WO2011158593A1 - Photocurable ink jet ink, method for forming image, maleimide derivative and photocurable composition - Google Patents

Photocurable ink jet ink, method for forming image, maleimide derivative and photocurable composition Download PDF

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Publication number
WO2011158593A1
WO2011158593A1 PCT/JP2011/061395 JP2011061395W WO2011158593A1 WO 2011158593 A1 WO2011158593 A1 WO 2011158593A1 JP 2011061395 W JP2011061395 W JP 2011061395W WO 2011158593 A1 WO2011158593 A1 WO 2011158593A1
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group
maleimide derivative
general formula
ink
photocurable
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PCT/JP2011/061395
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French (fr)
Japanese (ja)
Inventor
孝由 戸枝
正樹 中村
宏毅 川嶋
悠介 ▲高▼久
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コニカミノルタホールディングス株式会社
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Priority to JP2012520335A priority Critical patent/JPWO2011158593A1/en
Publication of WO2011158593A1 publication Critical patent/WO2011158593A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • 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

Definitions

  • the present invention relates to a photocurable inkjet ink, an image forming method, a maleimide derivative, and a photocurable composition. More specifically, the present invention relates to a photocurable inkjet ink used in an inkjet printer equipped with a light irradiation device and the inkjet ink. Relates to maleimide derivatives used in
  • the inkjet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields.
  • a recording medium or ink jet ink hereinafter also simply referred to as ink
  • ink ink jet ink
  • ink is ejected from an ink jet head and landed on a recording medium to form an image.
  • the ink In order to eject the ink from the ink jet head, the ink needs to have a low viscosity.
  • high-viscosity inks are necessary to prevent color mixing called bleeding.
  • an ultraviolet curable ink jet using a photocurable ink has been put into practical use. This is achieved by adding a photocurable monomer and a photopolymerization initiator to the ink, irradiating the recording medium with light and then curing the ink, thereby ensuring both emission and prevention of bleeding. . But it has another essential problem.
  • the radical polymerization system is inhibited by oxygen, and the cationic polymerization system is inhibited by water in the air. In the method of forming small droplet dots in a non-contact manner on the substrate like inkjet, these inhibition factors
  • the radical polymerization system has a drawback that it is necessary to use a large ultraviolet irradiator with high illuminance and high light quantity in the radical polymerization system, and it is necessary to control the humidity in the cationic polymerization system.
  • oxygen inhibition As a method for reducing oxygen inhibition, a monomer system that is less susceptible to oxygen inhibition can be employed. For one thing, oxygen inhibition can be reduced by using the ene-thiol reaction (see, for example, Patent Document 3), but there is a odor peculiar to thiols, and there are some that are unbearable for use in inkjet inks.
  • CT polymerization charge transfer complex polymerization
  • an electron-rich donor monomer such as vinyl ether
  • an electron-deficient monomer such as maleic anhydride or maleimide
  • This reaction was known to have little oxygen inhibition, but when used as an inkjet ink, it must be stored in a liquid state for a long time, so maleic anhydride has poor storage and maleimide has poor solubility.
  • the inkjet nozzles were clogged and could not be emitted.
  • maleimide compounds having high solubility As maleimide compounds having high solubility, maleimides (see, for example, Patent Document 4) in which an alkylene oxide is arranged at the center, and maleimides derived from a dimer of oleic acid (for example, see Patent Document 5) have been proposed. The combination with vinyl ether was also described. However, with these compounds, the molecular weight was too large, and only a highly viscous ink could be produced, and good emission was not possible.
  • liquid maleimide compounds see, for example, Patent Document 4
  • Patent Document 6 liquid maleimide compounds having a length and a branch sufficient to form a liquid are also disclosed, but when both are applied to inkjet inks, it is not possible to achieve both photocuring sensitivity and ejectability. It was enough and improvement was expected.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a photocurable composition, a photocurable inkjet ink, and an image forming method that have high photocuring sensitivity and can be emitted by an inkjet printer. There is to do. Another object is to provide a liquid maleimide derivative suitable for the application.
  • a photocurable inkjet ink comprising a maleimide derivative represented by the following general formula (1).
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring.
  • a 1 , A 3 independently represents an alkylene group
  • a 2 represents a hydrocarbon group having an asymmetric center
  • Y represents carbonyloxy (—C ⁇ O—O—) or oxycarbonyl (—O—C ⁇ O).
  • P represents 1 or 2.
  • R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2.
  • a 1 and A 3 are methylene groups, A 2 is CHR 4 , R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group, and R 4 is 1 to 4 carbon atoms.
  • R 4 said 2 represents R 4 group having the same meaning as described, p has the same meaning as p in the general formula (1) .
  • R 5 is an alkyl group having 4 to 12 carbon atoms linear, Or represents an alkylene group.
  • a maleimide derivative represented by the following general formula (1) represented by the following general formula (1).
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring.
  • a 1 , A 3 independently represents an alkylene group
  • a 2 represents a hydrocarbon group having an asymmetric center
  • Y represents carbonyloxy (—C ⁇ O—O—) or oxycarbonyl (—O—C ⁇ O).
