the general formula (3) having an aryloxy group as a substituent on the anthracene ring include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
  • anthracene compounds in particular, 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-bis (n-propoxy) anthracene, 9, 10-bis (i- propoxy) anthracene , 9, 10-bis (n-butoxy) anthracene or 9 , 10-bis ( i-butoxy) anthracene can be adopted because of being easily synthesized, having a high sensitization effect of the ultraviolet curable liquid composition, and exerting an excellent sensitization effect when used in combination with the compound represented by the general formula (4) or the compound represented by the general formula (5) .
  • the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) can be used singly or in combinations of two or more.
  • the total content of the compound selected from the group consisting of the compound represented by the compound represented by the general formula (2) and the compound represented by the general formula (3) in the entire ultraviolet curable liquid composition is defined as B% by mass, and the content of the compound represented by the general formula (1) in the entire ultraviolet curable liquid composition is defined as A% by mass.
  • the B/A here is preferably 1.0 or more, further preferably 5.0 or more.
  • the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) is used in combination of two or more, the total content of two or more is defined as B% by mass.
  • the B/A is 1.0 or more, the amount of energy transfer from the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) to the
  • photopolymerization initiator can be increased to result in a further enhancement in sensitivity.
  • q and r each independently represent an integer of 0 to 4
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group, or an aralkyl group
  • s represents an integer of 1 to 3
  • each R 11 is independently defined as above when a plurality of R n (s) are present
  • each R 12 is
  • R 12 (s) are present, and each R 13 is independently
  • the compound represented by the general formula (4) can be the compound represented by the general formula ( 6 ) .
  • R 18 and R 19 each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group, or an aralkyl group, each R 16 is independently defined as above when a
  • each R 17 is
  • R 17 (s) are present.
  • examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with a substituent having an oxygen atom, represented by each of R 13 , R 18 and R 19 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom.
  • substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group.
  • Examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2- hydroxyethyl group, a 3-hydroxyethyl group, a 2- hydroxypropyl group, a 2-methoxyethyl group, a 2- ethoxyethyl group and a 2-phenoxyethyl group.
  • Examples of the glycidyl group include a glycidyl group and a 2- methylglycidyl group.
  • examples of the halogen atom in each of R 11 , R 12 , R 16 and R 17 include a fluorine atom, a chlorine atom and a bromine atom.
  • examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t- butyl group.
  • examples of the aralkyl group include a benzyl group and a phenethyl group.
  • examples of the alkoxy group include a methoxy group and an ethoxy group.
  • Examples of the aryloxy group include a phenoxy group .
  • Examples of the aralkyl group include a benzyl group.
  • halogen atom examples include a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the naphthalene compound represented by the general formula (4) and the naphthalene compound represented by the general formula (6) include the following compounds (2-1) to (2-25):
  • examples of the naphthalene compound represented by the general formula (4) and the naphthalene compound represented by the general formula (6) further include the following compounds:
  • substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 5-positions ;
  • substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 6-positions ;
  • substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 8-positions ;
  • substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 2 , 7-positions .
  • examples of the compound of each of the general formulae (4) and (6), having an alkyl group as a substituent on the naphthalene ring include the following compounds:
  • examples of the compound of the general formula (4), having an alkyl group as a substituent on the naphthalene ring include the following compounds:
  • Examples of the compound of the general formula (4) having an alkyl group as a substituent on the naphthalene ring further include the following
  • Examples of the compound of the general formula (4) having an alkyl group as a substituent on the naphthalene ring further include the following
  • examples of the compound of each of the general formulae (4) and (6), having a halogen atom as a substituent on the naphthalene ring include the following . compounds :
  • 2-chloro-l 4-dimethoxynaphthalene, 2-chloro-l, 4- diethoxynaphthalene, 2-chloro-l, 4-bis (i- propoxy) naphthalene, 2-chloro-l, 4-bis (n- butoxy) naphthalene, 2-chloro-l , 4-bis (n- octyloxy) naphthalene, 2-chloro-l, 4-bis (2- ethylhexyloxy) naphthalene, 2-chloro-l, 4- dibenzyloxynaphthalene, 2-chloro-l, 4- diphenethyloxynaphthalene, 2-chloro-l , 4- diglycidyloxynaphthalene, 2-chloro-4-methoxy-l-naphthol ,
  • examples of the compound of the general formula (4), having a halogen atom as a substituent on the naphthalene ring include the
  • Examples of the compound of the general formula (4) having a halogen atom as a substituent on the naphthalene ring further include the following
  • examples of the compound of each of the general formulae (4) and (6), having alkoxy as a substituent on the naphthalene ring include the
  • examples of the compound of the general formula (4), having alkoxy as a substituent on the naphthalene ring include the following compounds :
  • Examples of the compound of the general formula (4) having alkoxy as a substituent on the naphthalene ring further include the following compounds:
  • examples of the compound of each of the general formulae (4) and (6), having aryloxy as a substituent on the naphthalene ring include the following compounds:
  • Examples of the compound of the general formula (4) having aryloxy as a substituent on the naphthalene ring further include the following compounds:
  • R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom
  • u represents an integer of 0 to 4
  • R 15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with an oxygen atom, a glycidyl group or an aralkyl group
  • t represents an integer of 1 or 2
  • each R 14 is independently defined as above when a plurality of R 14 (s) are present, and each R 15 is independently defined as above when a plurality of R 15 (s) are present
  • u represents an integer of 0 to 4
  • R 15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with an oxygen atom, a glycidyl group or an aralkyl group
  • t represents an integer of 1 or 2
  • each R 14 is independently defined as above when a plurality of R 14 (s) are present
  • the compound represented by the general formula (5) can be the compound represented by the general formula ( 7 ) .
  • R 20 represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom
  • w represents an integer of 0 to 4
  • R 21 and R 22 each independently represent a
  • each R 20 is independently defined as above when a plurality of R 20 (s) are present.
  • substituent having an oxygen atom in each of R 15 , R 21 and R 22 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom.
  • substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group.
  • alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2-hydroxyethyl group, a 3- hydroxyethyl group, a 2-hydroxypropyl group, a 2- methoxyethyl group, a 2-ethoxyethyl group and a 2- phenoxyethyl group.
  • Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group.
  • Examples of the aralkyl group include a benzyl group.
  • examples of the halogen atom in each of R 14 and R 20 include a fluorine atom, a chlorine atom and a bromine atom.
  • Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t-butyl group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group
  • examples of the alkoxy group include a methoxy group and an ethoxy group
  • examples of the aryloxy group include a phenoxy group.
  • Examples of the benzene compound represented by the general formula (5) and the benzene compound represented by the general formula (7) include the following compounds:
  • examples of the benzene compound represented by the general formula (5) include the following compounds:
  • examples of the compound of each of the general formulae (5) and (7) having an alkyl group as a substituent on the benzene ring include the following compounds:
  • examples of the compound of the general formula (5) having an alkyl group as a substituent on the benzene ring include the following compounds :
  • examples of the compound of each of the general formulae (5) and (7) having a halogen atom as a substituent on the benzene ring include the following compounds:
  • examples of the compound of the general formula (5) having a halogen atom as a substituent on the benzene ring include the following compounds :
  • examples of the compound of each of the general formulae (5) and (7) having alkoxy as a substituent on the benzene ring include the following compounds :
  • examples of the compound of the general formula (5) having alkoxy as a substituent on the benzene ring include the following compounds: 1,2, 3-trimethoxybenzene, 3-methoxy-l, 2-diethoxybenzene, 3-methoxy-l, 2-bis (i-propoxy) benzene, 3-methoxy-l, 2- bis (n-butoxy) benzene, 3-methoxy-l, 2-bis (n- octyloxy) benzene, 3-methoxy-l, 2-bis (2- ethylhexyloxy) benzene, 3-methoxy-l, 2-dibenzyloxybenzene, 3-methoxy-l, 2-diphenethyloxybenzene, 3-methoxy-l, 2- diglycidyloxybenzene, 2-methoxy-l , 3-diethoxybenzene, 2- methoxy-1, 3-bis ( i-propoxy) benzene, 2-methoxy-
  • examples of the compound of each of the general formulae (5) and (7) having aryloxy as a substituent on the benzene ring include the following compounds :
  • examples of the compound of the general formula (5) having aryloxy as a substituent on the benzene ring include the following compounds:
  • 1, 4-dimethoxynaphthalene, 1,4- diethoxynaphthalene, 1, 4-bis (n-propoxy) naphthalene, 1, 4-bis (i-propoxy) naphthalene, 1, 4-bis (n- butoxy) naphthalene or 1, 4-bis (i-butoxy) naphthalene can be adopted because of having a higher sensitization effect of the ultraviolet curable liquid composition and exhibiting an excellent storage stability when used in combination with the compound represented by the general formula (1) .
  • the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) can be used singly or in combinations of two or more.
  • the total content of the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) in the entire ultraviolet curable liquid composition is defined as C% by mass, and the content of the compound represented by the general formula (1) in the entire ultraviolet curable liquid composition is defined as A% by mass.
  • the C/A here is preferably 1.0 or more, further preferably 5.0 or more.
  • the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) is used in combination of two or more, the total content of two or more is defined as C% by mass.
  • the C/A is 1.0 or more, the amount of an electrons that
  • the photopolymerization initiator can be increased to further enhance sensitivity and to further enhance storage stability.
  • a vinyl ether compound is used as a polymerizable liquid monomer.
  • the vinyl ether compound can be used to thereby provide an ultraviolet curable liquid composition having high resistivity, low viscosity and high sensitivity.
  • the acrylic monomer however, has the bias in electron density in the molecule, and such bias causes the electrostatic interaction between molecules to make the ultraviolet curable liquid composition difficult to have low viscosity. Accordingly, the acrylic monomer is difficult to use in an application as a component of a liquid developer or an inkjet ink having low viscosity, which is an object of the present invention.
  • composition including the acrylic monomer.
  • cyclic ether monomer has again difficulty in providing a liquid composition having high resistivity, and furthermore the cyclic ether monomer is
  • the cyclic ether monomer is also difficult to use in an application as a component of a liquid developer or an inkjet ink, which is an object of the present invention.
  • the present inventors suppose the following: when the vinyl ether compound is used as the polymerizable liquid monomer, a small bias in electron density in the molecule can allow an ultraviolet curable liquid composition having low viscosity, high resistivity and high sensitivity to be provided.
  • the cationically polymerizable liquid monomer is a vinyl ether compound having no hetero atom in a moiety other than the vinyl ether group.
  • hetero atom here refers to any atom other than a carbon atom and a hydrogen atom.
  • resistance value of a liquid composition in which a vinyl ether compound having a hetero atom is used may be lower than the resistance value of a liquid
  • the vinyl ether compound having no hetero atom in a moiety other than the vinyl ether group can be used.
  • the cationically polymerizable liquid monomer is a vinyl ether compound having no carbon-carbon double bond in a moiety other than the vinyl ether group. While a carbon-carbon double bond has an electron occupied orbital with a high energy level and an electron unoccupied orbital with a low energy level, such orbitals may serve as a passage for electrons or holes. Therefore, the resistance value of a liquid composition in which a vinyl ether compound having a carbon-carbon double bond in a moiety other than the vinyl ether group is used may be lower than the resistance value of a liquid composition in which the vinyl ether compound not having such a double bond is used. Accordingly, in order to efficiently control the resistance value of the liquid composition, the vinyl ether compound not having such a double bond in a moiety other than the vinyl ether group can be used.
  • the cationically polymerizable liquid monomer can further contain a vinyl ether compound having a cyclic structure in the molecule.
  • the vinyl ether compound having a cyclic structure in the molecule can be used to thereby impart excellent sensitivity and strength after curing.
  • Examples of the vinyl ether compound having a cyclic structure in the molecule include an aromatic vinyl ether compound as well as a vinyl ether compound having an alicyclic backbone.
  • the resistance value of a liquid composition in which an aromatic vinyl ether compound is used may be lower than the resistance value of a liquid composition in which an alicyclic vinyl ether compound is used. Accordingly, in order to efficiently control the resistance value of the liquid composition, a vinyl ether compound having an alicyclic backbone can be adopted.
  • the vinyl ether compound having a cyclic structure in the molecule can be a compound which has at least one, preferably 1 to 4 vinyl ether groups, and in which the moiety other than the vinyl ether group is a hydrocarbon group having 6 to 18 carbon atoms.
  • the hydrocarbon group used here can be selected from the group consisting of hydrocarbon groups included in exemplary compounds B-l to B-30 described later.
  • One aspect can also be provided in which the vinyl ether compound having a cyclic structure in the molecule and a vinyl ether compound having no cyclic structure in . the molecule are used in combination as the cationically polymerizable liquid monomer.
  • the ratio of the content of the vinyl ether compound having a cyclic structure in the molecule to the total amount of the vinyl ether compounds is
  • the molecular weight of each of the vinyl ether compound having a cyclic structure in the molecule and the vinyl ether compound having no cyclic structure in the molecule, as the cationically polymerizable monomer is preferably 130 or more, further preferably 170 or more. When the molecular weight is 130 or more,
  • volatility of the cationically polymerizable monomer can be reduced and the amount of radiation can be reduced. While the upper limit of the molecular weight of the cationically polymerizable monomer to be used is not defined, vinyl ether having a molecular weight of 300 or less can be used as a main component because low viscosity of the liquid composition is easily achieved.
  • Examples of the vinyl ether compound having no cyclic structure include a compound represented by the following formula (A) .
  • R" represents 2 or 3 and R" represents a hydrogen atom or a methyl group] .
  • the alkyl group substituted with a vinyloxy group can have 1 to 4 vinyloxy groups .
  • Examples of the vinyl ether compound having a cyclic structure include a compound represented by the following formula (B) .
  • Rb represents a direct bond, an alkylene group having 1 to 3 carbon atoms or an alkenyl group having 3 carbon atoms.
  • Rc represents any of the following cyclic structures.
  • cyclohexanedimethanol divinyl ether (B-17) or 2,2- bis (4-hydroxycyclohexyl) propane divinyl ether (B-29) can be contained in the ultraviolet curable liquid composition in order to enhance sensitivity and
  • the ultraviolet curable liquid composition of the present invention can contain the following additive (s), if necessary.
  • a cationic polymerization inhibitor can also be added, to the ultraviolet curable liquid composition of the present invention.
  • Examples of the cationic polymerization inhibitor can also be added, to the ultraviolet curable liquid composition of the present invention. Examples of the cationic
  • polymerization inhibitor include an alkali metal
  • Such amines can be alkanolamines , N,N- dimethylalkylamines, N, N-dimethylalkenylamines , N,N- dimethylalkynylamines or the like.
  • Examples include triethanolamine, triisopropanolamine, tributanolamine, N-ethyldiethanolamine, propanolamine, n-butylamine, sec-butylamine, 2-aminoethanol , 2-methylaminoethanol , 3-methylamino-l-propanol, 3-methylamino-l , 2-propanediol, 2-ethylaminoethanol, 4-ethylamino-l-butanol , 4- (n- butylamino) -1-butanol, 2- (t-butylamino) ethanol , N,N- dimethylundecanol, N, N-dimethyldodecanolamine, N,N- dimethyltride
  • the cationic polymerization inhibitor can be a secondary amine.
  • inhibitor to be added can be 10 to 5000 ppm based on the ultraviolet curable liquid composition of the present invention.
  • a radical polymerization inhibitor may also be added to the ultraviolet curable liquid composition of the present invention.
  • photopolymerization initiator may be slightly
  • radical compound decomposed during storage over time to form a radical compound, and the radical compound may cause
  • the radical polymerization inhibitor can be added in order to prevent such radical polymerization.
  • radical polymerization inhibitor examples include a phenolic hydroxyl group- containing compound, quinones such as methoquinone
  • hydroquinone monomethyl ether hydroquinone and 4- methoxy-l-naphthol, a hindered amine type antioxidant, 1 , l-diphenyl-2-picrylhydrazyl free radical, an N-oxyl free radical compound, a nitrogen-containing
  • heterocyclic mercapto type compound a thioether type antioxidant, a hindered phenol type antioxidant, ascorbic acids, zinc sulfate, thiocyanates , a thiourea derivative, various saccharides, a phosphoric acid type antioxidant, nitrites, sulfites, thiosulfates , a hydroxylamine derivative, aromatic amines,
  • oximes a polycondensate of dicyandiamide and polyalkylenepolyamine, a sulfur-containing compound such as phenothiazine, a tetra azaannulene (TAA) -based complexing agent, and hindered amines.
  • a sulfur-containing compound such as phenothiazine, a tetra azaannulene (TAA) -based complexing agent
  • TAA tetra azaannulene
  • the amount of the radical polymerization inhibitor to be added can be 1 to 5000 ppm based on the ultraviolet curable liquid composition of the present invention.
  • the ultraviolet curable liquid composition of the present invention When the ultraviolet curable liquid composition of the present invention is applied to an inkjet ink, a wet electrophotographic liquid developer or the like, a pigment as a coloring material can be contained.
  • any pigment can be adopted without particular limitation as long as such a pigment is adapted to the intended applications of the ultraviolet curable liquid composition of the present invention.
  • At least one selected from the group consisting of generally commercially available organic pigment and inorganic pigment one obtained by
  • dispersion medium or one obtained by grafting the surface of a pigment by a resin can be used.