  • P represents 1 or 2.
  • R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2.
  • a 1 and A 3 are methylene groups
  • a 2 is CHR 4
  • R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group
  • R 4 is 1 to 4 carbon atoms. 6.
  • R 4 the 6 represents R 4 group having the same meaning as described, p has the same meaning as p in the general formula (1) .
  • R 5 is an alkyl group having 4 to 12 carbon atoms linear, Or represents an alkylene group.
  • 8 A photocurable composition comprising the maleimide derivative according to any one of 5 to 7 above.
  • a liquid maleimide derivative can be provided without reducing photocuring sensitivity, and an inkjet ink that can be emitted by an inkjet head without being diluted with a solvent can be provided. it can.
  • the present inventors have introduced a trivalent hydrocarbon group having an asymmetric center into a maleimide derivative, thereby reducing the photocuring sensitivity and reducing the viscosity of the liquid.
  • an ink-jet ink which can be emitted by an ink-jet head without being diluted with a solvent and can be obtained with a maleimide derivative and which can provide an excellent high-quality image is obtained.
  • the maleimide of the present invention becomes a mixture of the D-form and L-form by a trivalent hydrocarbon group having an asymmetric center, and by introducing it near the maleimide group, the crystallization of maleimide is hindered by steric hindrance. It is presumed that, even with a relatively low molecular weight, no precipitation occurred in the ink, and good light emission was obtained.
  • the liquid maleimide derivative is intended to be liquid (including oil) at room temperature.
  • the maleimide derivative of the present invention preferably has an asymmetric center group at the position of ⁇ or ⁇ position with respect to the maleimide ring.
  • the molecular weight of R 3 is 56 to 168.
  • R 3 represents an alkyl group or alkylene group having 4 to 12 carbon atoms.
  • examples of the alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • R 1 and R 2 may combine to form a cyclopropene ring, a cyclobutylene ring, a cyclopentene ring, a cyclohexene ring, or the like.
  • Examples of the divalent organic linking group represented by A 1 or A 3 include a methylene group, an ethylene group, a butylene group, a hexylene group, an ethyleneoxy group, a polyethyleneoxy group, a butyleneoxy group, a polybutyleneoxy group, and an ethyleneoxycarbonyl group. Hexyleneoxycarbonyl group, methylene ester group, hexylene ester group, phenylene group, methylphenylene group, oxycarbonylphenylenecarbonyloxy group, and carbonyloxyphenyleneoxycarbonyl group.
  • a 2 represents a group having an asymmetric carbon (chiral carbon).
  • R 4 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, an alkylcarbonyloxy group having 1 to 18 carbon atoms, or a hydroxyl group.
  • R 4 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, an alkylcarbonyloxy group having 1 to 18 carbon atoms, or a hydroxyl group.
  • More preferred is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, isobutyl group, etc.).
  • the alkyl group having a molecular weight of 15 to 600 represented by R 3 preferably represents an alkyl group having 1 to 18 carbon atoms which may be branched. Specifically, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, neopentyl group, dodecylyl group, 2,2,4-octyl group and the like.
  • the alkylene group having a molecular weight of 14 to 600 represented by R 3 when p is 2 preferably represents an alkylene group having 1 to 18 carbon atoms which may be branched, and specifically includes a methylene group, an ethylene group , Propylene group, butylene group, hexylene group, neopentylene group, dodecylene group, 2,2,4-octylene group, and the like.
  • alkyleneoxy group represented by R 3 when p is 1 examples include, but are not limited to, a hydroxy or alkoxy polyethyleneoxy group, a hydroxy or alkoxypolyproleneoxy group, a hydroxy or alkoxypolybutyleneoxy group, and the like. It is not something.
  • R 3 is preferably an alkylene group having 1 to 18 carbon atoms which may be branched, or an alkyl group having 1 to 18 carbon atoms which may be branched, and more preferably a branched chain having 4 to 12 carbon atoms.
  • An alkylene group By using these groups, further crystallization in the ink does not occur, and a good photocurable inkjet ink can be obtained.
  • a 1 and A 3 are methylene, A 2 is the aforementioned formula —CHR 4 ⁇ , and R 3 is an alkyl group having 4 to 12 carbon atoms or an alkylene group.
  • maleimide derivatives represented by the general formulas (2) to (4).
  • the general formulas (1) to (4) represent symmetric maleimide derivatives in which two identical groups are bonded to R 3.
  • the ink-jet ink and the photocurable composition may contain an asymmetric maleimide derivative in which two different groups are bonded to R 3 together with a symmetric maleimide derivative.
  • maleimide derivative represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.
  • the maleimide derivative obtained in the present invention can be suitably used as a photocurable composition.
  • the photocurable composition can be used with a maleimide derivative alone, it is often used with other polymerizable compounds having an ethylenic double bond such as a vinyl ether compound, a (meth) acryloyl compound, and an N-vinyl compound. It is preferable.
  • Vinyl ether compound which may be added to a photocurable composition.
  • the monofunctional monovinyl ether compound examples include butyl vinyl ether, hexyl vinyl ether, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether, and the like.