  • pigments described in "Dictionary of Pigments" edited by Seijiro ITO examples include pigments described in "Dictionary of Pigments" edited by Seijiro ITO
  • examples of a pigment exhibiting a yellow color include the following :
  • Examples of a pigment exhibiting a red or magenta color include the following:
  • Examples of a pigment exhibiting a blue or cyan color include the following:
  • Phthalocyanine pigments having 1 to 5 phthalimidemethyl groups as substituent ( s ) on the phthalocyanine backbone.
  • Examples of a pigment exhibiting a green color include the following:
  • Examples of a black color pigment include the following :
  • Examples of a white pigment include the following:
  • Titanium oxide here is smaller in specific
  • titanium oxide can be utilized as the white pigment.
  • white pigment which may be a pigment other than the white pigments recited.
  • other white pigment may also be used, if necessary.
  • a ball mill such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill or a wet jell mill can be used.
  • dispersant can also be added in dispersing of the pigment.
  • examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular acid ester, a salt of a high molecular polycarboxylic acid, a high molecular unsaturated acid ester, a high molecular copolymerized product, a modified
  • polyacrylate an aliphatic polyvalent carboxylic acid, a formalin condensate of naphthalenesulfonic acid, a polyoxyethylene alkyl phosphoric acid , ester, and a pigment derivative.
  • a commercially an aliphatic polyvalent carboxylic acid, a formalin condensate of naphthalenesulfonic acid, a polyoxyethylene alkyl phosphoric acid , ester, and a pigment derivative.
  • polymeric dispersant such as Solsperse Series produced by Lubrizol Corporation can also be used.
  • a synergist according to various pigments can also be used as a dispersion auxiliary material.
  • the dispersant and the dispersion auxiliary material can be added in an amount of 1 to 50 parts by mass based on 100 parts by mass of the pigment.
  • the pigment can be used in the form of a
  • any medium can be selected from various liquid materials and used depending on the objects as long as the intended functions in the
  • the vinyl ether compound that can also be used as the liquid monomer can be used as the liquid medium for dispersing of the pigment because the vinyl ether compound can be utilized as a monomer component as it is.
  • electrophotographic liquid developer an electrostatic inkjet ink or the like
  • a toner particle insoluble in the liquid monomer can be contained as a coloring material.
  • electrophoretic fine particle can be contained in the electrostatic inkjet ink, and the toner particle
  • the insoluble in the liquid monomer can also be utilized as a charged particle as a coloring material.
  • the toner particle contains a binder resin and a pigment, and can contain a charge director, if necessary.
  • Examples of the method for producing the toner particle include a coacervation method and a wet
  • the toner particle obtained by such a method preferably has an average particle size of 0.05 to 5 ⁇ , more preferably 0.05 to 1 ⁇ , from the viewpoint that a highly fine image is obtained.
  • the toner particle can be used in the form of a dispersion including a pigment dispersed in a liquid medium, for preparing a liquid developer using the ultraviolet curing liquid composition.
  • a liquid medium for preparation of such a toner particle As the liquid medium for preparation of such a toner particle
  • any medium can be selected from various . liquid materials and used depending on the objects as long as the intended functions in the ultraviolet curing liquid developer are not impaired.
  • the vinyl ether compound that can also be utilized as the liquid monomer can be used as the liquid medium for dispersing of the toner particle because the vinyl ether compound can be utilized as a monomer component as it is.
  • binder resin any of various binder resins having fixability to an adherend such as . paper or a plastic film can be used, a resin such as an epoxy resin, an ester resin, an acrylic resin, a styrene- acrylic resin, an alkyd resin, a polyethylene resin, an ethylene-acrylic resin or a rosin-modified resin can be used, and such a resin can be used singly or in
  • the content of the binder resin can be 50 to 1000 parts by mass based on 100 parts by mass of the pigment.
  • Various agents can be used as the charge director.
  • oils and fats such as a linseed oil and a soybean oil; an alkyd resin, a halogen polymer, an aromatic polycarboxylic acid, an acidic group- containing water-soluble dye, an oxidation condensate of an aromatic polyamine, metal soaps such as cobalt naphthenate, nickel naphthenate, iron naphthenate, zinc naphthenate, cobalt octylate, nickel octylate, zinc octylate, cobalt dodecylate, nickel dodecylate, zinc dodecylate, aluminum stearate and cobalt 2- ethylhexanoate; sulfonic acid metal salts such as a petroleum-based sulfonic acid metal salt and a metal salt of a sulfosuccinic acid ester; phospholipids such as lecithin; salicylic acid metal salts such as a t- butylsalicylic acid metal
  • polyvinylpyrrolidone resin a polyamide resin, a sulfonic acid-containing resin and a hydroxybenzoic acid derivative.
  • the ultraviolet curable liquid composition of the present invention appropriately selected and used in the ultraviolet curable liquid composition of the present invention, if necessary, depending on objects such as an enhancement in adaptivity to a recording medium, storage stability, image storing property and other various performances.
  • the additives include a surfactant, a lubricant, a filler, a defoamer, an ultraviolet
  • electrophotographic liquid developer an electrostatic inkjet ink or the like, the developer and the ink can be prepared and used so as to have the same physical properties as physical properties of common liquid developer and electrostatic inkjet ink.
  • the viscosity can be 0.5 to 10 mPa «s at 25°C and the volume resistivity can be 1 x 10 10 to 1 x 10 13 Qcm when the concentration of the toner particle included in the liquid developer is 2% by mass.
  • a too high viscosity may reduce the electrophoretic velocity of the toner particle in the liquid developer, resulting in a reduction in printing rate.
  • a too low volume resistivity may easily drop the potential of an electrostatic latent, image, imparting a high optical density hardly or causing image blurring.
  • a too high volume resistivity may reduce the
  • an ultraviolet curing liquid developer that achieves high ultraviolet curability and that satisfies the above values of physical properties can be prepared.
  • the ultraviolet curable liquid composition of the present invention can be used in an ultraviolet curing inkjet ink, an ultraviolet curing wet
  • electrophotographic liquid developer and an ultraviolet curing electrostatic inkjet ink can also be used in other applications.
  • composition of the present invention and the surface thereof is subjected to photocuring with being left to be opened include various applications described below: a paint for automobiles, woodwork coating, polyvinyl chloride (PVC) floor coating, ceramic wall coating, coating for building materials, resin hard coat, metallized base coat, film coating, coating for liquid crystal displays (LCDs) , coating for plasma displays
  • PDPs coating for optical disks, metal coating, optical fiber coating, a printing ink, a planographic ink, a metal can ink, a screen printing ink and gravure varnish .
  • Such usage can also be adopted in the fields of a resist, a display, a seal agent, a dental material, a photo forming material. and the like.
  • composition of the present invention and the surface thereof is bonded with other substrate and subjected to photocuring include an adhesive, a pressure sensitive adhesive, a tackifier and a sealing agent.
  • ultraviolet curable liquid composition can be appropriately used in applications illustrated in the following literatures.
  • ultraviolet curable liquid composition of the present invention for example, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a hot cathode tube, a black light or an LED (light emitting diode) can be applied.
  • a mercury lamp for example, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a hot cathode tube, a black light or an LED (light emitting diode)
  • the ultraviolet curable liquid composition is applied to an inkjet ink, a wet electrophotographic liquid developer, an electrostatic inkjet ink or the like, the
  • ultraviolet curable liquid composition can be any ultraviolet curable liquid composition.
  • irradiated with ultraviolet ray after ink impact or transfer to a recording medium such as paper or a film.
  • a band metal halide lamp, a cold cathode tube, a hot cathode tube, a mercury lamp, a black light, an LED or the like can be used.
  • the amount of irradiation with ultraviolet ray can be 0.1 to 1000 mJ/cm 2 .
  • ultraviolet curing liquid composition of the present invention is more specifically described with reference to Examples, but the present invention is not limited thereto without departing from the gist and the scope of application thereof.
  • parts(s) and “%” mean “part(s) by mass” and “% by mass”, respectively, in the following description unless particularly noted.
  • a polyethylene terephthalate film was coated with each ultraviolet curable liquid composition at 25°C by a wire bar (No. 3) , and irradiated with ultraviolet ray by a high pressure mercury lamp with a lamp output of 120 mW/cm 2 at a predetermined amount of light to form a film (cured film) .
  • the thickness of the film formed was 6 um.
  • the surface of the film immediately after curing was touched by fingers, and the presence of the surface tackiness (stickiness) was confirmed and rated according to the following criteria.
  • Tackiness was observed in curing at an amount of light of 300 mJ/cm 2 , and tackiness was not observed in curing at an amount of light of 1000 mJ/cm 2 .
  • the volume resistivity was measured using R8340
  • a light shielding bottle was charged with each
  • E of the value of each volume resistivity in Tables 1 to 3 means “xlO", and the number at the right of “E” means exponent.
  • "1.8E + 10" in Example 1 means “1.8 x 10 10 ".
  • compositions were changed from the photopolymerization initiator in the ultraviolet curable liquid composition of the present invention, had difficulty in
  • the resulting ultraviolet curing inkjet ink was loaded in an UV curing inkjet printer UJF-3042HG manufactured by Mimaki Engineering Co., Ltd. and subjected to
  • the toner particle precursor (59.40 parts) was loaded in a planetary bead mill (Classic Line P- 6/Fritsch) together with the following respective components, and pulverized at room temperature at 200 rpm for 4 hours to provide a toner particle dispersion (solid content: 20% by mass) .
  • the resulting toner particle had an average particle size of 0.85 ⁇ m (measured by Nanotrac 150 manufactured by Nikkiso Co., Ltd.).
  • the following respective components were added to 10.0 parts of the toner particle dispersion to provide an ultraviolet curing liquid developer.
  • the volume resistivity was measured using R8340
  • An electrostatic pattern was formed on electrostatic recording paper at a surface charge of 150 to 500 V, and the ultraviolet curing liquid developer was used to perform development by a roller developing machine. The quality of the resulting image was confirmed, and as a result, a high-density and highly-fine image was obtained. While the variation in density and image blurring were observed due to attenuation of the surface charge at a low electric resistivity of the liquid developer, the variation in density and image blurring were not observed by use of the ultraviolet curing liquid developer.
  • a polyethylene terephthalate film was coated with the ultraviolet curing liquid developer at 25°C by a wire bar (No. 6), and irradiated by a high pressure mercury lamp with a lamp output of 120 mW/cm 2 at an amount of light of 45 mJ/cm 2 (measurement wavelength: 365 nm) to form a cured film.
  • the surface of the film immediately after curing was touched by fingers, and the presence of the surface tackiness (stickiness) was confirmed, but tackiness was not observed at all and it could be confirmed that sufficient fixability was achieved.
  • the resulting ultraviolet curing liquid developer was used to evaluate the volume resistivity, developability and fixability, as described below.
  • the volume resistivity was measured using R8340 manufactured by Advantest Corporation, and was found to be 4.9 x 10 7 ⁇ cm.
  • Example 27 The same evaluation as in Example 27 was tried, but development could not be conducted. The reason for this was considered as follows: a too low volume resistivity of the liquid developer caused the surface charge to be significantly attenuated.
  • Example 27 The same evaluation as in Example 27 was performed, and tackiness was not observed at all and it could be confirmed that sufficient fixability was achieved.
  • the ultraviolet curing liquid developer prepared in Example 27 was used for an ultraviolet curing
  • electrostatic inkjet ink The ink was used for
  • the ink solid density of the ink fixed onto the medium subjected to printing was measured by a thermal
  • the medium subjected to printing was irradiated by a high pressure mercury lamp with a lamp output of 120 mW/cm 2 at an amount of light of 45 mJ/cm 2
  • the ultraviolet curing liquid developer prepared in Comparative Example 9 was used for an ultraviolet curing electrostatic inkjet ink.
  • the ink was tried to be used for printing on a medium by use of an inkjet printing apparatus described in PCT Publication No. WO 93/11866, but the ink was not ejected.
  • the ultraviolet curable liquid composition of the present invention includes at least the following respective components:
  • general formula (3) and at least one selected from the group consisting of compounds represented by general formula (4) and general formula (5), as a
  • the vinyl ether compound can be combined with the combination of the specific compounds as the
  • photopolymerization sensitizer to thereby provide an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after ultraviolet curing.
  • the ultraviolet curable liquid composition can be used to provide an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an ultraviolet curing inkjet ink, an
  • the liquid developer and inks are also high in sensitivity, low in viscosity and

Abstract

An object of the present invention is to provide an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after ultraviolet curing. The ultraviolet curable liquid composition of the present invention is an ultraviolet curable liquid composition containing a cationically polymerizable liquid monomer, a photopolymerization initiator and a photopolymerization sensitizer, wherein the cationically polymerizable liquid monomer is a vinyl ether compound, the photopolymerization initiator includes a compound represented by general formula (1), and the photopolymerization sensitizer includes, (A) at least one compound selected from the group consisting of a compound represented by general formula (2) and a compound represented by general formula (3), and (B) at least one compound selected from the group consisting of a compound represented by general formula (4) and a compound represented by general formula (5).

Description

DESCRIPTION
Title of Invention:
ULTRAVIOLET CURABLE LIQUID COMPOSITION,
ULTRAVIOLET CURING INKJET INK, ULTRAVIOLET CURING WET ELECTROPHOTOGRAPHIC LIQUID DEVELOPER, ULTRAVIOLET CURING ELECTROSTATIC INKJET INK, AND IMAGE FORMING METHOD USING THEREOF
Technical Field
[0001] The present invention relates to an ultraviolet curing wet electrophotographic liquid developer that can be used in an image forming apparatus utilizing an electrophotographic system such as an
electrophotographic method, an electrostatic recording method or electrostatic printing and an ultraviolet curable liquid composition that can be used as an ultraviolet curing inkjet ink and an ultraviolet curing electrostatic inkjet ink. In the other embodiment, the present invention also relates to an image forming method by using of the ultraviolet curable liquid composition, the ultraviolet curing inkjet ink, the ultraviolet curable liquid composition, and the
ultraviolet curing electrostatic inkjet ink.
Background Art
[0002] Conventionally, a printing machine utilizing a printing plate has been used for producing printed products required to be provided in a certain number, such as local advertisings, documents distributed in company, and large posters.
[0003] In recent years, an on-demand printing machine capable of rapidly responding to diversified needs and also allowing stock to be reduced has been increasingly utilized instead of such a conventional printing
machine. As such an on-demand printing machine, an electrophotographic printing machine using a liquid developer and an inkjet printer capable of high-speed and high-image quality printing have been expected. The liquid developer, in which an electrically
insulating liquid is used as a carrier liquid, thus hardly causes the problem of aggregation of a coloring resin particle in the liquid developer during storage, as compared with a dry developer, and a fine toner can be used therein. As a result, the liquid developer has the following characteristics: reproducibility of a fine line image is good, gradation reproducibility is good, color reproducibility is excellent, and
availability in a high-speed image forming method is excellent, as compared with a dry developer. A high- image quality and high-speed digital printing apparatus that utilizes such excellent characteristics and that utilizes an electrophotographic technique using the liquid developer is increasingly actively developed.
[0004] In view of such circumstances, a liquid developer having better properties is demanded to be developed. As the liquid developer, a photocuring liquid developer is known. The photocuring liquid developer can be prepared by using a monomer or oligomer having a reactive functional group as an electrically insulating liquid, and further adding and dissolving a
photopolymerization initiator. The photocuring liquid developer can be cured by a polymerization reaction due to irradiation with light such as ultraviolet ray, and thus address a high-speed developing treatment. As the polymerization type for such photocuring, a radical polymerization type and a cationic polymerization type are widely known. As a photopolymerization initiator to be contained in a cationic polymerization type photocuring liquid developer, an ionic photo-acid generator is known as described in Examples in PTL 1 and in NPL 1.
[0005] On the other hand, various inks such as a water- based ink, a solvent-based type ink and an. ultraviolet curing ink are used in an inkjet printer.
[0006]As a technique for reductions in thermal energy to be consumed and the amount of a volatile organic solvent vapor to be diffused, an electrostatic inkjet system is known. The electrostatic inkjet system is a system which an ink including a charged particle dispersed in an electrically insulating liquid is used and the charged particle is electrophoresed by
application of an electrostatic field, and concentrated and ejected. The ultraviolet curing ink includes an ultraviolet curable liquid, and a colorant such as a dye and a pigment. Also as the ultraviolet curing ink, a radical polymerization type ink and a cationic polymerization type ink are widely known.
[0007] PTL 2 describes the following: a combination of a plurality of vinyl ether compounds as ultraviolet curable liquid components allow a cationic
polymerization type ultraviolet curing ink to obtain a high sensitivity and enhanced adhesiveness to a
recording medium.
[0008]Cited Literature 3 discloses the following: a cationic polymerization type ink has the problem of insufficient storage stability due to a reaction based on an acid generated over time, and the instability is a large obstacle to practical use. PTL 3 describes an active radiation-curing inkjet ink composition to which a basic compound including a tertiary hindered amine structure in the molecule is added in order to suppress deterioration in storage stability due to generation of the acid. Such a technique is an attempt where the basic compound including a photodecomposable tertiary hindered amine structure is contained in the ink and the compound is decomposed during exposure to allow storage stability of the ink during storage and
sensitivity thereof during exposure to be
simultaneously satisfied. [0009] PTL 4 describes use of a thioxanthone derivative and a naphthalene derivative as a sensitizer for a cationically polymerizable composition to thereby allow an excellent sensitization effect to be exerted.
PTL 5 describes a cationic polymerization type
ultraviolet curable composition in which an ionic aromatic onium salt is used as a photopolymerization initiator, and an anthracene derivative and a
naphthalene derivative or a benzene derivative are used in combination as a photopolymerization sensitizer composition .
Citation List
Patent Literatures
[0010] PTL 1: Japanese Patent No. 3442406
PTL 2: Japanese Patent Application Laid-Open No. 2005-154734
PTL 3: Japanese Patent Application Laid-Open No. 2009-84448
PTL 4: Japanese Patent Application Laid-Open No. 2007-126612
PTL 5: Japanese Patent Application Laid-Open No. 2011-246606
Non-Patent Literature
[0011]NPL 1: Koji ARIMITSU, Fine Chemical Vo. 139
(No.2) P36 (2010)
Summary of Invention
Technical Problem
[0012] In a radical polymerization type photocurable liquid developer including a liquid acrylic monomer or oligomer, volume resistivity is easily reduced and the potential of an electrostatic latent image in a
developing step is easily dropped. Therefore, a high optical density may be difficult to achieve in the developing step, and image blurring may be caused. In addition, a radical polymerization type photocuring liquid developer including an acrylic monomer may be inhibited by oxygen from being cured, and is required to be used in combination with an acrylic monomer or oligomer having a relatively high molecular weight. As a result, the viscosity of the liquid developer may be increased to result in a reduction in the
electrophoretic velocity of a toner charged, namely, a reduction in the rate of production in image formation.
[0013] On the contrary, cationic polymerization is a polymerization system less affected by oxygen and suitable for a photocuring liquid developer. In particular, a vinyl ether monomer can be used as an electrically insulating liquid to thereby easily provide a liquid developer having a high volume
resistivity, increasing the reaction rate in a
photocuring reaction and also facilitating a reduction in the viscosity of the liquid developer. Therefore, the vinyl ether monomer is suitable as an electrically insulating liquid for use in a photocuring liquid developer by cationic polymerization.
[0014]As a photoinitiator for use in such cationic polymerization, an ionic photo-acid generator is generally used.
[0015] The ionic photo-acid generator, however, may cause the volume resistivity of the liquid developer to be significantly reduced, and thus the potential of an electrostatic latent image in a . developing step may be easily dropped, a high optical density may be difficult to achieve in the developing step, or image blurring may be caused.
[0016] The increase in viscosity of the ink described above, which is problematic in the radical
polymerization type photocuring liquid developer, is again problematic in an inkjet photocuring ink in terms of a reduction in ink ejection performance, and a cationic polymerization type photocuring ink that can address a reduction in viscosity of the ink is suitable [0017]As described above, however, PTL 3 describes the following: the cationic polymerization type ink has the problem of being not sufficient in stability during storage due to a reaction based on an acid generated over time, and has a large obstacle to practical use. Then, in PTL 3, the basic compound including a tertiary hindered amine structure in the molecule is added to the active radiation-curing inkjet ink composition for the purpose of suppressing the action of an acid generated during storage. Such a technique is an attempt where the basic compound including a
photodecomposable tertiary hindered amine structure is decomposed during exposure to allow storage stability of the ink during storage and sensitivity thereof during exposure to be simultaneously satisfied.
[ 0018 ] Meanwhile, the rates of an acid release reaction from a photopolymerization initiator during exposure and a subsequent polymerization reaction of vinyl ether are very high, and therefore it is very difficult to complete photodecomposition of a photodecomposable basic compound before initiation of the polymerization reaction in exposure.
[0019] Accordingly, storage stability of the cationic polymerization type ultraviolet curing ink and
sensitivity thereof with respect to photocurability are not sufficiently satisfied simultaneously. Such storage stability and sensitivity with respect to photocurability, not sufficiently satisfied
simultaneously, are also technically problematic again in the liquid developer described above.
[0020] The aromatic onium salt is used as a
photopolymerization initiator in both of PTL 4 and PTL 5, but the aromatic onium salt cannot be applied to the liquid developer or the electrostatic inkjet ink because of significantly reducing the volume
resistivity of the ultraviolet curable liquid even when added in a trace amount. In addition, no descriptions about storage stability and sensitivity satisfied simultaneously are made at all in both of PTL 4 and PTL 5.
[0021]An object of the present invention is to provide an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after ultraviolet curing, as well as a liquid developer and an inkjet ink using the ultraviolet curing liquid composition.
Solution to Problem
[0022] The ultraviolet curable liquid composition of the present invention is an ultraviolet curable liquid composition containing a cationically polymerizable liquid monomer, a photopolymerization initiator and a photopolymerization sensitizer, wherein the
cationically polymerizable liquid monomer is a vinyl ether compound, the photopolymerization initiator includes a compound represented by the following
general formula (1), and the photopolymerization
sensitizer includes (A) at least one compound selected from the group consisting of a compound represented by the following general formula (2) and a compound
represented by the following general formula (3) , and (B) at least one compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5) .
General formula
Figure imgf000008_0001
[0023] In the general formula (1), x represents an integer of 1 to 8, y represents an integer of 3 to 17, and R1 and R2 are bound to each other to form a cyclic structure .
General formula (2)
Figure imgf000009_0001
[0024] In the general formula (2), R3, R4, R5 and R6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or
unsubstituted alkoxy group, a substituted or
unsubstituted aryloxy group, a cyano group, a
substituted or unsubstituted aralkyl group, a
substituted or unsubstituted alkoxycarbonyl group, or a halogen atom.
General formula
Figure imgf000009_0002
[0025] In the general formula (3), R and R each
independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R9 and R10 each independently
represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, or a glycidyl group. General formula
Figure imgf000010_0002
[0026] In the general formula (4), R and R each independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, q and r each independently represent an integer of 0 to 4, R13 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, or a glycidyl group, s represents an integer of 1 to 3, each R11 is independently defined as above when a plurality of Ru(s) are present, each R12 is independently defined as above when a plurality of R12(s) are present, and each R13 is independently defined as above when a plurality of R13(s) are present.
General formula (5)
Figure imgf000010_0001
[0027] In the general formula (5), R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, u represents an integer of 0 to 4, R15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, or a glycidyl group, t represents an integer of 1 or 2, each R14 is independently defined as above when a plurality of R14(s) are present, and each R15 is
independently defined as above when a plurality of R15(s) are present.
[0028] In addition, the image forming method of the present invention is an image forming method to fix an image formed on a recording medium with the ultraviolet curable liquid composition and a colorant to the recording medium by an ultraviolet light irradiation. Advantageous Effects of Invention
[0029] According to the present invention, a vinyl ether compound can be combined with the combination of the specific compounds as the photopolymerization initiator and the photopolymerization sensitizer, thereby
providing an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after
ultraviolet curing.
[0030] Further features of the present invention will become apparent from the following description of exemplary embodiments.
Description of Embodiments
[0031] Hereinafter, the present invention is described in detail.
[0032] The ultraviolet curable liquid composition of the present invention includes the following components:
• At least one vinyl ether compound as a cationically polymerizable liquid monomer;
• At least one compound represented by the general formula (1) as a photopolymerization initiator;
• At least one compound selected from the group
consisting of a compound represented by the general formula (2) and a compound represented by the general formula (3), and at least one compound selected from the group consisting of a compound represented by the general formula (4) and a compound represented by the general formula (5), as a photopolymerization
sensitizer.
[0033] [Ultraviolet curable liquid composition] The ultraviolet curable liquid composition of the present invention contains a photopolymerization initiator, a photopolymerization sensitizer and a vinyl ether compound as a cationically polymerizable liquid monomer .
[ 0034 ] Hereinafter, the respective constitutive
components contained in the ultraviolet curable liquid composition of the present invention are sequentially described.
[0035] [Photopolymerization initiator]
The photopolymerization initiator in the present invention is represented by the following general formula ( 1 ) .
General formula (1)
Figure imgf000012_0001
[0036] In the general formula (1), x represents an integer of 1 to 8, y represents an integer of 3 to 17, and R1 and R2 are bound to each other to form a cyclic structure in which the cyclic backbone is partially formed from an imide structure. The
photopolymerization initiator represented by the general formula (1) can be contained to thereby provide an ultraviolet curable liquid composition that is high in resistivity unlike an ionic photo-acid generator while having sufficient fixability, and can be combined with a photopolymerization sensitizer described later to thereby realize an excellent storage stability.
[0037]The photopolymerization initiator in the present invention is photo-decomposed by irradiation with ultraviolet ray to generate sulfonic acid that is a strong acid. In addition, the photopolymerization initiator is used in combination with a
photopolymerization sensitizer described later, and absorption of ultraviolet ray by the sensitizer serves as a trigger to allow decomposition of the initiator and generation of sulfonic acid to be performed. CxFy having a large electron withdrawing property is an essential functional group for decomposing a sulfonic acid ester moiety by irradiation with ultraviolet ray, and the number of carbon atoms is 1 to 8 (x = 1 to 8) and the number of fluorine atoms is 3 to 17 (y = 3 to 17).
[0038] When the number of carbon atoms is 1 or more, a strong acid is easily synthesized, and when the number of, carbon atoms is 8 or less, storage stability is excellent. When the number of fluorine atoms is 3 or more, the action as a strong acid is enabled, and when the number of fluorine atoms is 17 or less, a strong acid is easily synthesized.
CxFy in the general formula (1) can be CF3, C2F5, C3F7, C4F9 or C6F5.
[0039] Examples of CxFy in the general formula (1) include the following respective groups.
• A linear alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (RF1 group)
• A branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (RF2 group)
• A cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom (RF3 group)
• An aryl group in which at least one hydrogen atom is substituted with a fluorine atom (RF4 group)
[0040]As the RF1 group, one in which all hydrogen atoms are not substituted with fluorine can be utilized, but one in which all hydrogen atoms are substituted with fluorine can be adopted. Examples include a
trifluoromethyl group (x = 1, y = 3) , a
pentafluoroethyl group (x = 2, y = 5), a nonafluorobutyl group (x = 4, y = 9) , a perfluorohexyl group (x = 6, y = 13) and a perfluorooctyl group (x = 8, Y = 17) .
[0041]As the RF2 group, one in. which all hydrogen atoms are not substituted with fluorine can be utilized, but one in which all hydrogen atoms are substituted with fluorine can be adopted. Examples include a
perfluoroisopropyl group (x = 3, y = 7), a perfluoro- tert-butyl group (x = 4, y = 9) and a perfluoro-2- ethylhexyl group (x = 8, y = 17).
[0042]As the RF3 group, one in which all hydrogen atoms are not substituted with fluorine can be utilized, but one in which all hydrogen atoms are substituted with fluorine can be adopted. Examples include a
perfluorocyclobutyl group (x = 4, y = 7), a
perfluorocyclopentyl group (x = 5, y = 9), a
perfluorocyclohexyl group (x = 6, y = 11) and a
perfluoro (l-cyclohexyl)methyl group (x = 7, y = 13).
[0043]As the RF4 group, one in which all hydrogen atoms are not substituted with fluorine can be utilized, but one in which all hydrogen atoms are substituted with fluorine can be adopted. Examples include a
pentafluorophenyl group (x = 6, y = 5) and a 3- trifluoromethyltetrafluorophenyl group (x = 7, y = 7).
[0044]As CxFy in the general formula (1), the RF1 group, the RF2 group and the RF4 group are preferable, and the RF1 group and the RF4 group are further preferable in terms of availability and a decomposition property of the sulfonic acid ester moiety. A trifluoromethyl group (x = 1, y = 3) , a pentafluoroethyl group (x = 2, y = 5) , a heptafluoropropyl group (x = 3, y = 7), a nonafluorobutyl group (x = 4, y = 9) and a
pentafluorophenyl group (x = 6, y = 5) are particularly preferable .
[0045] The cyclic structure included in the
photopolymerization initiator that can be used in the present invention, in which the cyclic backbone is partially formed from an imide structure, can be selected from the group consisting of structures utilized for absorption of ultraviolet ray among a nitrogen-containing monocyclic structure, a nitrogen- containing bicyclic structure, a nitrogen-containing tricyclic structure and a nitrogen-containing
tetracyclic structure each having a cyclic imide structure. The cyclic structure selected, in which the cyclic backbone is partially formed from an imide structure, can be utilized in combination with various moieties for sulfonic acid release. As such a cyclic structure, a cyclic structure included in a compound described later can be adopted, and can be used in combination with a sulfonic acid release moiety
represented as CxFy in the general formula (1) .
[ 0046] Examples of the cyclic structure having an imide structure forming a light absorption moiety in the compound represented by the general formula (1) include the following respective groups.
[0047]
Figure imgf000016_0001
[0048] R' in the formula (1-4) can be selected from the group consisting of a hydrogen atom, an alkylthio group having 1 to 6 carbon atoms, such as C4H9-S-, or an arylthio group having any structure represented below.
[004
Figure imgf000016_0002
[ 0050 ] Specific examples [exemplary compounds A-l to A- 27] of the photopolymerization initiator that can be used in the present invention include the following, but the photopolymerization initiator is not limited to such specific examples in the present invention.
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
[0054]
Figure imgf000020_0001
(A--27J
[0055] The photopolymerization initiator can be used singly or in combinations of two or more. The content of the photopolymerization initiator in the ultraviolet curable liquid composition of the present invention is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass, further preferably 0.1 to 0.5 parts by mass based on 100 parts by mass of the cationically polymerizable liquid monomer. If two or more compounds represented by the general formula (1) are combined, the content of the photopolymerization initiator is the total content of such compounds.
[0056] [Photopolymerization sensitizer]
Next, the photopolymerization sensitizer for use in the present invention is described.
In general, a photopolymerization sensitizer is often used in combination with a photopolymerization
initiator for the purposes of an enhancement in acid generation efficiency of a photo-acid generator and an increase in photosensitive wavelength. In the present invention, the photopolymerization initiator
represented by the general formula (1) can be used in combination with the vinyl ether compound as the
cationically polymerizable liquid monomer, and at least one compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) , and at least one compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) , as the photopolymerization sensitizer, thereby also imparting an excellent storage stability.
The compound represented by the general formula (2) is described.
General formula (2)
Figure imgf000021_0001
[0057] In the general formula (2), R3, R4, R5 and R6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or
unsubstituted alkoxy group, a substituted or
unsubstituted aryloxy group, a cyano group, a
substituted or unsubstituted aralkyl group, a
substituted or unsubstituted alkoxycarbonyl group, or a halogen atom.
[0058] In the general formula (2), examples of the unsubstituted alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i- propyl group, an n-butyl group, an i-butyl group and a t-butyl group. Examples of the unsubstituted
cycloalkyl group include a cyclohexyl group. Examples of the unsubstituted alkoxy group include linear or branched alkylalkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i- butoxy group and a t-butoxy group. Examples of the unsubstituted aryloxy group include a phenoxy group. Examples of the unsubstituted alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group .
[0059] Examples of the aralkyl group include a benzyl group .
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
[0060] The substituent included in each of the
substituted alkyl group, the substituted cycloalkyl group, the substituted alkoxy group, the substituted aryloxy group, the substituted aralkyl group and the substituted alkoxycarbonyl group may be any substituent that can allow the compound represented by the general formula (2) to function as the intended
photopolymerization sensitizer. Examples of the substituent can include substituents such as an
alkyloxy group having 1 to 4 carbon atoms, a phenyl group and a morpholino group. In addition, as the substituted alkoxycarbonyl group, a group in which a carboxyl group is esterified by polyethylene glycol can also be utilized.
[ 0061 ] Examples of the compound represented by the general formula (2) include the following compounds, for example, thioxanthone, 2-isopropylthioxanthone, 2- dodecylthioxanthone, 2-cyclohexylthioxanthone, 2,4- diethylthioxanthone, 2 , 4-dimethylthioxanthone, 1- phenoxythioxanthone, 1-methoxycarbonylthioxanthone, 2- ethoxycarbonylthioxanthone, 3- (2- methoxyethoxycarbonyl ) -thioxanthone, 4- butoxycarbonylthioxanthone, 3-butoxycarbonyl-7- methylthioxanthone, 3, 4-di- [2- (2-methoxyethoxy) - ethoxycarbonyl ] -thioxanthone, 2-chlorothioxanthone, 1- ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl- 3-chlorothioxanthone, 1-chloro-4 -n-propoxythioxanthone, 2-methy1-6-dimethoxymethyl-thioxanthone, 2-methy1-6- (1, 1-dimethoxybenzyl) -thioxanthone, 6-ethoxycarbonyl-2- methoxy-thioxanthone, 6-ethoxycarbonyl-2- methylthioxanthone, l-ethoxycarbonyl-3- (1-methyl-l- morpholinoethyl ) -thioxanthone, 2- morpho1inomethy1thioxanthone, 2-methyl-6- morpholinomethy1thioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, l-cyano-3- chlorothioxanthone and l-ethoxycarbonyl-3- phenylsulfurylthioxanthone .
[0062] In particular, 2-isopropylthioxanthone, 2- cyclohexylthioxanthone, 2 , 4-diethylthioxanthone, 2- chlorothioxanthone or l-chloro-4-n-propoxythioxanthone can be adopted because of being easily synthesized, having a high sensitization effect of the ultraviolet curable liquid composition, and exerting an excellent sensitization effect when used in combination with the compound represented by the general formula (4) or the compound represented by the general formula (5) .
The compound represented by the general formula (3) is described .
Figure imgf000023_0001
[0063] In the general formula (3), R and R each
independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R9 and R10 each independently
represent a hydrogen atom, an aralkyl group, an alkyl group having 1 to 9 carbon atoms optionally substituted with an oxygen atom, or a glycidyl group.
[0064] In the general formula (3), examples of the alkyl group in each of R7 and R8 include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t-butyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group.
[0065] Examples of the aralkyl group include a benzyl group.