  • bifunctional vinyl ether compound examples include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, neopentyl glycol divinyl ether. And cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinyl resorcin, and divinyl hydroquinone.
  • Trifunctional vinyl ether compound examples include glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition moles of ethylene oxide 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether (addition moles 3 of ethylene oxide). Etc.
  • Tetrafunctional or higher vinyl ether compounds examples include pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether, and oxyethylene adducts thereof.
  • vinyl ether compounds more preferred are bifunctional or higher vinyl ether compounds.
  • a bifunctional or higher vinyl ether compound When a bifunctional or higher vinyl ether compound is used, a polymerization reaction with an acid occurs rapidly, which is more preferable in terms of photocuring sensitivity.
  • examples of the vinyl ether compound having an alicyclic skeleton include, for example, cyclohexyl vinyl ether and adamantyl vinyl ether in the case of monofunctionality.
  • examples of the vinyl ether compound having an alicyclic skeleton include, for example, cyclohexyl vinyl ether and adamantyl vinyl ether in the case of monofunctionality.
  • cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, and isovinyl divinyl ether are listed as examples.
  • examples of compounds that may be added to the photocurable composition include N-vinyl compounds such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and N-vinylcaprolactam.
  • examples of the polymerizable compound having an ethylenic double bond include maleic acid, maleic acid esters, fumaric acid, and fumaric acid esters.
  • the maleimide derivative of the present invention itself works as a photoinitiator.
  • a photoinitiator in combination. The following is mentioned as another photoinitiator which may be used together.
  • Benzophenones such as benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and salts thereof
  • Thioxanthone 2 Thioxanthones such as 1,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, and salts thereof
  • anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone
  • acetophenones 5) benzoin methyl Benzoin ethers such as ether 6) 2,4,6-trihalomethyltriazines 7) 1-hydroxycyclohexyl phenyl ket
  • the form to be added to the ink can be added as a dissolved product or a dispersion as required.
  • a sensitizer can be used for the purpose of increasing the absorption wavelength.
  • photosensitizers include benzophenones, thioxanthones, styryl ketones, coumarins, rhodamines, cyanines, merocyanines and the like. Further, dihydrobenzothiain-4-one sensitizers described in JP 2010-018728 A and the like may also be used.
  • the addition amount of the photosensitizer is preferably in the range of 0.1 to 2 times the addition amount of the photoinitiator.
  • ethyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, triethanolamine, etc. may be added.
  • both a dye and a pigment can be used as the colorant, but it is preferable to use a pigment that is not easily photodegraded as a coloring material because of the characteristics of photocuring.
  • a pigment that is not easily photodegraded as a coloring material because of the characteristics of photocuring.
  • colorless inorganic pigments or colored organic pigments such as carbon black, titanium oxide and calcium carbonate can be used.
  • organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red, soluble azo pigments such as ritole red, heliobordeaux, pigment scarlet, and permanent red 2B; alizarin, indanthrone, thio Derivatives from vat dyes such as indigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; isoindolinone Isoindolinone organic pigments such as yellow and isoindolinone orange; Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange; Thioindigo Machine pigments, condensed azo organic pigments, benzimidazolone organic pigments,
  • Organic pigment is color index (CI) No. This is illustrated below.
  • quinacridone-based, phthalocyanine-based, benzimidazolone-based, isoindolinone-based, condensed azo-based, quinophthalone-based, and isoindoline-based organic pigments are preferable because of their excellent light resistance.
  • the organic pigment is preferably fine particles having an average particle diameter in the inkjet ink of 15 to 250 nm as measured by laser scattering.
  • the average particle diameter of the pigment is less than 15 nm, the light resistance is reduced due to the small particle diameter.
  • the average particle diameter exceeds 250 nm, a large amount of coarse particles are contained, and therefore the inkjet head is clogged. This causes problems such as deterioration in ejection stability and generation of minute mist called satellite.
  • the average particle diameter is set to 150 to 300 nm, preferably 180 to 250 nm, in order to provide whiteness and concealment.
  • coarse particles are removed by sufficient dispersion or filtration so that the maximum particle size of the pigment in the inkjet ink does not exceed 1 ⁇ m. If coarse particles are present, the ejection stability is also lowered. Refinement of the organic pigment can be performed using a known dispersion method.
  • the pigment ranges from 1.5 to 8% by mass in the case of colors other than white in the ink-jet ink, and from 10 to 30% by mass in the case of white ink using titanium oxide. It is preferable that it is contained.
  • the pigment dispersant for dispersing the pigment used include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, and a high molecular weight Unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester , Polyoxyethylene nonylphenyl ether, stearylamine acetate, pigment derivatives and the like.
  • Anti-Terra-U polyaminoamide phosphate
  • Anti-Terra-203 / 204 high molecular weight polycarboxylate
  • Disbyk-101 polyaminoamide phosphate manufactured by BYK Chemie.
  • Salt (acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ) "," 400 ",” Bykumen “(high molecular weight unsaturated acid ester),” BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ",” P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid) And silicon) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid and Recon) ", and the like.