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
[0066] In the general formula (3), examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with a substituent having an oxygen atom, in R9 and R10 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom. Examples of the substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group.
[0067] Examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom, include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2- hydroxyethyl group, a 3-hydroxyethyl group, a 2- hydroxypropyl group, a 2-methoxyethyl group, a 2- ethoxyethyl group and a 2-phenoxyethyl group. Examples of the glycidyl group include a glycidyl group and a 2- methylglycidyl group.
[ 0068 ] Examples of an anthracene-9, 10-dioxy compound represented by the general formula (3) include the following compounds:
(1) 9, 10-dimethoxyanthracene,
(2) 9, 10-diethoxyanthracene,
(3) 9, 10-bis (n-propoxy) anthracene,
(4) 9, 10-bis (i-propoxy) anthracene,
(5) 9, 10-bis (n-butoxy) anthracene,
(6) 9, 10-bis ( i-butoxy) anthracene,
(7) 9, 10-bis (n-pentyloxy) anthracene,
(8) 9, 10-bis (i-pentyloxy) anthracene,
(9) 9, 10-bis (n-hexyloxy) anthracene,
(10) 9, 10-bis (n-heptyloxy) anthracene,
(11) 9, 10-bis (n-octyloxy) anthracene,
(12) 9, 10-bis (2-ethylhexyloxy) anthracene,
(13) 9, 10-bis (n-nonyloxy) anthracene,
(14) 9, 10-bis (2-methylglycidyloxy) anthracene,
(15) 9, 10-dibenzyloxyanthracene,
(16) 9 , 10-diphenethyloxyanthracene and
(17) 9, 10-diglycidyloxyanthracene .
[0069] In addition, examples of the anthracene-9, 10- dioxy compound of the general formula (3), having an alkyl group as a substituent on the anthracene ring, include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
compounds (1) to (17) described above is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group or a t-butyl group.
[0070] In addition, examples of the anthracene-9, 10- dioxy compound of the general formula (3), having a halogen atom as a substituent on the anthracene ring, include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
compounds (1) to (17) described above is substituted with a chlorine atom.
[0071] In addition, examples of the anthracene-9 , 10- dioxy compound of the general formula (3), having an alkoxy group as a substituent on the anthracene ring, include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
compounds (1) to (17) described above is substituted with a methoxy group.
[0072] In addition, examples of the anthracene-9, 10- dioxy compound of the general formula (3) having an aryloxy group as a substituent on the anthracene ring include a compound in which the hydrogen atom at the 2- position of the anthracene ring in each of the
compounds (1) to (17) described above is substituted with a phenoxy group.
[0073]Among such anthracene compounds, in particular, 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-bis (n-propoxy) anthracene, 9, 10-bis (i- propoxy) anthracene , 9, 10-bis (n-butoxy) anthracene or 9 , 10-bis ( i-butoxy) anthracene can be adopted because of being easily synthesized, having a high sensitization effect of the ultraviolet curable liquid composition, and exerting an excellent sensitization effect when used in combination with the compound represented by the general formula (4) or the compound represented by the general formula (5) .
[0074] In the present invention, the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) can be used singly or in combinations of two or more.
[0075] The total content of the compound selected from the group consisting of the compound represented by the compound represented by the general formula (2) and the compound represented by the general formula (3) in the entire ultraviolet curable liquid composition is defined as B% by mass, and the content of the compound represented by the general formula (1) in the entire ultraviolet curable liquid composition is defined as A% by mass. The B/A here is preferably 1.0 or more, further preferably 5.0 or more. When the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) is used in combination of two or more, the total content of two or more is defined as B% by mass. When the B/A is 1.0 or more, the amount of energy transfer from the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) to the
photopolymerization initiator can be increased to result in a further enhancement in sensitivity.
[0076] The compound represented by the general formula (4) and the compound represented by the general formula (6) are described.
General formula
Figure imgf000027_0001
[0077] In the general formula (4), R and each independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, q and r each independently represent an integer of 0 to 4, R13 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group, or an aralkyl group, s represents an integer of 1 to 3, each R11 is independently defined as above when a plurality of Rn(s) are present, each R12 is
independently defined as above when a plurality of
R12(s) are present, and each R13 is independently
defined as above when a plurality of R13(s) are present.
General formula
Figure imgf000028_0001
[0078] The compound represented by the general formula (4) can be the compound represented by the general formula ( 6 ) .
In the general formula (6), R16 and R17 each
independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, u and v each independently represent an integer of 0 to 4, R18 and R19 each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group, or an aralkyl group, each R16 is independently defined as above when a
plurality of R16(s) are present, and each R17 is
independently defined as above when a plurality of
R17(s) are present. In each of the general formulae (4) and (6), examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with a substituent having an oxygen atom, represented by each of R13, R18 and R19 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom. [0079] Examples of the substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group.
Examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom, include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2- hydroxyethyl group, a 3-hydroxyethyl group, a 2- hydroxypropyl group, a 2-methoxyethyl group, a 2- ethoxyethyl group and a 2-phenoxyethyl group. Examples of the glycidyl group include a glycidyl group and a 2- methylglycidyl group.
[0080] In each of the general formulae (4) and (6), examples of the halogen atom in each of R11, R12, R16 and R17 include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t- butyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group .
[0081] Examples of the aralkyl group include a benzyl group.
Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
[ 0082 ] Examples of the naphthalene compound represented by the general formula (4) and the naphthalene compound represented by the general formula (6) include the following compounds (2-1) to (2-25):
(2-1) 1, 4-dihydroxynaphthalene, (2 -2) 1, 4-dimethoxynaphthalene,
(2 -3) 1, 4-diethoxynaphthalene,
(2 -4) 1, 4-bis (n-propoxy) naphthalene,
(2 -5) 1, 4-bis (i-propoxy) naphthalene,
(2 -β) 1, 4-bis (n-butoxy) naphthalene,
(2 -7) 1, 4-bis (i-butoxy) naphthalene,
(2 -8) 1, 4-bis (n-octyloxy) naphthalene,
(2 -9) 1, 4-bis (2-ethylhexyloxy) naphthalene,
(2 -10) 1, 4-dibenzyloxynaphthalene,
(2 -11) 1, 4-diphenethyloxynaphthalene,
(2 -12) 1, 4-diglycidyloxynaphthalene,
(2 -13) 1, 4-bis (2-methylglycidyloxy) naphthalene,
(2 -14) 4-methoxy-l-naphthol,
(2 -15) 4-ethoxy-l-naphthol,
(2 -16) 4- (n-propoxy) -1-naphthol,
(2 -17) 4- (i-propoxy) -1-naphthol,
(2 -18) 4- (n-butoxy) -1-naphthol,
(2 -19) 4- (i-butoxy) -1-naphthol,
(2 -20) 4- (n-octyloxy) -1-naphthol,
(2 -21) 4- (2-ethylhexyloxy) -1-naphthol,
(2 -22) 4 -benzyloxy-1-naphthol,
(2 -23) 4 -phenethyloxy-1-naphthol ,
(2- -24) 4-glycidyloxy-l-naphthol and
(2- -25) 4- (2-methylglycidyloxy) -1-naphthol .
[0083] Besides the above, examples of the naphthalene compound represented by the general formula (4) and the naphthalene compound represented by the general formula (6) further include the following compounds:
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 2-positions ;
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 5-positions ;
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 6-positions ;
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 1 , 8-positions ;
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 2 , 3-positions ;
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 2 , 6-positions ; and
• a compound in which positions, at which two
substituents on the naphthalene ring in each of the compounds (2-1) to (2-25) are bound, are 2 , 7-positions . In addition, examples of the compound of each of the general formulae (4) and (6), having an alkyl group as a substituent on the naphthalene ring, include the following compounds:
2-methyl-l, 4-dimethoxynaphthalene, 2-methyl-l ,4- diethoxynaphthalene , 2-methyl-l, 4-bis (i- propoxy) naphthalene, 2-methyl-l, 4-bis (n- butoxy) naphthalene, 2-methyl-l, 4-bis (n- octyloxy) naphthalene, 2-methyl-l, 4-bis (2- ethylhexyloxy) naphthalene, 2-methyl-l, 4- dibenzyloxynaphthalene, 2-methyl-l, 4- diphenethyloxynaphthalene, 2-methyl-l, 4- diglycidyloxynaphthalene, 2-methyl-4-methoxy-l-naphthol, 2-methyl-4-ethoxy-l-naphthol, 2-methyl-4- (i-propoxy) -1- naphthol, 2-methyl-4- (n-butoxy) -1-naphthol, 2-methyl-4- (n-octyloxy) -1-naphthol, 2-methyl-4- (2-ethylhexyloxy) - 1-naphthol, 2-methyl-4-benzyloxy-l-naphthol , 2-methyl- 4 -phenethyloxy-1-naphthol, 2-methyl-4-glycidyloxy-l- naphthol and 2-methyl-l , 4-dihydroxynaphthalene .
[0084 ] Besides the above, examples of the compound of the general formula (4), having an alkyl group as a substituent on the naphthalene ring, include the following compounds:
3-methyl-l, 2-dimethoxynaphthalene , 3-methyl-l, 2- diethoxynaphthalene, 3-methyl-l, 2-bis (i- propoxy) naphthalene, 3-methyl-l , 2-bis (n- butoxy) naphthalene, 3-methyl-l, 2-bis (n- octyloxy) naphthalene, 3-methyl-l, 2-bis (2- ethylhexyloxy) naphthalene, 3-methyl-l, 2- dibenzyloxynaphthalene, 3-methyl-l, 2- diphenethyloxynaphthalene, 3-methyl-l, 2- diglycidyloxynaphthalene, 3-methyl-l , 2- dihydroxynaphthalene, 2-methyl-l, 6-dimethoxynaphthalene, 2-methyl-l, 6-diethoxynaphthalene, 2-methyl-l, 6-bis (i- propoxy) naphthalene, 2-methyl-l, 6-bis (n- butoxy) naphthalene, 2-methyl-l , 6-bis (n- octyloxy) naphthalene, 2-methyl-l, 6-bis (2- ethylhexyloxy) naphthalene, 2-methyl-l, 6- dibenzyloxynaphthalene, 2-methyl-l, 6- diphenethyloxynaphthalene, 2-methyl-l, 6- diglycidyloxynaphthalene and 2-methyl-l, 6- dihydroxynaphthalene .
[0085] Examples of the compound of the general formula (4) having an alkyl group as a substituent on the naphthalene ring further include the following
compounds :
2-methyl-l, 5-dimethoxynaphthalene, 2-methyl-l, 5- diethoxynaphthalene, 2-methyl-l, 5-bis (i- propoxy) naphthalene, 2-methyl-l, 5-bis (n- butoxy) naphthalene, 2-methyl-l, 5-bis (n- octyloxy) naphthalene, 2-methyl-l, 5-bis (2- ethylhexyloxy) naphthalene, 2-methyl-l , 5- dibenzyloxynaphthalene, 2-methyl-l, 5- diphenethyloxynaphthalene, 2-methyl-l, 5- diglycidyloxynaphthalene , 2-methyl-l, 5- dihydroxynaphthalene, 3-methyl-2, 7-dimethoxynaphthalene,
3-methyl-2, 7 -diethoxynaphthalene, 3-methyl-2, 7-bis (i- propoxy) naphthalene, 3-methyl-2 , 7-bis (n- butoxy) naphthalene, 3-methyl-2, 7-bis (n- octyloxy) naphthalene, 3-methyl-2 , 7-bis (2- ethylhexyloxy) naphthalene , 3-methyl-2 , 7- dibenzyloxynaphthalene, 3-methyl-2, 7- diphenethyloxynaphthalene, 3-methyl-2 , 7- diglycidyloxynaphthalene, 3-methyl-2, 7- dihydroxynaphthalene, 2-methyl-l, 8-dimethoxynaphthalene ,
2-methyl-l, 8-diethoxynaphthalene, 2-methyl-l, 8-bis (i- propoxy) naphthalene, 2-methyl-l, 8-bis (n- butoxy) naphthalene, 2-methyl-l, 8-bis (n- octyloxy) naphthalene, 2-methyl-l, 8-bis (2- ethylhexyloxy) naphthalene, 2-methyl-l , 8- dibenzyloxynaphthalene, 2-methyl-l, 8- diphenethyloxynaphthalene, 2-methyl-l, 8- diglycidyloxynaphthalene and 2-methyl-l , 8- dihydroxynaphthalene .
[ 0086] Examples of the compound of the general formula (4) having an alkyl group as a substituent on the naphthalene ring further include the following
compounds :
3-methyl-2, 6-dimethoxynaphthalene, 3-methyl-2, 6- diethoxynaphthalene, 3-methyl-2, 6-bis (i- propoxy) naphthalene, 3-methyl-2 , 6-bis (n- butoxy) naphthalene, 3-methyl-2, 6-bis (n- octyloxy) naphthalene, 3-methyl-2, 6-bis (2- ethylhexyloxy) naphthalene, 3-methyl-2, 6- dibenzyloxynaphthalene, 3-methyl-2, 6- diphenethyloxynaphthalene, 3-methyl-2 , 6- diglycidyloxynaphthalene, 3-methyl-2 , 6- dihydroxynaphthalene, 5-methyl-2, 3-dimethoxynaphthalene, 5-methyl-2, 3-diethoxynaphthalene, 5-methyl-2, 3-bis (i- propoxy) naphthalene, 5-methyl-2 , 3-bis (n- butoxy) naphthalene, 5-methyl-2, 3-bis (n- octyloxy) naphthalene, 5-methyl-2, 3-bis (2- ethylhexyloxy) naphthalene, 5-methyl-2, 3- dibenzyloxynaphthalene, 5-methyl-2, 3- diphenethyloxynaphthalene, 5-methyl-2, 3- diglycidyloxynaphthalene and 5-methyl-2 , 3- dihydroxynaphthalene .
[0087] In addition, examples of the compound of each of the general formulae (4) and (6), having a halogen atom as a substituent on the naphthalene ring, include the following . compounds :
2-chloro-l, 4-dimethoxynaphthalene, 2-chloro-l, 4- diethoxynaphthalene, 2-chloro-l, 4-bis (i- propoxy) naphthalene, 2-chloro-l, 4-bis (n- butoxy) naphthalene, 2-chloro-l , 4-bis (n- octyloxy) naphthalene, 2-chloro-l, 4-bis (2- ethylhexyloxy) naphthalene, 2-chloro-l, 4- dibenzyloxynaphthalene, 2-chloro-l, 4- diphenethyloxynaphthalene, 2-chloro-l , 4- diglycidyloxynaphthalene, 2-chloro-4-methoxy-l-naphthol ,
2-chloro-4-ethoxy-l-naphthol, 2-chloro-4- (i-propoxy), -1- naphthol, 2-chloro-4- (n-butoxy) -1-naphthol , 2-chloro-4- (n-octyloxy) -l-naphthol, 2-chloro-4- (2-ethylhexyloxy) - 1-naphthol, 2-chloro-4-benzyloxy-l-naphthol , 2-chloro-
4 -phenethyloxy-1-naphthol, 2-chloro-4-glycidyloxy-l- naphthol and 2-chloro-l, 4-dihydroxynaphthalene .
[ 0088 ] Besides the above, examples of the compound of the general formula (4), having a halogen atom as a substituent on the naphthalene ring, include the
following compounds:
3-chloro-l, 2-dimethoxynaphthalene> 3-chloro-l, 2- diethoxynaphthalene, 3-chloro-l, 2-bis (i- propoxy) naphthalene, 3-chloro-l, 2-bis (n- butoxy) naphthalene, 3-chloro-l, 2-bis (n- octyloxy) naphthalene, 3-chloro-l, 2-bis (2- ethylhexyloxy) naphthalene, 3-chloro-l, 2- dibenzyloxynaphthalene, 3-chloro-l , 2- diphenethyldxynaphthalene, 3-chloro-l, 2- diglycidyloxynaphthalene, 3-chloro-l, 2- dihydroxynaphthalene, 2-chloro-l, 6-dimethoxynaphthalene, 2-chloro-l, 6-diethoxynaphthalene, 2-chloro-l, 6-bis (i- propoxy) naphthalene, 2-chloro-l , 6-bis (n- butoxy) naphthalene, 2-chloro-l, 6-bis (n- octyloxy) naphthalene, 2-chloro-l, 6-bis (2- ethylhexyloxy) naphthalene, 2-chloro-l, 6- dibenzyloxynaphthalene, 2-chloro-l, 6- diphenethyloxynaphthalene, 2-chloro-l, 6- diglycidyloxynaphthalene, 2-chloro-l , 6- dihydroxynaphthalene, 2-chloro-l, 5-dimethoxynaphthalene,
2-chloro-l, 5-diethoxynaphthalene , 2-chloro-l, 5-bis (i- propoxy) naphthalene, 2-chloro-l, 5-bis (n- butoxy) naphthalene, 2-chloro-l, 5-bis (n- octyloxy) naphthalene, 2-chloro-l, 5-bis (2- ethylhexyloxy) naphthalene, 2-chloro-l, 5- dibenzyloxynaphthalene, 2-chloro-l, 5- diphenethyloxynaphthalene, 2-chloro-l , 5- diglycidyloxynaphthalene and 2-chloro-l, 5- dihydroxynaphthalene .
[0089] Examples of the compound of the general formula (4) having a halogen atom as a substituent on the naphthalene ring further include the following
compounds :
3-chloro-2, 7-dimethoxynaphthalene, 3-chloro-2, 7- diethoxynaphthalene, 3-chloro-2, 7-bis (i- propoxy) naphthalene, 3-chloro-2, 7-bis (n- butoxy) naphthalene, 3-chloro-2, 7-bis (n- octyloxy) naphthalene, 3-chloro-2, 7-bis (2- ethylhexyloxy) naphthalene, 3-chloro-2, 7- dibenzyloxynaphthalene, 3-chloro-2 , 7- diphenethyloxynaphthalene, 3-chloro-2, 7- diglycidyloxynaphthalene, 3-chloro-2 , 7- .
dihydroxynaphthalene, 2-chloro-l, 8-dimethoxynaphthalene, 2-chloro-l, 8-diethoxynaphthalene, 2-chloro-l, 8-bis (i- propoxy) naphthalene, 2-chloro-l, 8-bis (n- butoxy) naphthalene, 2-chloro-l, 8-bis (n- octyloxy) naphthalene, 2-chloro-l, 8-bis (2- ethylhexyloxy) naphthalene, 2-chloro-l, 8- dibenzyloxynaphthalene, 2-chloro-l, 8- diphenethyloxynaphthalene, 2-chloro-l, 8- diglycidyloxynaphthalene, 2-chloro-l, 8- dihydroxynaphthalene, 3-chloro-2, 6-dimethoxynaphthalene, 3-chloro-2, 6-diethoxynaphthalene , 3-chloro-2, 6-bis (i- propoxy) naphthalene, 3-chloro-2, 6-bis (n- butoxy) naphthalene, 3-chloro-2 , 6-bis (n- octyloxy) naphthalene, 3-chloro-2, 6-bis (2- ethylhexyloxy) naphthalene, 3-chloro-2, 6- dibenzyloxynaphthalene, 3-chloro-2, 6- diphenethyloxynaphthalene and 3-chloro-2 , 6- diglycidyloxynaphthalene .
[0090] In addition, examples of the compound of each of the general formulae (4) and (6), having alkoxy as a substituent on the naphthalene ring, include the
following compounds:
1,2, 4-trimethoxynaphthalene, 2-methoxy-l, 4- diethoxynaphthalene, 2-methoxy-l, 4-bis (i- propoxy) naphthalene, 2-methoxy-l, 4-bis (n- butoxy) naphthalene, 2-methoxy-l, 4-bis (n- octyloxy) naphthalene, 2-methoxy-l, 4-bis (2- ethylhexyloxy) naphthalene, 2-methoxy-l, 4- dibenzyloxynaphthalene, 2-methoxy-l, 4- diphenethyloxynaphthalene, 2-methoxy-l, 4- diglycidyloxynaphthalene, 2-methoxy-4-methoxy-l- naphthol, 2-methoxy-4-ethoxy-l-naphthol , 2-methoxy-4- (i-propoxy) -l-naphthol, 2-methoxy-4- (n-butoxy) -1- naphthol, 2-methoxy-4- (n-octyloxy) -l-naphthol , 2- methoxy-4- ( 2-ethylhexyloxy) -l-naphthol, 2-methoxy-4- benzyloxy- l-naphthol, 2-methoxy-4-phenethyloxy-l- naphthol, 2-methoxy-4-glycidyloxy-l-naphthol and 2- methoxy-1, 4-dihydroxynaphthalene .
[ 0091 ] Besides the above, examples of the compound of the general formula (4), having alkoxy as a substituent on the naphthalene ring, include the following compounds :
1, 2, 3-trimethoxynaphthalene,
3-methoxy-l , 2 diethoxynaphthalene ,
3-methoxy-l, 2-bis (i-propoxy) naphthalene,
3-methoxy-l, 2-bis (n-butoxy) naphthalene,
3-methoxy-l, 2-bis (n-octyloxy) naphthalene,
3-methoxy-l, 2-bis (2-ethylhexyloxy) naphthalene,
3-methoxy-l, 4-dibenzyloxynaphthalene,
3-methoxy-l , 4-diphenethyloxynaphthalene,
3-methoxy-l, 2-diglycidyloxynaphthalene,
3-methoxy-l, 2-dihydroxynaphthalene,
1, 2, 6-trimethoxynaphthalene,
2-methoxy-l, 6-diethoxynaphthalene,
2-methoxy-l, 6-bis (i-propoxy) naphthalene,
2-methoxy-l, 6-bis (n-butoxy) naphthalene,
2-methoxy-l, 6-bis (n-octyloxy) naphthalene,
2-methoxy-l, 6-bis (2-ethylhexyloxy) naphthalene,
2-methoxy-l, 6-dibenzyloxynaphthalene,
2-methoxy-l, 6-1, 4-diphenethyloxynaphthalene,
2-methoxy-l , 6-diglycidyloxynaphthalene ,
2-methoxy-l , 6-dihydroxynaphthalene,
1,2, 5-trimethoxynaphthalene,
2-methoxy-l , 5-diethoxynaphthalene,
2-methoxy-l, 5-bis (i-propoxy) naphthalene,
2-methoxy-l , 5-bis (n-butoxy) naphthalene,
2-methoxy-l , 5-bis (n-octyloxy) naphthalene ,
2-methoxy-l, 5-bis (2-ethylhexyloxy) naphthalene,
2-methoxy-l , 5-dibenzyloxynaphthalene,
2-methoxy-l , 5-diphenethyloxynaphthalene,
2-methoxy-l, 5-diglycidyloxynaphthalene and
2-methoxy-l , 5-dihydroxynaphthalene .
[ 0092 ] Examples of the compound of the general formula (4) having alkoxy as a substituent on the naphthalene ring further include the following compounds:
3-methoxy-2 , 7 -diethoxynaphthalene,
3-methoxy-2, 7-bis (i-propoxy) naphthalene, 3-methoxy-2 , 7-bis (n-butoxy) naphthalene,
3-methoxy-2, 7-bis (n-octyloxy) naphthalene,
3-methoxy-2, 7-bis (2-ethylhexyloxy) naphthalene,
3-methoxy-2 , 7 -dibenzyloxynaphthalene,
3-methoxy-2 , 7-diphenethyloxynaphthalene,
3-methoxy-2 , 7-diglycidyloxynaphthalene,
3-methoxy-2, 7-dihydroxynaphthalene ,
1,2, 8-trimethoxynaphthalene,
2-methoxy-l , 8-diethoxynaphthalene,
2-methoxy-l, 8-bis (i-propoxy) naphthalene,
2-methoxy-l, 8-bis (n-butoxy) naphthalene,
2-methoxy-l, 8-bis (n-octyloxy) naphthalene,
2-methoxy-l, 8-bis (2-ethylhexyloxy) naphthalene,
2-methoxy-l , 8 -dibenzyloxynaphthalene,
2-methoxy-l , 8-diphenethyloxynaphthalene,
2-methoxy-l , 8-diglycidyloxynaphthalene ,
2-methoxy-l , 8-dihydroxynaphthalene ,
2, 3, 6-trimethoxynaphthalene,
3-methoxy-2 , 6-diethoxynaphthalene,
3-methoxy-2, 6-bis (i-propoxy) naphthalene,
3-methoxy-2, 6-bis (n-butoxy) naphthalene,
3-methoxy-2, 6-bis (n-octyloxy) naphthalene,
3-methoxy-2, 6-bis (2-ethylhexyloxy) naphthalene,
3-methoxy-2 , 6-dibenzyloxynaphthalene,
3-methoxy-2 , 6-diphenethyloxynaphthalene,
3-methoxy-2, 6-diglycidyloxynaphthalene and
3-methoxy-2 , 6-dihydroxynaphthalene .
[0093] In addition, examples of the compound of each of the general formulae (4) and (6), having aryloxy as a substituent on the naphthalene ring, include the following compounds:
2-phenoxy-l, 4-dimethoxynaphthalene, 2-phenoxy-l, 4- diethoxynaphthalene, 2-phenoxy-l, 4-bis (i- propoxy) naphthalene, 2-phenoxy-l, 4-bis (n- butoxy) naphthalene, 2-phenoxy-l , 4-bis (n- octyloxy) naphthalene, 2-phenoxy-l, 4-bis (2- ethylhexyloxy) naphthalene, 2-phenoxy-l, 4- dibenzyloxynaphthalene, 2-phenoxy-l, 4- diphenethyloxynaphthalene, 2-phenoxy-l, 4- diglycidyloxynaphthalene, 2-phenoxy-4-methoxy-l- naphthol, 2-phenoxy-4-ethoxy-l-naphthol, 2-phenoxy-4- (i-propoxy) -1-naphthol, 2-phenoxy-4- (n-butoxy) -1- naphthol, 2-phenoxy-4- (n-octyloxy) -1-naphthol , 2- phenoxy-4- (2-ethylhexyloxy) -1-naphthol, 2-phenoxy-4- benzyloxy-1-naphthol, 2-phenoxy-4-phenethyloxy-l- naphthol, 2-phenoxy-4-glycidyloxy-l-naphthol and 2- phenoxy-1, 4-dihydroxynaphthalene .
[ 0094 ] Besides the above, examples of the compound of the general formula (4), having aryloxy as a
substituent on the naphthalene ring, include the
following compounds:
3-phenoxy-l, 2-dimethoxynaphthalene, 3-phenoxy-l, 2- diethoxynaphthalene, 3-phenoxy-l, 2-bis (i- propoxy) naphthalene, 3-phenoxy-l, 2-bis (n- butoxy) naphthalene, 3-phenoxy-l , 2-bis (n- octyloxy) naphthalene, 3-phenoxy-l, 2-bis (2- ethylhexyloxy) naphthalene, 3-phenoxy-l, 2- dibenzyloxynaphthalene, 3-phenoxy-l, 2- diphenethyloxynaphthalene, 3-phenoxy-l, 2- diglycidyloxynaphthalene, 2-phenoxy-l , 6- dimethoxynaphthalene, 2-phenoxy-l, 6-diethoxynaphthalene, 2-phenoxy-l, 6-bis (i-propoxy) naphthalene, 2-phenoxy-l, 6- bis (n-butoxy) naphthalene , 2-phenoxy-l , 6-bis (n- octyloxy) naphthalene, 2-phenoxy-l, 6-bis (2- ethylhexyloxy) naphthalene, 2-phenoxy-l, 6- dibenzyloxynaphthalene, 2-phenoxy-l, 6- diphenethyloxynaphthalene, 2-phenoxy-l, 6- diglycidyloxynaphthalene , 2-phenoxy-l, 5- dimethoxynaphthalene, 2-phenoxy-l, 5-diethoxynaphthalene, 2-phenoxy-l, 5-bis (i-propoxy) naphthalene, 2-phenoxy-l, 5- bis (n-butoxy) naphthalene, 2-phenoxy-l, 5-bis (n- octyloxy) naphthalene, 2-phenoxy-l, 5-bis (2- ethylhexyloxy) naphthalene, 2-phenoxy-l, 5- dibenzyloxynaphthalene, 2-phenoxy-l, 5- diphenethyloxynaphthalene and 2-phenoxy-l , 5- diglycidyloxynaphthalene .
[0095] Examples of the compound of the general formula (4) having aryloxy as a substituent on the naphthalene ring further include the following compounds:
3-phenoxy-2, 7-dimethoxynaphthalene , 3-phenoxy-2, 7- diethoxynaphthalene, 3-phenoxy-2 , 7-bis ( i- propoxy) naphthalene, 3-phenoxy-2, 7-bis (n- butoxy) naphthalene, 3-phenoxy-2 , 7-bis (n- octyloxy) naphthalene, 3-phenoxy-2, 7-bis (2- ethylhexyloxy) naphthalene, 3-phenoxy-2, 7- dibenzyloxynaphthalene, 3-phenoxy-2, 7- diphenethyloxynaphthalene, 3-phenoxy-2 , 7- diglycidyloxynaphthalene, 2-phenoxy-l, 8- dimethoxynaphthalene, 2-phenoxy-l, 8-diethoxynaphthalene,
2-phenoxy-l, 8-bis (i-propoxy) naphthalene, 2-phenoxy-l, 8- bis (n-butoxy) naphthalene, 2-phenoxy-l, 8-bis (n- octyloxy) naphthalene, 2-phenoxy-l, 8-bis (2- ethylhexyloxy) naphthalene, 2-phenoxy-l , 8- dibenzyloxynaphthalene, 2-phenoxy-l, 8- diphenethyloxynaphthalene, 2-phenoxy-l, 8- diglycidyloxynaphthalene, 3-phenoxy-2, 6- dimethoxynaphthalene, 3-phenoxy-2, 6-diethoxynaphthalene,
3-phenoxy-2, 6-bis (i-propoxy) naphthalene, 3-phenoxy-2, 6- bis (n-butoxy) naphthalene, 3-phenoxy-2 , 6-bis (n- octyloxy) naphthalene, 3-phenoxy-2, 6-bis (2- ethylhexyloxy) naphthalene, 3-phenoxy-2, 6- dibenzyloxynaphthalene, 3-phenoxy-2, 6- diphenethyloxynaphthalene and 3-phenoxy-2 , 6- diglycidyloxynaphthalene .
The compound represented by the general formula (5) and the compound represented by the general formula (7) are described. General formula
Figure imgf000041_0001
[0096] In the general formula (5), R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, u represents an integer of 0 to 4, R15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with an oxygen atom, a glycidyl group or an aralkyl group, t represents an integer of 1 or 2, each R14 is independently defined as above when a plurality of R14(s) are present, and each R15 is independently defined as above when a plurality of R15(s) are present Alternatively,
General formula
Figure imgf000041_0002
[0097] The compound represented by the general formula (5) can be the compound represented by the general formula ( 7 ) .
In the general formula (7), R20 represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, w represents an integer of 0 to 4, R21 and R22 each independently represent a
hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with an oxygen atom, a glycidyl group or an aralkyl group, and each R20 is independently defined as above when a plurality of R20(s) are present.
[0098] In each of the general formulae (5) and (7), examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with a
substituent having an oxygen atom in each of R15, R21 and R22 include a linear or branched alkyl group in which at least one hydrogen atom may be substituted with a substituent having an oxygen atom. Examples of the substituent having an oxygen atom include a hydroxy group, alkyloxy groups having 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and aryloxy groups such as a phenoxy group. Examples of the alkyl group having 1 or more and 9 or less carbon atoms optionally substituted with the substituent having an oxygen atom include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, a 2-hydroxyethyl group, a 3- hydroxyethyl group, a 2-hydroxypropyl group, a 2- methoxyethyl group, a 2-ethoxyethyl group and a 2- phenoxyethyl group.
Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group.
[ 0099] Examples of the aralkyl group include a benzyl group.
In each of the general formulae (5) and (7), examples of the halogen atom in each of R14 and R20 include a fluorine atom, a chlorine atom and a bromine atom.
[0100] Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a t-butyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group, examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the aryloxy group include a phenoxy group. [0101] Examples of the benzene compound represented by the general formula (5) and the benzene compound represented by the general formula (7) include the following compounds:
1 , 4-dihydroxybenzene, 1 , 4-dimethoxybenzene, 1,4- diethoxybenzene, 1, 4-bis (i-propoxy) benzene, 1, 4-bis (n- butoxy) benzene, 1, 4-bis (n-octyloxy) benzene, 1, 4-bis (2- ethylhexyloxy) benzene, 1 , 4-dibenzyloxybenzene, 1,4- diphenethyloxybenzene, 1 , 4-diglycidyloxybenzene, 4- methoxy-l-phenol , 4-ethoxy-l-phenol, 4- ( i-propoxy) -1- phenol, 4- (n-butoxy) -1-phenol , 4- (n-octyloxy) -1-phenol , 4- (2-ethylhexyloxy) -1-phenol, 4-benzyloxy-l-phenol, 4- phenethyloxy-l-phenol and 4-glycidyloxy-l-phenol.
[ 0102 ] Besides the above, examples of the benzene compound represented by the general formula (5) include the following compounds:
1 , 3-dimethoxybenzene, 1, 3-diethoxybenzene, 1, 3-bis (i- propoxy) benzene, 1, 3-bis (n-butoxy) benzene, 1, 3-bis (n- octyloxy) benzene, 1 , 3-bis (2-ethylhexyloxy) benzene, 1,3- dibenzyloxybenzene, 1, 3-diphenethyloxybenzene, 1,3- diglycidyloxybenzene, resorcin, 1 , 2-dimethoxybenzene , 1, 2-diethoxybenzene, 1 , 2-bis ( i-propoxy) benzene , 1,2- bis (n-butoxy) benzene, 1, 2-bis (n-octyloxy) benzene, 1,2- bis (2-ethylhexyloxy) benzene, 1, 2-dibenzyloxybenzene, 1 , 2-diphenethyloxybenzene, 1 , 2-diglycidyloxybenzene and catechol .
[0103] In addition, examples of the compound of each of the general formulae (5) and (7) having an alkyl group as a substituent on the benzene ring include the following compounds:
2-methyl-l, 4-dimethoxybenzene, 2-methyl-l, 4- diethoxybenzene, 2-methyl-l, 4-bis (i-propoxy) benzene, 2- methyl-1, 4-bis (n-butoxy) benzene, 2-methyl-l, 4-bis (n- octyloxy) benzene, 2-methyl-l , 4-bis ( 2- ethylhexyloxy) benzene, 2-methyl-l, 4-dibenzyloxybenzene, 2-methyl-l, 4-diphenethyloxybenzene, 2-methyl-l, 4- diglycidyloxybenzene, 2-methyl-4-methoxy-l-phenol , 2- methyl-4-ethoxy-l-phenol, 2-methyl-4- (i-propoxy) -1- phenol, 2-methyl-4- (n-butoxy) -1-phenol, 4- (n-octyloxy) -
1-phenol, 2-methyl-4- (2-ethylhexyloxy) -1-phenol, 2- methyl-4-benzyloxy-1-phenol, 2-methyl-4-phenethyloxy-l- phenol, 2-methyl-4-diglycidyloxy-l-phenol and 2-methyl- 1, 4-dihydroxybenzene .