  • Demol RN N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18” manufactured by Kao Corporation.
  • These pigment dispersants are preferably contained in an amount of 5 to 70% by mass, preferably 10 to 50% by mass, based on the pigment 100.
  • the amount is less than 5% by mass, the dispersion stability cannot be obtained, and when it is more than 70% by mass, the ejection stability is deteriorated.
  • these pigment dispersants preferably have a solubility of 5% by mass or more in the entire polymerizable compound at 0 ° C.
  • solubility is less than 5% by mass, an undesirable polymer gel or pigment soft aggregate is generated when the inkjet ink is stored at a low temperature, and the storage stability and ejection stability of the inkjet ink are deteriorated.
  • ⁇ Polymerization inhibitor> In the photocurable composition of the present invention, it is preferable to add a radical polymerization inhibitor in order to obtain storage stability.
  • radical polymerization inhibitors methoquinone (hydroquinone monomethyl ether), hydroquinone, 4-methoxy-1-naphthol, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants Agents, ascorbic acids, zinc sulfate, thiocyanates, thiourea derivatives, various sugars, phosphate antioxidants, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, nitrosyl radicals, dicyandiamide and polyalkylene polyamines Examples include polycondensates. In particular, nitrosyl radicals are preferred.
  • the addition amount of the radical polymerization inhibitor is preferably 10 to 5000 ppm. If it is less than 10 ppm, the storage stability cannot be obtained, and the ejection stability is impaired, for example, the viscosity of the ink cannot be increased or the liquid repellency with respect to the inkjet nozzle cannot be obtained. If it exceeds 5000 ppm, the photocuring sensitivity is lowered.
  • the photocurable composition of the present invention contains various additives such as a surfactant, a lubricant, a filler, a rust inhibitor, an antifoaming agent, a thickener, a gelling agent, and polymers as necessary. I can do it.
  • solvent such as an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a nitrogen-containing organic solvent can be added.
  • the photocurable composition of the present invention is preferably cured by irradiating with ultraviolet rays after being applied to a substrate.
  • an irradiation apparatus of the light irradiation method for example, an ultraviolet LED, an ultraviolet laser, a mercury arc lamp, a xenon arc lamp, a low-pressure mercury lamp, a fluorescent lamp, a carbon arc lamp, a tungsten-halogen copying lamp, and sunlight can be used.
  • the photocurable composition of the present invention is more preferably used as an inkjet ink. Since inkjet ink is ejected from a thin micron-order inkjet head nozzle, the viscosity is 5 to 100 mPa ⁇ s at 25 ° C, and the shear rate dependence is as small as possible, and the surface tension is 22 to 35 mN / m at 25 ° C. It is preferable that the inkjet ink has no gel-like substance exceeding 1 ⁇ m other than the pigment, has an electric conductivity of 10 ⁇ S / cm or less, and has no electrical corrosion inside the head. . In the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.
  • the method of light irradiation by inkjet is the above-described multi-pass serial recording method in which inkjet ink is overlaid and cured by an inkjet printer equipped with an irradiation device that applies ultraviolet rays, or a line for recording in one pass. Any recording method can be used.
  • the inkjet ink is applied onto the substrate, and the inkjet ink on the substrate is irradiated with ultraviolet rays so that the inkjet ink is cured or semi-cured. It includes a step of curing the ink-jet ink with lines.
  • polyester polyvinyl chloride, polyethylene, polyurethane, polypropylene
  • acrylic resin polycarbonate, polystyrene, acrylonitrile / butadiene / styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like, and the thickness and shape of these synthetic resin substrates are not limited.
  • metals, glass, printing paper, etc. can be used.
  • Synthesis Example 1 (Synthesis of maleimide derivative 1-1 of the present invention) Into a 300 ml eggplant type flask equipped with a stirrer, a decompression device and a trap, 5.0 g of N- ⁇ -oxyisopropylmaleimide synthesized by the method described in the literature “Organic Synthetic Chemistry Association Vol. 23, No. 2 (1965)” 2.82 g of azelaic acid, 0.7 g of p-toluenesulfonic acid monohydrate, 0.05 g of 2,6-tert-butyl-p-cresol and 20 ml of toluene were sequentially added, and the resulting water and toluene were combined under reduced pressure.
  • reaction was terminated by stirring for 12 hours under the condition of a reaction temperature of 80 ° C.
  • the reaction solution was cooled to room temperature, dissolved in 300 ml of ethyl acetate, and washed 3 times with 100 ml of saturated aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine.
  • the organic layer was dried over magnesium sulfate and concentrated to obtain 3.2 g of maleimide derivative 1-1 of the present invention.
  • the resulting composition was oily at room temperature.
  • Synthesis Example 2 (Synthesis of maleimide derivative 1-2 of the present invention) By synthesizing under the same conditions as in Synthesis Example 1 except that 3.03 g of sebacic acid was used instead of 2.82 g of azelaic acid used in Synthesis Example 1, 3 of the maleimide derivative 1-2 of the present invention was obtained. .3 g was obtained. The resulting composition was oily at room temperature.