[0104 ] Besides the above, examples of the compound of the general formula (5) having an alkyl group as a substituent on the benzene ring include the following compounds :
2-methyl-l, 3-dimethoxybenzene , 2-methyl-l, 3- diethoxybenzene, 2-methyl-l, 3-bis (i-propoxy) benzene, 2- methyl-1 , 3-bis (n-butoxy) benzene, 2-methyl-l , 3-bis (n- octyloxy) benzene, 2-methyl-l, 3-bis (2- ethylhexyloxy) benzene, 2-methyl-l, 3-dibenzyloxybenzene ,
2-methyl-l, 3-diphenethyloxybenzene, 2-methyl-l, 3- diglycidyloxybenzene, 2-methylresorcin, 3-methyl-l , 2- dimethoxybenzene, 3-methyl-l, 2-diethoxybenzene, 3- methyl-1, 2-bis (i-propoxy) benzene, 3-methyl-l, 2-bis (n- butoxy) benzene, 3-methyl-l, 2-bis (n-octyloxy) benzene, 3- methyl-1, 2-bis (2-ethylhexyloxy) benzene, 3-methyl-l, 2- dibenzyloxybenzene, 3-methyl-l, 2-diphenethyloxybenzene ,
3-methyl-l , 2-diglycidyloxybenzene and 3-methylcatechol.
[0105] In addition, examples of the compound of each of the general formulae (5) and (7) having a halogen atom as a substituent on the benzene ring include the following compounds:
2-chloro-l, 4-dimethoxybenzene, 2-chloro-l, 4- diethoxybenzene, 2-chloro-l, 4-bis (i-propoxy) benzene, 2- chloro-1, 4-bis (n-butoxy) benzene, 2-chloro-l , 4-bis (n- octyloxy) benzene, 2-chloro-l, 4-bis (2- ethylhexyloxy) benzene, 2-chloro-l, 4-dibenzyloxybenzene, 2-chloro-l, 4-diphenethyloxybenzene, 2-chloro-4-methoxy- 1-phenol, 2-chloro-4-ethoxy-l-phenol , 2-chloro-4- ( i- propoxy) -1-phenol, 2-chloro-4- (n-butoxy) -1-phenol, 2- chloro-4- (n-octyloxy) -1-phenol, 2-chloro-4- (2- ethylhexyloxy) -1-phenol, 2-chloro-4-benzyloxy-l-phenol, 2-chloro-4-phenethyloxy-1-phenol, 2-chloro-4- diglycidyloxy-l-phenol and 2-chloro-l, 4- dihydroxybenzene .
[ 0106] Besides the above, examples of the compound of the general formula (5) having a halogen atom as a substituent on the benzene ring include the following compounds :
2-chloro-l, 3-dimethoxybenzene, 2-chloro-l, 3- diethoxybenzene, 2-chloro-l, 3-bis (i-propoxy) benzene, 2- chloro-1, 3-bis (n-butoxy) benzene, 2-chloro-l, 3-bis (n- octyloxy) benzene, 2-chloro-l, 3-bis (2-,
ethylhexyloxy) benzene, 2-chloro-l, 3-dibenzyloxybenzene ,
2-chloro-l, 3-diphenethyloxybenzene, 2-chloro-l, 3- diglycidyloxybenzene, 3-chloro-l, 2-dimethoxybenzene, 3- chloro-1 , 2-diethoxybenzene, 3-chloro-l,2-bis (i- propoxy) benzene, 3-chloro-l, 2-bis (n-butoxy) benzene, 3- chloro-1, 2-bis (n-octyloxy) benzene, 3-chloro-l, 2-bis (2- ethylhexyloxy) benzene, 3-chloro-l , 2-dibenzyloxybenzene,
3-chloro-l , 2-diphenethyloxybenzene and 3-chloro-l, 2- diglycidyloxybenzene .
[0107] In addition, examples of the compound of each of the general formulae (5) and (7) having alkoxy as a substituent on the benzene ring include the following compounds :
1,2, 4-trimethoxybenzene, 2-methoxy-l, 4-diethoxybenzene, 2-methoxy-l, 4-bis (i-propoxy) benzene, 2-methoxy-l, 4- bis (n-butoxy) benzene, 2-methoxy-l , 4-bis (n- octyloxy) benzene, 2-methoxy-l , 4-bis (2- ethylhexyloxy) benzene, 2-methoxy-l, 4-dibenzyloxybenzene, 2-methoxy-l, 4-diphenethyloxybenzene and 2-methoxy-l , 4- diglycidyloxybenzene .
[0108] Besides the above, examples of the compound of the general formula (5) having alkoxy as a substituent on the benzene ring include the following compounds: 1,2, 3-trimethoxybenzene, 3-methoxy-l, 2-diethoxybenzene, 3-methoxy-l, 2-bis (i-propoxy) benzene, 3-methoxy-l, 2- bis (n-butoxy) benzene, 3-methoxy-l, 2-bis (n- octyloxy) benzene, 3-methoxy-l, 2-bis (2- ethylhexyloxy) benzene, 3-methoxy-l, 2-dibenzyloxybenzene, 3-methoxy-l, 2-diphenethyloxybenzene, 3-methoxy-l, 2- diglycidyloxybenzene, 2-methoxy-l , 3-diethoxybenzene, 2- methoxy-1, 3-bis ( i-propoxy) benzene, 2-methoxy-l, 3-bis (n- butoxy) benzene, 2-methoxy-l, 3-bis (n-octyloxy) benzene, 2-methoxy-l , 3-bis (2-ethylhexyloxy) benzene, 2-methoxy- 1, 3-dibenzyloxybenzene, 2-methoxy-l, 3- diphenethyloxybenzene and 2-methoxy-l , 3- diglycidyloxybenzene .
[0109] In addition, examples of the compound of each of the general formulae (5) and (7) having aryloxy as a substituent on the benzene ring include the following compounds :
2-phenoxy-l, 4-dimethoxybenzene, 2-phenoxy-l, 4- diethoxybenzene, 2-phenoxy-l , 4-bis ( i-propoxy) benzene, 2-phenoxy-l , 4-bis (n-butoxy) benzene, 2-phenoxy-l , 4- bis (n-octyloxy) benzene, 2-phenoxy-l, 4-bis (2- ethylhexyloxy) benzene, 2-phenoxy-l, 4-dibenzyloxybenzene,
2-phenoxy-l, 4-diphenethyloxybenzene and 2-phenoxy-l, 4- ' diglycidyloxybenzene .
[0110] Besides the above, examples of the compound of the general formula (5) having aryloxy as a substituent on the benzene ring include the following compounds:
3-phenoxy-l, 2-dimethoxybenzene , 3-phenoxy-l, 2- diethoxybenzene, 3-phenoxy-l, 2-bis (i-propoxy) benzene, 3-phenoxy-l, 2-bis (n-butoxy) benzene, 3-phenoxy-l, 2- bis (n-octyloxy) benzene, 3-phenoxy-l, 2-bis (2- ethylhexyloxy) benzene, 3-phenoxy-l, 2-dibenzyloxybenzene, 3-phenoxy-l, 2-diphenethyloxybenzene, 3-phenoxy-l, 2- diglycidyloxybenzene, 2-phenoxy-l, 3-dimethoxybenzene, 2-phenoxy-l, 3-diethoxybenzene, 2-phenoxy-l, 3-bis (i- propoxy) benzene, 2-phenoxy-l, 3-bis (n-butoxy) benzene, 2- phenoxy-1, 3-bis (n-octyloxy) benzene, 2-phenoxy-l, 3- bis (2-ethylhexyloxy) benzene, 2-phenoxy-l, 3- dibenzyloxybenzene, 2-phenoxy-l, 3-diphenethyloxybenzene and 2-phenoxy-l , 3-diglycidyloxybenzene .
[0111 ] Among such naphthalene compounds or benzene compounds represented by the general formulae (2) to
(5), 1 , 4-dimethoxynaphthalene, 1 , 4-diethoxynaphthalene, 1, 4-bis (n-propoxy) naphthalene, 1, 4-bis (i- propoxy) naphthalene, 1, 4-bis (n-butoxy) naphthalene, 1,4- bis ( i-butoxy) naphthalene, 1 , 4-dimethoxybenzene, 1,4- diethoxybenzene, 1 , 4-bis (n-propoxy) benzene, 1, 4-bis (i- propoxy) benzene, 1, 4-bis (n-butoxy) benzene or 1, 4-bis (i- butoxy) benzene can be adopted because of being easily synthesized, having a high sensitization effect of the ultraviolet curable liquid composition, and also enhancing storage stability when used in combination with the compound represented by the general formula
(1). In particular, 1, 4-dimethoxynaphthalene, 1,4- diethoxynaphthalene, 1, 4-bis (n-propoxy) naphthalene, 1, 4-bis (i-propoxy) naphthalene, 1, 4-bis (n- butoxy) naphthalene or 1, 4-bis (i-butoxy) naphthalene can be adopted because of having a higher sensitization effect of the ultraviolet curable liquid composition and exhibiting an excellent storage stability when used in combination with the compound represented by the general formula (1) .
[0112] In the present invention, the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) can be used singly or in combinations of two or more.
[0113] The total content of the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) in the entire ultraviolet curable liquid composition is defined as C% by mass, and the content of the compound represented by the general formula (1) in the entire ultraviolet curable liquid composition is defined as A% by mass. The C/A here is preferably 1.0 or more, further preferably 5.0 or more. When the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) is used in combination of two or more, the total content of two or more is defined as C% by mass. When the C/A is 1.0 or more, the amount of an electrons that
transfer from the compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) via the compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) to. the photopolymerization initiator can be increased to further enhance sensitivity and to further enhance storage stability.
[0114] [Vinyl ether compound]
In the ultraviolet curable liquid composition of the present invention, as one feature, a vinyl ether compound is used as a polymerizable liquid monomer.
The vinyl ether compound can be used to thereby provide an ultraviolet curable liquid composition having high resistivity, low viscosity and high sensitivity.
[0115]As the polymerizable liquid monomer, an acrylic monomer, a cyclic ether monomer such as epoxy and oxetane monomers, and the like are widely used.
[0116]The acrylic monomer, however, has the bias in electron density in the molecule, and such bias causes the electrostatic interaction between molecules to make the ultraviolet curable liquid composition difficult to have low viscosity. Accordingly, the acrylic monomer is difficult to use in an application as a component of a liquid developer or an inkjet ink having low viscosity, which is an object of the present invention.
[0117] In addition, the bias in electron density in the molecule is supposed to lead to difficulty of
achievement of a high resistivity in . a liquid
composition including the acrylic monomer. Moreover, the cyclic ether monomer has again difficulty in providing a liquid composition having high resistivity, and furthermore the cyclic ether monomer is
considerably low in reaction rate as compared with the vinyl ether compound. Accordingly, the cyclic ether monomer is also difficult to use in an application as a component of a liquid developer or an inkjet ink, which is an object of the present invention. The present inventors suppose the following: when the vinyl ether compound is used as the polymerizable liquid monomer, a small bias in electron density in the molecule can allow an ultraviolet curable liquid composition having low viscosity, high resistivity and high sensitivity to be provided.
[0118] In the present invention, furthermore, one aspect can be provided in which the cationically polymerizable liquid monomer is a vinyl ether compound having no hetero atom in a moiety other than the vinyl ether group. The term "hetero atom" here refers to any atom other than a carbon atom and a hydrogen atom. When a hetero atom is contained in the vinyl ether compound, the difference in electronegativity between a hetero atom and a carbon atom may cause the bias in electron density in the molecule to be easily generated, or may cause an unshared electron pair or an empty electron orbital, which a hetero atom has, to be a passage for conduction electrons or holes. Therefore, the
resistance value of a liquid composition in which a vinyl ether compound having a hetero atom is used may be lower than the resistance value of a liquid
composition in which the vinyl ether compound having no hetero atom is used. Accordingly, in order to
efficiently control the resistance value of the liquid composition, the vinyl ether compound having no hetero atom in a moiety other than the vinyl ether group can be used.
[0119] Furthermore, in the present invention, one aspect can be provided in which the cationically polymerizable liquid monomer is a vinyl ether compound having no carbon-carbon double bond in a moiety other than the vinyl ether group. While a carbon-carbon double bond has an electron occupied orbital with a high energy level and an electron unoccupied orbital with a low energy level, such orbitals may serve as a passage for electrons or holes. Therefore, the resistance value of a liquid composition in which a vinyl ether compound having a carbon-carbon double bond in a moiety other than the vinyl ether group is used may be lower than the resistance value of a liquid composition in which the vinyl ether compound not having such a double bond is used. Accordingly, in order to efficiently control the resistance value of the liquid composition, the vinyl ether compound not having such a double bond in a moiety other than the vinyl ether group can be used.
[0120] The cationically polymerizable liquid monomer can further contain a vinyl ether compound having a cyclic structure in the molecule. The vinyl ether compound having a cyclic structure in the molecule can be used to thereby impart excellent sensitivity and strength after curing. Examples of the vinyl ether compound having a cyclic structure in the molecule include an aromatic vinyl ether compound as well as a vinyl ether compound having an alicyclic backbone. The resistance value of a liquid composition in which an aromatic vinyl ether compound is used may be lower than the resistance value of a liquid composition in which an alicyclic vinyl ether compound is used. Accordingly, in order to efficiently control the resistance value of the liquid composition, a vinyl ether compound having an alicyclic backbone can be adopted.
[0121] Furthermore, the vinyl ether compound having a cyclic structure in the molecule can be a compound which has at least one, preferably 1 to 4 vinyl ether groups, and in which the moiety other than the vinyl ether group is a hydrocarbon group having 6 to 18 carbon atoms. The hydrocarbon group used here can be selected from the group consisting of hydrocarbon groups included in exemplary compounds B-l to B-30 described later.
[0122] One aspect can also be provided in which the vinyl ether compound having a cyclic structure in the molecule and a vinyl ether compound having no cyclic structure in . the molecule are used in combination as the cationically polymerizable liquid monomer. In such a case, the ratio of the content of the vinyl ether compound having a cyclic structure in the molecule to the total amount of the vinyl ether compounds is
preferably 10% by mass or more, further preferably 20% by mass or more.
[0123] The molecular weight of each of the vinyl ether compound having a cyclic structure in the molecule and the vinyl ether compound having no cyclic structure in the molecule, as the cationically polymerizable monomer, is preferably 130 or more, further preferably 170 or more. When the molecular weight is 130 or more,
volatility of the cationically polymerizable monomer can be reduced and the amount of radiation can be reduced. While the upper limit of the molecular weight of the cationically polymerizable monomer to be used is not defined, vinyl ether having a molecular weight of 300 or less can be used as a main component because low viscosity of the liquid composition is easily achieved.
[0124 ] Examples of the vinyl ether compound having no cyclic structure include a compound represented by the following formula (A) .
CH2=CH-0-Ra (A)
Ra represents an alkyl group having 3 to 19 carbon atoms optionally substituted with a vinyloxy group or a glycidyloxy group, or - (CHR"-CH2-0) n-CH=CH2 [n
represents 2 or 3 and R" represents a hydrogen atom or a methyl group] . The alkyl group substituted with a vinyloxy group can have 1 to 4 vinyloxy groups .
[0125] Examples of the vinyl ether compound having a cyclic structure include a compound represented by the following formula (B) .
CH2=CH-Rb-Rc (B)
Rb represents a direct bond, an alkylene group having 1 to 3 carbon atoms or an alkenyl group having 3 carbon atoms. Rc represents any of the following cyclic structures.
[0126]
Figure imgf000052_0001
(R-11 ) (R-12)
[ 0127 ] Specific examples [exemplary compounds B-l to B- 30] of the vinyl ether compound that can be used in the present invention include the following, but the vinyl ether compound is not limited to such specific examples in the present invention.
[0128]
Figure imgf000053_0001
( B - 1 2 ) ( B— 1 3 )
Figure imgf000054_0001
Figure imgf000054_0002
Figure imgf000054_0003
(B- 25) (B 26) [0130]
Figure imgf000055_0001
(B— 27 ) (B— 28 )
Figure imgf000055_0002
- 29)
Figure imgf000055_0003
(B— 30)
[0131]Among the above structures, 5,6- dihydrodicyclopentadienevinyl ether (B-8),
tricyclo [5.2.1.02'6] decane vinyl ether (B-10) ,
cyclohexanedimethanol divinyl ether (B-17), neopentyl glycol divinyl ether (B-23), trimethylolpropane
trivinyl ether (B-24), 2-ethyl-l , 3-hexanediol divinyl ether (B-25) , 2, 4-diethyl-l, 5-pentanediol divinyl ether (B-26) , 2-butyl-2-ethyl-l, 3-propanediol divinyl ether (B-27), pentaerythritoltetravinyl ether (B-28), 2,2- bis (4-hydroxycyclohexyl) propane divinyl ether (B-29) or 1,2-decane diol divinyl ether (B-30) can be adopted because of easily providing an ultraviolet curable liquid composition having high resistivity, low
viscosity and high sensitivity. In particular, 5,6- dihydrodicyclopentadienevinyl ether (B-8),
tricyclo [5.2.1.02'6] decane vinyl ether (B-10),
cyclohexanedimethanol divinyl ether (B-17) or 2,2- bis (4-hydroxycyclohexyl) propane divinyl ether (B-29) can be contained in the ultraviolet curable liquid composition in order to enhance sensitivity and
strength after curing.