  • Synthesis Example 3 (Synthesis of Maleimide Derivative 2-1 of Comparative Example) In place of 5.0 g of N- ⁇ -oxyisopropylmaleimide used in Synthesis Example 1, N- ⁇ -oxyethyl synthesized by the method described in the document “Organic Synthetic Chemistry, Vol. 23, No. 2 (1965)” By synthesizing under the same conditions as in Synthesis Example 1, except that 4.55 g of maleimide was used, 3.3 g of maleimide derivative 2-1 of Comparative Example was obtained. The resulting composite was a solid at room temperature.
  • Synthesis Example 4 (Synthesis of maleimide derivative 1-3 of the present invention) In a 300 ml eggplant-shaped flask equipped with a stirrer, a decompression device and a trap, 33.8 g of 2-maleimido-2-methylacetic acid synthesized by the method described in Patent Document “3599160”, 10.2 g of diethylene glycol, p-toluenesulfone Acid monohydrate (4.47 g), 2,6-tert-butyl-p-cresol (0.35 g), and toluene (20 ml) were sequentially added. The reaction was terminated by stirring for 5 hours under the conditions described above.
  • the reaction solution was cooled to room temperature, dissolved in 300 ml of ethyl acetate, and washed 3 times with 100 ml of saturated aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine.
  • the organic layer was dried over magnesium sulfate and concentrated to obtain 24.7 g of maleimide derivative 1-3 of the present invention.
  • the resulting composition was oily at room temperature.
  • Synthesis Example 5 (Synthesis of maleimide derivative 1-4 of the present invention) Instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4, 39.4 g of 2-maleimido-2-isobutyrylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used. Was synthesized under the same conditions as in Synthesis Example 4 to obtain 28.1 g of maleimide derivative 1-4 of the present invention. The resulting composition was oily at room temperature.
  • Synthesis Example 6 Synthesis of maleimide derivative 1-5 of the present invention
  • Synthesis Example 4 Synthesis of maleimide derivative 1-5 of the present invention
  • 42.2 g of 2-maleimido-2-isovalerylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used.
  • the resulting composition was oily at room temperature.
  • Synthesis Example 7 (Synthesis of Maleimide Derivative 2-2 of Comparative Example) Synthetic Example 4 except that 31.2 g of maleimidoacetic acid synthesized by the method described in Patent Document “No. 3599160” was used instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthetic Example 4. By synthesizing under the same conditions, 30.2 g of maleimide derivative 2-2 of Comparative Example was obtained. The resulting composite was a solid at room temperature.
  • Synthesis Example 8 (Synthesis of maleimide derivative 1-6 of the present invention) The maleimide derivative 1-6 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 11.4 g of 1,6-hexanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 25.4g was obtained. The resulting composition was oily at room temperature.
  • Synthesis Example 9 (Synthesis of maleimide derivative 1-7 of the present invention)
  • the maleimide derivative 1-7 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 15.4 g of 1,9-nonanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 22.3 g was obtained.
  • the resulting composition was oily at room temperature.
  • Synthesis Example 10 (Synthesis of maleimide derivative 1-8 of the present invention) The maleimide derivative 1-8 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 24.8 g of 1,16-hexadecanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 32.5 g was obtained. The resulting composition was oily at room temperature.
  • Synthesis Example 11 Synthesis of maleimide derivative 1-9 of the present invention
  • 15.4 g of 2-butyl-2-ethyl-1,3-propanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4.
  • 26.2 g of maleimide derivative 1-9 of the present invention was obtained.
  • the resulting composition was oily at room temperature.
  • Synthesis Example 12 (Synthesis of maleimide derivative 1-10 of the present invention) Synthesis was performed under the same conditions as in Synthesis Example 4 except that 15.4 g of 2,4-diethyl-1,5-pentanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 27.8 g of the maleimide derivative 1-10 was obtained. The resulting composition was oily at room temperature.
  • Synthesis Example 13 Synthesis of maleimide derivative 1-11 of the present invention
  • Synthesis Example 4 instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4, 36 mg of 2- (3-maleimido) -2-methylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used.
  • 31.2 g of maleimide derivative 1-11 of the present invention was obtained by synthesis under the same conditions as in Synthesis Example 20 except that 0.6 g was used. The resulting composition was oily at room temperature.
  • Synthesis Example 14 (Synthesis of maleimide derivative 1-12 of the present invention) 2- (3,4,5,6-tetrahydro-phthaloimide) synthesized by the method described in Patent Document “No. 3599160” instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4 By synthesizing under the same conditions as in Synthesis Example 4 except that 44.6 g of -2-methylacetic acid was used, 35.4 g of maleimide derivative 1-12 of the present invention was obtained. The resulting composition was oily at room temperature.
  • Synthesis Example 15 (Synthesis of maleimide derivative 1-13 of the present invention) By synthesizing under the same conditions as in Synthesis Example 4 except that 14.2 g of 1-butanol was used in place of 10.2 g of diethylene glycol used in Synthesis Example 4, 36. 5 g was obtained. The resulting composition was oily at room temperature.