[0132] The ultraviolet curable liquid composition of the present invention can contain the following additive (s), if necessary.
[ 0133 ] <Cationic polymerization inhibitor>
A cationic polymerization inhibitor can also be added, to the ultraviolet curable liquid composition of the present invention. Examples of the cationic
polymerization inhibitor include an alkali metal
compound and/or an alkali earth metal compound, and amines.
[0134] Such amines can be alkanolamines , N,N- dimethylalkylamines, N, N-dimethylalkenylamines , N,N- dimethylalkynylamines or the like. Examples include triethanolamine, triisopropanolamine, tributanolamine, N-ethyldiethanolamine, propanolamine, n-butylamine, sec-butylamine, 2-aminoethanol , 2-methylaminoethanol , 3-methylamino-l-propanol, 3-methylamino-l , 2-propanediol, 2-ethylaminoethanol, 4-ethylamino-l-butanol , 4- (n- butylamino) -1-butanol, 2- (t-butylamino) ethanol , N,N- dimethylundecanol, N, N-dimethyldodecanolamine, N,N- dimethyltridecanolamine, N, N-dimethyltetradecanolamine, N, N-dimethylpentadecanolamine, N, N- dimethylnonadecylamine, N, N-dimethylicosylamine, N,N- dimethyleicosylamine, N, N-dimethylhenicosylamine, N,N- dimethyldocosylamine, N, N-dimethyltricosylamine, N,N- dimethyltetracosylamine, N, N-dimethylpentacosylamine, N, N-dimethylpentanolamine, N, N-dimethylhexanolamine, N, N-dimethylheptanolamine, N, N-dimethyloctanolamine, N, N-dimethylnonanolamine, N, N-dimethyldecanolamine, N, N-dimethylnonylamine, N, N-dimethyldecylamine, N,N- dimethylundecylamine, N, N-dimethyldodecylamine, N,N- dimethyltridecylamine, N, N-dimethyltetradecylamine, N, N-dimethylpentadecylamine, N, N-dimethylhexadecylamine, N, N-dimethylheptadecylamine and N,N- dimethyloctadecylamine . Besides such amines, a
quaternary ammonium salt or the like can also be used. The cationic polymerization inhibitor can be a secondary amine.
[0135] The amount of the cationic polymerization
inhibitor to be added can be 10 to 5000 ppm based on the ultraviolet curable liquid composition of the present invention.
[ 0136] <Radical polymerization inhibitor>
A radical polymerization inhibitor may also be added to the ultraviolet curable liquid composition of the present invention.
[0137] In an ultraviolet curable liquid composition containing the vinyl ether compound, the
photopolymerization initiator may be slightly
decomposed during storage over time to form a radical compound, and the radical compound may cause
polymerization. When such radical polymerization during storage over time is supposed to be caused, the radical polymerization inhibitor can be added in order to prevent such radical polymerization.
Examples of the radical polymerization inhibitor that can be applied include a phenolic hydroxyl group- containing compound, quinones such as methoquinone
(hydroquinone monomethyl ether) , hydroquinone and 4- methoxy-l-naphthol, a hindered amine type antioxidant, 1 , l-diphenyl-2-picrylhydrazyl free radical, an N-oxyl free radical compound, a nitrogen-containing
heterocyclic mercapto type compound, a thioether type antioxidant, a hindered phenol type antioxidant, ascorbic acids, zinc sulfate, thiocyanates , a thiourea derivative, various saccharides, a phosphoric acid type antioxidant, nitrites, sulfites, thiosulfates , a hydroxylamine derivative, aromatic amines,
phenylenediamines , imines, sulfonamides, a urea
derivative, oximes, a polycondensate of dicyandiamide and polyalkylenepolyamine, a sulfur-containing compound such as phenothiazine, a tetra azaannulene (TAA) -based complexing agent, and hindered amines. [0138] From the viewpoint of preventing the viscosity of the ultraviolet curable liquid composition from being increased due to polymerization of the vinyl ether compound, phenols, N-oxyl free radical compounds, 1,1- diphenyl-2-picrylhydrazyl free radical, phenothiazine, quinones and hindered amines are preferable, and N-oxyl free radical compounds are particularly preferable.
The amount of the radical polymerization inhibitor to be added can be 1 to 5000 ppm based on the ultraviolet curable liquid composition of the present invention.
[0139] <Pigment>
When the ultraviolet curable liquid composition of the present invention is applied to an inkjet ink, a wet electrophotographic liquid developer or the like, a pigment as a coloring material can be contained.
As the pigment, any pigment can be adopted without particular limitation as long as such a pigment is adapted to the intended applications of the ultraviolet curable liquid composition of the present invention.
For example, at least one selected from the group consisting of generally commercially available organic pigment and inorganic pigment, one obtained by
dispersing a pigment in an insoluble resin as a
dispersion medium or one obtained by grafting the surface of a pigment by a resin can be used.
Examples of such a pigment include pigments described in "Dictionary of Pigments" edited by Seijiro ITO
(2000), W. Herbst, K. Hunger "Industrial Organic
Pigments", Japanese Patent Application Laid-Open No.
2002-12607, Japanese Patent Application Laid-Open No.
2002-188025, Japanese Patent Application Laid-Open No.
2003-26978 and Japanese Patent Application Laid-Open No. 2003-342503.
[0140] Among the organic . pigment and inorganic pigment that can be used in the present invention, examples of a pigment exhibiting a yellow color include the following :
C.I. Pigment Yellows 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181 and 185; and C.I. Vat Yellows 1, 3 and 20.
[0141] Examples of a pigment exhibiting a red or magenta color include the following:
C.I. Pigment Reds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3,48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238 and 269; C.I. Pigment Violet 19; and C.I. Vat Reds 1, 2, 10, 13, 15, 23, 29 and 35.
[ 0142 ] Examples of a pigment exhibiting a blue or cyan color include the following:
C.I. Pigment Blues 2, 3, 15:2, 15:3, 15:4, 16 and 17; C.I. Vat Blue 6; C.I. Acid Blue 45, and Copper
Phthalocyanine pigments having 1 to 5 phthalimidemethyl groups as substituent ( s ) on the phthalocyanine backbone.
[0143] Examples of a pigment exhibiting a green color include the following:
C.I. Pigment Greens 7, 8 and 36.
Examples of a pigment exhibiting an orange color
include the following:
C.I. Pigment Oranges 66 and 51.
[0144] Examples of a black color pigment include the following :
carbon black, titanium black and aniline black.
Examples of a white pigment include the following:
basic lead carbonate, zinc oxide, titanium oxide and strontium titanate.
[0145] Titanium oxide here is smaller in specific
gravity, higher in refractive index, and chemically and physically more stable than other white pigments, and therefore has large hiding power and coloring power as a pigment and furthermore is also excellent in
resistances against an acid and an alkali, and other environments. Accordingly, titanium oxide can be utilized as the white pigment. Of course, other white pigment (which may be a pigment other than the white pigments recited.) may also be used, if necessary.
[0146] In dispersing of the pigment, a dispersing
apparatus such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill or a wet jell mill can be used.
[0147JA dispersant can also be added in dispersing of the pigment. Examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular acid ester, a salt of a high molecular polycarboxylic acid, a high molecular unsaturated acid ester, a high molecular copolymerized product, a modified
polyacrylate, an aliphatic polyvalent carboxylic acid, a formalin condensate of naphthalenesulfonic acid, a polyoxyethylene alkyl phosphoric acid , ester, and a pigment derivative. In addition, a commercially
available polymeric dispersant such as Solsperse Series produced by Lubrizol Corporation can also be used.
[0148] In addition, a synergist according to various pigments can also be used as a dispersion auxiliary material. The dispersant and the dispersion auxiliary material can be added in an amount of 1 to 50 parts by mass based on 100 parts by mass of the pigment.
[0149] The pigment can be used in the form of a
dispersion thereof dispersed in a liquid medium, for preparing an ultraviolet curing ink or a liquid
developer using the ultraviolet curing liquid
composition. As the liquid medium for preparation of such a pigment dispersion, any medium can be selected from various liquid materials and used depending on the objects as long as the intended functions in the
ultraviolet curing ink and the liquid developer are not impaired. In particular, the vinyl ether compound that can also be used as the liquid monomer can be used as the liquid medium for dispersing of the pigment because the vinyl ether compound can be utilized as a monomer component as it is.
[0150]<Toner particle>
When the ultraviolet curable liquid composition of the present invention is applied to a wet
electrophotographic liquid developer, an electrostatic inkjet ink or the like, a toner particle insoluble in the liquid monomer can be contained as a coloring material. A charged particle insoluble in the liquid monomer for use in the field, such as an
electrophoretic fine particle, can be contained in the electrostatic inkjet ink, and the toner particle
insoluble in the liquid monomer can also be utilized as a charged particle as a coloring material. The toner particle contains a binder resin and a pigment, and can contain a charge director, if necessary.
[0151] Examples of the method for producing the toner particle include a coacervation method and a wet
crushing method.
The coacervation method is described in detail in, for example, Japanese Patent Application Laid-Open No.
2003-241439 and International Re-Publication (WO
2009/041634, WO 2007/000974 and WO 2007/000975) . In addition, the wet crushing method is described in detail in, for example, International Re-Publication (WO 2006/126566 and WO 2007/108485) .
[0152] The toner particle obtained by such a method preferably has an average particle size of 0.05 to 5 μπι, more preferably 0.05 to 1 μτη, from the viewpoint that a highly fine image is obtained.
[0153] The toner particle can be used in the form of a dispersion including a pigment dispersed in a liquid medium, for preparing a liquid developer using the ultraviolet curing liquid composition. As the liquid medium for preparation of such a toner particle
dispersion, any medium can be selected from various . liquid materials and used depending on the objects as long as the intended functions in the ultraviolet curing liquid developer are not impaired. In
particular, the vinyl ether compound that can also be utilized as the liquid monomer can be used as the liquid medium for dispersing of the toner particle because the vinyl ether compound can be utilized as a monomer component as it is.
[0154] <Binder resin>
As the binder resin, any of various binder resins having fixability to an adherend such as . paper or a plastic film can be used, a resin such as an epoxy resin, an ester resin, an acrylic resin, a styrene- acrylic resin, an alkyd resin, a polyethylene resin, an ethylene-acrylic resin or a rosin-modified resin can be used, and such a resin can be used singly or in
combinations of two or more, if necessary.
The content of the binder resin can be 50 to 1000 parts by mass based on 100 parts by mass of the pigment.
[0155] <Charge director>
Various agents can be used as the charge director.
Examples include oils and fats such as a linseed oil and a soybean oil; an alkyd resin, a halogen polymer, an aromatic polycarboxylic acid, an acidic group- containing water-soluble dye, an oxidation condensate of an aromatic polyamine, metal soaps such as cobalt naphthenate, nickel naphthenate, iron naphthenate, zinc naphthenate, cobalt octylate, nickel octylate, zinc octylate, cobalt dodecylate, nickel dodecylate, zinc dodecylate, aluminum stearate and cobalt 2- ethylhexanoate; sulfonic acid metal salts such as a petroleum-based sulfonic acid metal salt and a metal salt of a sulfosuccinic acid ester; phospholipids such as lecithin; salicylic acid metal salts such as a t- butylsalicylic acid metal complex; and a
polyvinylpyrrolidone resin, a polyamide resin, a sulfonic acid-containing resin and a hydroxybenzoic acid derivative.
[0156]<Other additives>
Various additives other than the above can be
appropriately selected and used in the ultraviolet curable liquid composition of the present invention, if necessary, depending on objects such as an enhancement in adaptivity to a recording medium, storage stability, image storing property and other various performances. Examples of the additives include a surfactant, a lubricant, a filler, a defoamer, an ultraviolet
absorber, an antioxidant, a discoloration inhibitor, an antifungal agent and an antirust agent.
[0157] <Physical properties>
When the ultraviolet curable liquid composition of the present invention is applied to a wet
electrophotographic liquid developer, an electrostatic inkjet ink or the like, the developer and the ink can be prepared and used so as to have the same physical properties as physical properties of common liquid developer and electrostatic inkjet ink.
[0158] When the ultraviolet curable liquid composition of the present invention is applied to a wet
electrophotographic liquid developer, the viscosity can be 0.5 to 10 mPa«s at 25°C and the volume resistivity can be 1 x 1010 to 1 x 1013 Qcm when the concentration of the toner particle included in the liquid developer is 2% by mass. A too high viscosity may reduce the electrophoretic velocity of the toner particle in the liquid developer, resulting in a reduction in printing rate. A too low volume resistivity may easily drop the potential of an electrostatic latent, image, imparting a high optical density hardly or causing image blurring. A too high volume resistivity may reduce the
electrophoretic velocity of the toner particle,
resulting in a reduction in printing rate.
[0159] When the ultraviolet curable liquid composition of the present invention is applied to a wet
electrophotographic liquid developer, an ultraviolet curing liquid developer that achieves high ultraviolet curability and that satisfies the above values of physical properties can be prepared.
[0160] <Applications>
The ultraviolet curable liquid composition of the present invention can be used in an ultraviolet curing inkjet ink, an ultraviolet curing wet
electrophotographic liquid developer and an ultraviolet curing electrostatic inkjet ink, and can also be used in other applications.
[0161] Examples of an application in which a substrate is coated with the ultraviolet curable liquid
composition of the present invention and the surface thereof is subjected to photocuring with being left to be opened include various applications described below: a paint for automobiles, woodwork coating, polyvinyl chloride (PVC) floor coating, ceramic wall coating, coating for building materials, resin hard coat, metallized base coat, film coating, coating for liquid crystal displays (LCDs) , coating for plasma displays
(PDPs) , coating for optical disks, metal coating, optical fiber coating, a printing ink, a planographic ink, a metal can ink, a screen printing ink and gravure varnish .
[0162] Such usage can also be adopted in the fields of a resist, a display, a seal agent, a dental material, a photo forming material. and the like.
[0163] Examples of an application in which a substrate is coated with the ultraviolet curable liquid
composition of the present invention and the surface thereof is bonded with other substrate and subjected to photocuring include an adhesive, a pressure sensitive adhesive, a tackifier and a sealing agent. Furthermore, the ultraviolet curable liquid composition can be appropriately used in applications illustrated in the following literatures.
• "Latest Trend III of Photosensitive Material for
Electronic Components-Development Status in
Semiconductor, Electronic Substrate and Display Fields- " (S.B. Research Co., Ltd., July 2006)
• "Latest Trend of UV/EB Curing Technique" (RadTech Japan, March 2006)
• "Applied Optical Technology/Material Dictionary"
(edited by Tsuguo YAMAOKA, April 2006)
• "Photocuring Technology" (Technical Information
Institute Co., Ltd., March 2000)
• " Photocurable Materials-Production Technology and Application Development-" (Toray Research Center, Inc., September 2007) .
[0164] <Ultraviolet light source>
As an ultraviolet light source for curing the
ultraviolet curable liquid composition of the present invention, for example, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a hot cathode tube, a black light or an LED (light emitting diode) can be applied. When the ultraviolet curable liquid composition is applied to an inkjet ink, a wet electrophotographic liquid developer, an electrostatic inkjet ink or the like, the
ultraviolet curable liquid composition can be
irradiated with ultraviolet ray after ink impact or transfer to a recording medium such as paper or a film. In irradiation with ultraviolet ray, a band metal halide lamp, a cold cathode tube, a hot cathode tube, a mercury lamp, a black light, an LED or the like can be used. The amount of irradiation with ultraviolet ray can be 0.1 to 1000 mJ/cm2.
Examples
[0165] Hereinafter, the method for producing the
ultraviolet curing liquid composition of the present invention is more specifically described with reference to Examples, but the present invention is not limited thereto without departing from the gist and the scope of application thereof. Herein, "part(s)" and "%" mean "part(s) by mass" and "% by mass", respectively, in the following description unless particularly noted.
Respective materials used in Examples and Comparative Examples below are described.
[0166] <Example 1>
The following respective components were mixed and dissolved to provide an ultraviolet curable liquid composition .
• Cyclohexanedimethanol (exemplary compound B-17) as cationically polymerizable liquid monomer: 97.8 parts
• Exemplary compound A-3 recited above as
photopolymerization initiator: 0.2 parts
• 9, 10-Bis (n-propoxy) anthracene as photopolymerization sensitizer: 1.0 part
• 1, 2, 3-Trimethoxybenzene: 1.0 part
[0167 ] <Examples 2 to 25 and Comparative Examples 1 to 8>
The cationically polymerizable liquid monomer, the photopolymerization initiator and the
photopolymerization sensitizer used in Example 1 were changed so that each composition shown in Table 1, Table 2 and Table 3 was achieved, to provide an
ultraviolet curable liquid composition in each of
Example 2 to 25 and Comparative Examples 1 to 8. Herein, "B-10", "B-17" and "B-19" as monomers in Tables 1 to 3 denoted the respective exemplary compound
numbers of the vinyl ether compounds recited above.
Polymerization initiators used in Comparative Examples were as follows.
• Photopolymerization initiator (D-l) : CPI-llOP
( triarylsulfonium salt type photocationic
polymerization initiator produced by San-Apro Ltd.)
• Photopolymerization initiator (D-2) : WPI-113
(diphenyliodonium salt type photocationic
polymerization initiator produced by Wako Pure Chemical Industries, Ltd.)
[0168] <Performance evaluation>
(Sensitivity)
A polyethylene terephthalate film was coated with each ultraviolet curable liquid composition at 25°C by a wire bar (No. 3) , and irradiated with ultraviolet ray by a high pressure mercury lamp with a lamp output of 120 mW/cm2 at a predetermined amount of light to form a film (cured film) . The thickness of the film formed was 6 um. The surface of the film immediately after curing was touched by fingers, and the presence of the surface tackiness (stickiness) was confirmed and rated according to the following criteria.
• Rank "5": Tackiness was not observed in curing at an amount of light of 45 mJ/cm2.
• Rank "4": Tackiness was observed in curing at an amount of light of 45 mJ/cm2, and tackiness was not observed in curing at an amount of light of 150 mJ/cm2.
• Rank "3": Tackiness was observed in curing at an amount of light of 150 mJ/cm2, and tackiness was not observed in curing at an amount of light of 300 mJ/cm2.
• Rank "2": Tackiness was observed in curing at an amount of light of 300 mJ/cm2, and tackiness was not observed in curing at an amount of light of 1000 mJ/cm2.
• Rank "1": Tackiness was observed even in curing at an amount of light of 1000 mJ/cm2.
[0169] (Volume resistivity)
The volume resistivity was measured using R8340
manufactured by Advantest Corporation.
[0170] (Storage property)
A light shielding bottle was charged with each
ultraviolet curable liquid composition and tightly sealed under a storage environment of 25°C/50% RH, and the change in viscosity before and after storage was calculated as the ratio of viscosity after
storage/viscosity before storage and rated according to the following criteria.
• Rank "5": The change in viscosity was 1.1 or less even after storage for 1 year, and the change in viscosity was not almost observed.
e Rank "4": The change in viscosity was 1.1 or less after storage for 6 months, and the change in viscosity was 1.1 or more after storage for 1 year.
• Rank "3": The change in viscosity was 1.1 or less after storage for 3 months, and the change in viscosity was 1.1 or more after storage for 6 months.
• Rank "2": The change in viscosity was 1.1 or more after storage for 3 months.
• Rank "1": Solidification was observed after storage for 3 months, and the viscosity could not be measured.
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
[0174] "E" of the value of each volume resistivity in Tables 1 to 3 means "xlO", and the number at the right of "E" means exponent. For example, "1.8E + 10" in Example 1 means "1.8 x 1010".
[0175] It was found from the rating results in
Comparative Examples 1 to 4 that, in the prior art in which the basic compound was added for an improvement in storage stability, the basic compound inhibited the function of an acid generated by exposure and thus storage stability and sensitivity were difficult to simultaneously be satisfied.
[0176] On the contrary, it was found from the rating results in Examples 1 to 25 that the ultraviolet curable liquid composition of the present invention could allow excellent storage stability and sensitivity to be simultaneously satisfied.
[0177] It was found that the ultraviolet curable liquid compositions prepared in Comparative Examples 5 to 8 that the photopolymerization initiator in the
compositions were changed from the photopolymerization initiator in the ultraviolet curable liquid composition of the present invention, had difficulty in
simultaneously satisfying storage stability and
sensitivity and also had a significantly reduced volume resistivity.
[0178] <Example 26>
(Preparation of ink)
The following respective components were loaded in a planetary bead mill (Classic Line P-6/Fritsch) together with zirconia beads having a diameter of 0.5 mm, and mixed and dispersed at room temperature at 200 rpm for 4 hours to provide a pigment dispersion.
• Pigment Blue 15:3 as pigment: 20 parts
• Solsperse 24000GR produced by Lubrizol Corporation as dispersant of pigment: 7 parts
• Dodecylvinyl ether (exemplary compounds . (B-3)): 73 parts
The following respective components were added to 10.0 parts of the pigment dispersion to provide an
ultraviolet curing inkjet ink.
• Cyclohexanedimethanol divinyl ether (exemplary
compound B-17) as polymerizable liquid monomer: 87.8 parts
• Compound represented as exemplary compound A-3 as photopolymerization initiator: 0.2 parts
• 2 , 4-Diethylthioxanthone as photopolymerization
sensitizer: 1.0 part
• 1, 4-Diethoxynaphthalene: 1.0 part
The resulting ultraviolet curing inkjet ink was loaded in an UV curing inkjet printer UJF-3042HG manufactured by Mimaki Engineering Co., Ltd. and subjected to
evaluation of printing characteristics, and as a result, could be confirmed to have good printing
characteristics.
[0179] <Example 27>
(Production of ultraviolet curing liquid developer) A separable flask was charged with 25 parts of Nucrel N1525 (ethylene-methacrylic acid resin/produced by Du Pont-Mitsui Polychemicals ) and 75 parts of dodecylvinyl ether (exemplary compound (B-3) ) . The resulted mixture was stirred at 200 rpm by using of a three-one motor was used while heating the mixture to 130°C in an oil bath over 1 hour. After being held at 130°C for 1 hour, the resultant was gradually cooled at a rate of -15°C per hour to prepare a toner particle precursor. The resulting toner particle precursor was a white paste.
[0180] The toner particle precursor (59.40 parts) was loaded in a planetary bead mill (Classic Line P- 6/Fritsch) together with the following respective components, and pulverized at room temperature at 200 rpm for 4 hours to provide a toner particle dispersion (solid content: 20% by mass) . • Pigment Blue 15:3 as pigment: 4.95 parts
• Aluminum tristearate as charge adjuvant: 0.2 parts
• Dodecylvinyl ether (exemplary compound B-3) : 35.45 parts
• Zirconia beads having a diameter of 0.5 mm
The resulting toner particle had an average particle size of 0.85 μm (measured by Nanotrac 150 manufactured by Nikkiso Co., Ltd.).
The following respective components were added to 10.0 parts of the toner particle dispersion to provide an ultraviolet curing liquid developer.
• Hydrogenated lecithin (Lecinol S-10/produced by Nikko Chemicals Co., Ltd.) as charge director: 0.1 parts
• Cyclohexanedimethanol divinyl ether (exemplary compound B-17) as polymerizable liquid monomer: 87.7 parts
• Photopolymerization initiator represented as
exemplary compound A-3: 0.2 parts
• 2 , 4-Diethylthioxanthone : 1.0 part and 1,4- diethoxynaphthalene : 1.0 part, as photopolymerization sensitizer
[0181] The resulting ultraviolet curing liquid developer was used to evaluate the volume resistivity,
developability and fixability, as described below.
[0182] (Volume resistivity)
The volume resistivity was measured using R8340
manufactured by Advantest Corporation, and was found to be 1.3 x 1011 Ωατι.
[0183] (Developability)
An electrostatic pattern was formed on electrostatic recording paper at a surface charge of 150 to 500 V, and the ultraviolet curing liquid developer was used to perform development by a roller developing machine. The quality of the resulting image was confirmed, and as a result, a high-density and highly-fine image was obtained. While the variation in density and image blurring were observed due to attenuation of the surface charge at a low electric resistivity of the liquid developer, the variation in density and image blurring were not observed by use of the ultraviolet curing liquid developer.
[0184] (Fixability)
A polyethylene terephthalate film was coated with the ultraviolet curing liquid developer at 25°C by a wire bar (No. 6), and irradiated by a high pressure mercury lamp with a lamp output of 120 mW/cm2 at an amount of light of 45 mJ/cm2 (measurement wavelength: 365 nm) to form a cured film. The surface of the film immediately after curing was touched by fingers, and the presence of the surface tackiness (stickiness) was confirmed, but tackiness was not observed at all and it could be confirmed that sufficient fixability was achieved.
[0185] <Comparative Example 9>
The following respective components were added to 10.0 parts of the toner particle dispersion produced in the same manner as in Example 27, to provide an ultraviolet curing liquid developer.
• Hydrogenated lecithin (Lecinol S-10/produced by Nikko Chemicals Co., Ltd.) as charge director: 0.1 parts
• Cyclohexanedimethanol divinyl ether (exemplary compound B-17) as polymerizable liquid monomer: 86.9 parts
• Photopolymerization initiator represented in D-l: 1.0 part
• 2 , 4-Diethylthioxanthone : 1.0 part and 1,4- diethoxynaphthalene : 1.0 part, as photopolymerization sensitizer
The resulting ultraviolet curing liquid developer was used to evaluate the volume resistivity, developability and fixability, as described below.
[0186] (Volume resistivity)
The volume resistivity was measured using R8340 manufactured by Advantest Corporation, and was found to be 4.9 x 107 Ωcm.
[0187] (Developability)
The same evaluation as in Example 27 was tried, but development could not be conducted. The reason for this was considered as follows: a too low volume resistivity of the liquid developer caused the surface charge to be significantly attenuated.
[0188] (Fixability)
The same evaluation as in Example 27 was performed, and tackiness was not observed at all and it could be confirmed that sufficient fixability was achieved.
[0189] <Example 28>
The ultraviolet curing liquid developer prepared in Example 27 was used for an ultraviolet curing
electrostatic inkjet ink. The ink was used for
printing on a medium by use of an inkjet printing apparatus described in PCT Publication No. WO 93/11866 and evaluated with respect to printing characteristics, and as a result, it could be confirmed that good printing characteristics were achieved. The apparatus was operated at an operating frequency of 2.5 kHz and a maximum discharge voltage of +2400 V.
The ink solid density of the ink fixed onto the medium subjected to printing was measured by a thermal
analysis apparatus, and it could be confirmed that the solid density was 18.8% and ejection was conducted after concentrating by a nozzle.
[0190] Next, the medium subjected to printing was irradiated by a high pressure mercury lamp with a lamp output of 120 mW/cm2 at an amount of light of 45 mJ/cm2
(measurement wavelength: 365 nm) , and subjected to UV curing. The surface of the printed product immediately after curing was touched by fingers and confirmed about the presence of surface tackiness (stickiness), and tackiness was not observed at all and it could be confirmed that sufficient fixability was achieved.
[0191] Comparative Example 10>
The ultraviolet curing liquid developer prepared in Comparative Example 9 was used for an ultraviolet curing electrostatic inkjet ink. The ink was tried to be used for printing on a medium by use of an inkjet printing apparatus described in PCT Publication No. WO 93/11866, but the ink was not ejected.
Industrial Applicability
[0192] The ultraviolet curable liquid composition of the present invention includes at least the following respective components:
• at least one vinyl ether compound as a cationically polymerizable liquid monomer;
• at least one compound represented by the general formula (1) as a photopolymerization initiator; and
• at least one selected from the group consisting of compounds represented by general formula (2) and
general formula (3) , and at least one selected from the group consisting of compounds represented by general formula (4) and general formula (5), as a
photopolymerization sensitizer.
[0193] The vinyl ether compound can be combined with the combination of the specific compounds as the
photopolymerization initiator and the
photopolymerization sensitizer, to thereby provide an ultraviolet curing liquid composition having high sensitivity, excellent storage stability, low viscosity, and excellent fixability after ultraviolet curing.
The ultraviolet curable liquid composition can be used to provide an ultraviolet curing inkjet ink, an
ultraviolet curing wet electrophotographic liquid developer, an ultraviolet curing electrostatic inkjet ink or the like. The liquid developer and inks are also high in sensitivity, low in viscosity and
excellent in storage stability, exhibit a high optical density and hardly causes image blurring, and has sufficient fixability.
[0194] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such
modifications and equivalent structures and functions.
[0195] This application claims the benefit of Japanese Patent Application No. 2015-003347, filed January 9, 2015, and Japanese Patent Application No. 2015-257003, filed December 28, 2015, which are hereby incorporated by reference herein their entirety.

Claims

[Claim 1]An ultraviolet curable liquid composition comprising:
a cationically polymerizable liquid monomer, a photopolymerization initiator and a photopolymerization sensitizer, wherein
the cationically polymerizable liquid monomer is a vinyl ether compound,
the photopolymerization initiator comprises a compound represented by the following general formula (1), and the photopolymerization sensitizer comprises:
(A) at least one compound selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3), and
(B) at least one compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5):
General formula (1)
Figure imgf000079_0001
in the general formula (1), x represents an integer of 1 to 8, y represents an integer of 3 to 17, and R1 and R2 are bound to each other to form a cyclic structure;
General formula in the general formula (2) , R3, R4, R5 and R6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or
unsubstituted alkoxy group, a substituted or
unsubstituted aryloxy group, a cyano group, a
substituted or unsubstituted aralkyl group, a
substituted or unsubstituted alkoxycarbonyl group, or a halogen atom;
General formula (3)
Figure imgf000080_0001
in the general formula (3), R7 and R8 each
independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, and R9 and R10 each independently
represent a hydrogen atom, an aralkyl group, an alkyl group having 1 to 9 carbon atoms optionally substituted with a group having an oxygen atom, or a glycidyl group;
General formula
Figure imgf000080_0002
in the general formula (4), R11 and R12 each
independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, q and r each independently represent an integer of 0 to 4, R represents a hydrogen atom, an alkyl
group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group, or an aralkyl group, s represents an integer of 1 to 3, each R11 is independently defined as above when a plurality of R1:L(s) are present, each R12 is independently defined as above when a plurality of R12(s) are present, and each R13 is independently defined as above when a plurality of R13(s) are present; and a (5)
Figure imgf000081_0001
in the general formula (5) , R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, u represents an integer of 0 to 4, R15 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group or an aralkyl group, t represents an integer of 1 or 2, each R14 is independently defined as above when a plurality of R14(s) are present, and each R15 is independently defined as above when a plurality of R15(s) are present.
[Claim 2] The ultraviolet curable liquid composition according to claim 1, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (6): General formula
Figure imgf000082_0001
in the general formula (6), R and R each
independently represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, u and v each independently represent an integer of 0 to 4, R18 and R19 each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group or an aralkyl group, each R16 is independently defined as above when a plurality of R16(s) are present, and each R17 is independently defined as above when a plurality of R17(s) are present. ] The ultraviolet curable liquid composition according ■ claim 1 or 2, wherein the compound represented by the general formula (5) is a compound represented by the following general formula (7):
General formula
Figure imgf000082_0002
in the general formula (7), R represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a halogen atom, w represents an integer of 0 to 4, R21 and R22 each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon
atoms optionally substituted with a substituent having an oxygen atom, a glycidyl group or an aralkyl group, and each R20 is independently defined as above when a plurality of R20(s) are present.
[Claim 4 ] The ultraviolet curable liquid composition according to claim 2, wherein the photopolymerization sensitizer comprises :
at least one compound selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula ( 3 ) , and
the compound represented by the general formula
(6) .
[Claim 5] The ultraviolet curable liquid composition according to any one of claims 1 to 4, wherein, when a content of at least one compound selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) is defined as C% by mass and a content of the compound represented by the general formula (1) is defined as A% by mass, C/A is 1.0 or more.
[Claim 6] The ultraviolet curable liquid composition according to any one of claims 1 to 5, wherein a content of the photopolymerization initiator is 0.01 to 5 parts by mass based on 100 parts by mass of the cationically polymerizable liquid monomer.
[Claim 7] The ultraviolet curable liquid composition according to any one of claims 1 to 6, wherein the vinyl ether compound is a vinyl ether compound having a cyclic structure in a molecule. [Claim 8] The ultraviolet curable liquid composition according to any one of claims 1 to 7, wherein CxFy in the general formula (1) is any of CF3, C2F5, C3F7 and C4F9.
[Claim 9] The ultraviolet curable liquid composition according to any one of claims 1 to 7, wherein CxFy in the general formula (1) is C6F5.
[Claim 10]An ultraviolet curing inkjet ink comprising:
the ultraviolet curable liquid composition according to any one of claims 1 to 9, and
a pigment or a dye.
[Claim 11]An ultraviolet curing wet electrophotographic liquid developer comprising:
the ultraviolet curable liquid composition according to any one of claims 1 to 9, and
a toner particle insoluble in the liquid monomer.
[Claim 12]An ultraviolet curing electrostatic inkjet ink
comprising:
the ultraviolet curable liquid composition according to any one of claims 1 to 9, and
an electrophoretic fine particle insoluble in the liquid monomer.
PCT/JP2016/051058 2015-01-09 2016-01-07 Ultraviolet curable liquid composition, ultraviolet curing inkjet ink, ultraviolet curing wet electrophotographic liquid developer, ultraviolet curing electrostatic inkjet ink, and image forming method using thereof WO2016111380A1 (en)

Priority Applications (4)

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CN201680005328.XA CN107108774A (en) 2015-01-09 2016-01-07 Ultra-violet solidified fluid composition, the uv-curing type ink jet ink using it, ultraviolet hardening wet type electrophotographic liquid developer, ultraviolet hardening electrostatic inkjet ink and image forming method
KR1020177021551A KR20170102325A (en) 2015-01-09 2016-01-07 An ultraviolet curable liquid composition, an ultraviolet curable inkjet ink, an ultraviolet curable liquid electrophotographic liquid developer, an ultraviolet curable electrostatic inkjet ink, and an image forming method using the same
US15/533,808 US20170336728A1 (en) 2015-01-09 2016-01-07 Ultraviolet curable liquid composition, ultraviolet curing inkjet ink, ultraviolet curing wet electrophotographic liquid developer, ultraviolet curing electrostatic inkjet ink, and image forming method using thereof
EP16735118.8A EP3242897A1 (en) 2015-01-09 2016-01-07 Ultraviolet curable liquid composition, ultraviolet curing inkjet ink, ultraviolet curing wet electrophotographic liquid developer, ultraviolet curing electrostatic inkjet ink, and image forming method using thereof

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