  • Example 1 Compatibility with maleimide derivative alone (Preparation of photocurable composition 1)
  • a photocurable composition 1 having the following composition was prepared and used for measurement of light emission and photocuring sensitivity.
  • Photocurable Composition Composition Maleimide Derivative 1-1 of the Present Invention 97.9 mass% Photoinitiator (Darocur 1173 manufactured by BASF) 2.0% by mass TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) 0.1% by mass (Preparation of photocurable compositions 2 to 17)
  • the photocurable compositions 2 to 2 were prepared in the same manner as the photocurable composition 1 except that the maleimide derivative 1-1 of the present invention was changed to the maleimide derivatives shown in Tables 1 to 4. 17 was produced.
  • ⁇ No missing nozzles were recognized. ⁇ : One or more missing nozzles occurred in less than 3% of the whole. ⁇ : Missing nozzles occurred in 3% or more and less than 10% of the whole. More than 10% occurred.
  • ⁇ was cured at a light volume 10mJ / cm 2: but did not cure in the amount of light 10mJ / cm 2, the amount of light 30mJ / cm 2 was cured in ⁇ : but did not cure in the amount of light 30mJ / cm 2, the amount of light 100mJ Cured at / cm 2 ⁇ : Not cured at 100 mJ / cm 2 .
  • the photocurable composition using the maleimide derivative of the present invention has good ink jetting properties and high photocuring sensitivity.
  • Example 2 (Implementation when using inkjet ink) ⁇ Production of inkjet ink> (Preparation of inkjet ink 1) TEGDVE (triethylene glycol divinyl ether) 33.4 g Maleimide derivative 1-1 55.5g Carbon black 2.0g Sulsperse 24000GR (made by Lubrizol) 1.0g TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) 0.1 g was mixed and dispersed with a zirconia bead having a particle size of 0.5 mm for 6 hours using a paint shaker.
  • TEGDVE triethylene glycol divinyl ether
  • Maleimide derivative 1-1 55.5g Carbon black
  • Sulsperse 24000GR made by Lubrizol
  • TEMPO 2,2,6,6-tetramethylpiperidinyl-N-oxyl
  • DAROCURE TPO phosphine
  • Quantacure ITX manufactured by thioxanthone photosensitizer manufactured by Aceto Chemical
  • the equivalent ratio of vinyl ether to maleimide derivative 1-1 in this ink is 50/50.
  • Ink jet ink 1 was prepared in the same manner as ink jet ink 1 except that the maleimide derivative shown in Table 5 was used instead of maleimide derivative 1-1 and the equivalent ratio was 50/50. To 17 were produced.
  • ⁇ One or more missing nozzles occurred in less than 3% of the total.
  • A Cured with a light amount of 10 mJ / cm 2 .

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  • Organic Chemistry (AREA)
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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract

A photocurable ink jet ink characterized by comprising a maleimide derivative represented by general formula (1).

Description

光硬化性のインクジェットインク、画像形成方法、マレイミド誘導体、及び光硬化性組成物Photocurable inkjet ink, image forming method, maleimide derivative, and photocurable composition
　本発明は、光硬化性のインクジェットインク、画像形成方法、マレイミド誘導体、及び光硬化性組成物に関し、更に詳しくは、光照射装置を具備したインクジェットプリンターに用いる光硬化性のインクジェットインク及び該インクジェットインクに用いるマレイミド誘導体に関する。 The present invention relates to a photocurable inkjet ink, an image forming method, a maleimide derivative, and a photocurable composition. More specifically, the present invention relates to a photocurable inkjet ink used in an inkjet printer equipped with a light irradiation device and the inkjet ink. Relates to maleimide derivatives used in
　インクジェット記録方法は、比較的簡単な装置で高精細な画像の記録が可能であり、各方面で急速な発展を遂げている。また、使用される用途も多岐に亘り、それぞれの目的にあった記録媒体、あるいはインクジェットインク（以下単にインクとも言う）が使用される。特に、近年では記録速度の大幅な向上がみられ、軽印刷用途にも耐え得る性能を持つプリンターの開発も行われている。 The inkjet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. In addition, there are a wide variety of uses, and a recording medium or ink jet ink (hereinafter also simply referred to as ink) suitable for each purpose is used. In particular, in recent years, the recording speed has been greatly improved, and printers having performance capable of withstanding light printing applications have been developed.
　このインクジェット記録方式は、インクジェットヘッドよりインクを吐出し、記録媒体に着弾して、画像を形成する。インクジェットヘッドより吐出させるためには、インクは低粘度であることが必要になる。一方、色の異なった複数のインクが記録媒体上で着弾するため、ブリードと呼ばれる色混ざりを防止するためには、高粘度のインクが必要である。 In this ink jet recording system, ink is ejected from an ink jet head and landed on a recording medium to form an image. In order to eject the ink from the ink jet head, the ink needs to have a low viscosity. On the other hand, since a plurality of inks having different colors land on the recording medium, high-viscosity inks are necessary to prevent color mixing called bleeding.
　このジレンマを解決するためのひとつの方法として、光硬化性インクを用いる紫外線硬化型インクジェットが実用化されている。これは、インク中に光硬化性モノマーと光重合開始剤を加えておき、記録媒体に着弾後に光を照射し、インクを硬化させることで、出射性の確保とブリードの防止を両立させている。しかし、別の本質的な問題を抱えている。 As one method for solving this dilemma, an ultraviolet curable ink jet using a photocurable ink has been put into practical use. This is achieved by adding a photocurable monomer and a photopolymerization initiator to the ink, irradiating the recording medium with light and then curing the ink, thereby ensuring both emission and prevention of bleeding. . But it has another essential problem.
　ラジカル重合系は酸素阻害により、カチオン重合系では空気中の水により阻害を受けるために、インクジェットのように基材の上に非接触で小液滴のドットを形成する方式では、これらの阻害要因が大きく働き、ラジカル重合系では高照度高光量の大型な紫外線照射装置を用いる必要がある、カチオン重合系では湿度をコントロールする必要があるなどの対策が必要になる欠点がある。 The radical polymerization system is inhibited by oxygen, and the cationic polymerization system is inhibited by water in the air. In the method of forming small droplet dots in a non-contact manner on the substrate like inkjet, these inhibition factors The radical polymerization system has a drawback that it is necessary to use a large ultraviolet irradiator with high illuminance and high light quantity in the radical polymerization system, and it is necessary to control the humidity in the cationic polymerization system.
　ラジカル重合系で酸素阻害を低減する一般的な方法としては、酸素ラジカルを捕捉するためにインク中にトリエタノールアミンのようなアミンを加えることがあげられる。また、最近、アミノ基を有するモノマーを用いる方法も提案されているが、（例えば、特許文献１、２参照）効果は限定的である。 As a general method for reducing oxygen inhibition in a radical polymerization system, an amine such as triethanolamine is added to the ink in order to trap oxygen radicals. Recently, a method using an amino group-containing monomer has also been proposed (for example, see Patent Documents 1 and 2), but the effect is limited.
　酸素阻害を減らす方法としては、酸素阻害を受けにくいモノマー系を採用することがあげられる。ひとつには、エン－チオール反応を用いることで、酸素阻害を減らすことが出来るが、（例えば、特許文献３参照）チオール特有の悪臭があり、インクジェットインクで用いるには耐え難いものがあった。 As a method for reducing oxygen inhibition, a monomer system that is less susceptible to oxygen inhibition can be employed. For one thing, oxygen inhibition can be reduced by using the ene-thiol reaction (see, for example, Patent Document 3), but there is a odor peculiar to thiols, and there are some that are unbearable for use in inkjet inks.
　他に、ビニルエーテルをはじめとする電子過多なドナーモノマーと、無水マレイン酸、マレイミドなど電子不足モノマーとの組み合わせで行う電荷移動錯体重合（ＣＴ重合）を用いることである。この反応は、酸素阻害が少ないことが知られていたが、インクジェットインクとして用いる場合、液体状態で長く保存する必要があるために、無水マレイン酸では保存性が悪く、マレイミドでは溶解性が乏しいために、インクジェットノズルが詰まり、出射出来なかった。 In addition, charge transfer complex polymerization (CT polymerization) performed using a combination of an electron-rich donor monomer such as vinyl ether and an electron-deficient monomer such as maleic anhydride or maleimide is used. This reaction was known to have little oxygen inhibition, but when used as an inkjet ink, it must be stored in a liquid state for a long time, so maleic anhydride has poor storage and maleimide has poor solubility. In addition, the inkjet nozzles were clogged and could not be emitted.
　溶解性の高いマレイミド化合物としては、中央部にアルキレンオキシドを配するマレイミド（例えば、特許文献４参照）、オレイン酸の二量体から誘導されるマレイミド（例えば、特許文献５参照）が提案されており、ビニルエーテルとの組み合わせも記載されていた。しかし、これらの化合物では、分子量が大きすぎて高粘度なインクしか出来ず、良好な出射が出来なかった。 As maleimide compounds having high solubility, maleimides (see, for example, Patent Document 4) in which an alkylene oxide is arranged at the center, and maleimides derived from a dimer of oleic acid (for example, see Patent Document 5) have been proposed. The combination with vinyl ether was also described. However, with these compounds, the molecular weight was too large, and only a highly viscous ink could be produced, and good emission was not possible.
　また、インクジェットインクを溶剤で希釈し粘度を下げてインクジェットインク吐出させる試みもあるが（例えば、特許文献６参照）、乾燥機がなければ定着しないなど、本来の紫外線硬化型インクジェットにふさわしいものではなく、ヘッド面でのインク乾燥による目詰まりが起こるなど、インクジェットインクの吐出も不十分であった。 In addition, there is an attempt to dilute an inkjet ink with a solvent and lower the viscosity to eject the inkjet ink (for example, see Patent Document 6). However, it is not suitable for an original ultraviolet curable inkjet because it does not fix without a dryer. Ink jet ink was also insufficiently discharged, such as clogging due to ink drying on the head surface.
　コーティング剤などの光硬化性組成物の臭気の改善と光感度の改良のために、液体のマレイミド化合物（例えば、特許文献４参照）を用いる試みもなされた。また、ビスアリルナジマレイミドとビスマレイミドを含有するインクジェットインク用光硬化性組成物を溶剤で希釈して粘度を下げる（例えば、特許文献６参照）ことも提案されている。更に、液体にするために十分な長さと分岐を有する液状マレイミド（例えば、特許文献５参照）も開示されているが、何れもインクジェットインクに適用した場合、光硬化感度と吐出性の両立が不十分であり改良がのぞまれていた。 Attempts have been made to use liquid maleimide compounds (see, for example, Patent Document 4) in order to improve odor and photosensitivity of photocurable compositions such as coating agents. It has also been proposed to dilute a photocurable composition for inkjet inks containing bisallyl nadimaleimide and bismaleimide with a solvent to lower the viscosity (see, for example, Patent Document 6). Furthermore, liquid maleimides (see, for example, Patent Document 5) having a length and a branch sufficient to form a liquid are also disclosed, but when both are applied to inkjet inks, it is not possible to achieve both photocuring sensitivity and ejectability. It was enough and improvement was expected.
特開２００９－３５６５０号公報JP 2009-35650 A 特開２００８－２０８２１６号公報JP 2008-208216 A 特開２００９－２４９５７２号公報JP 2009-249572 A 特開平１１－１２４４０３号公報Japanese Patent Laid-Open No. 11-124403 特開２００８－１３７７２号公報JP 2008-13772 A 国際公開第０６／０７５６５４号パンフレットInternational Publication No. 06/075654 Pamphlet
　本発明は上記課題に鑑みなされたものであり、本発明の目的は、光硬化感度が高く、インクジェットプリンターで出射可能である光硬化性組成物、光硬化性のインクジェットインクおよび画像形成方法を提供することにある。また、他の目的は、当該用途に適した液体のマレイミド誘導体を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a photocurable composition, a photocurable inkjet ink, and an image forming method that have high photocuring sensitivity and can be emitted by an inkjet printer. There is to do. Another object is to provide a liquid maleimide derivative suitable for the application.
　本発明の上記目的は、以下の構成により達成することができる。 The above object of the present invention can be achieved by the following configuration.
　１．下記一般式（１）で表されるマレイミド誘導体を含有することを特徴とする光硬化性インクジェットインク。 1. A photocurable inkjet ink comprising a maleimide derivative represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　（式中、Ｒ１、Ｒ２は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表し、Ｒ１、Ｒ２はそれぞれ結合して環を形成してもよい。Ａ１、Ａ３は、それぞれ独立にアルキレン基を表し、Ａ２は不斉中心を有する炭化水素基を表す。Ｙは、カルボニルオキシ（－Ｃ＝Ｏ－Ｏ－）またはオキシカルボニル（－Ｏ－Ｃ＝Ｏ－）を表す。ｐは１または２を表す。Ｒ３はｐが１の場合は分子量１５～６００のアルキル基、アルキレンオキシ基、ｐが２の場合は、分子量１４～６００のアルキレン基、アルキレンオキシ基を表す。ｍは０または１、ｎは０または１を表す。）
　２．前記一般式（１）における、Ａ１、およびＡ３はメチレン基、Ａ２はＣＨＲ４、Ｒ３は炭素数４～１２のアルキル基、又はアルキレン基であり、Ｒ４は炭素数１～４のアルキル基を表すことを特徴とする前記１記載の光硬化性インクジェットインク。 (Wherein R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring. A 1 , A 3 independently represents an alkylene group, A 2 represents a hydrocarbon group having an asymmetric center, and Y represents carbonyloxy (—C═O—O—) or oxycarbonyl (—O—C═O). P represents 1 or 2. R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2. Represents an oxy group, m represents 0 or 1, and n represents 0 or 1.)
2. In the general formula (1), A 1 and A 3 are methylene groups, A 2 is CHR 4 , R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group, and R 4 is 1 to 4 carbon atoms. 2. The photocurable ink-jet ink as described in 1 above, which represents an alkyl group of
　３．前記一般式（１）が、下記一般式（２）、一般式（３）又は一般式（４）で表されることを特徴とする前記１又は２項記載の光硬化性インクジェットインク。 3. 3. The photocurable inkjet ink according to 1 or 2, wherein the general formula (1) is represented by the following general formula (2), general formula (3), or general formula (4).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　（式中、Ｒ４は、前記２記載のＲ４と同義の基を表し、ｐは一般式（１）のｐと同義である。Ｒ５は直鎖の炭素数４～１２のアルキル基、又はアルキレン基を表す。）
　４．前記１～３のいずれか１項記載の光硬化性インクジェットインクを用いることを特徴とする画像形成方法。 (Wherein, R 4, said 2 represents R 4 group having the same meaning as described, p has the same meaning as p in the general formula (1) .R 5 is an alkyl group having 4 to 12 carbon atoms linear, Or represents an alkylene group.)
4). 4. An image forming method using the photocurable inkjet ink according to any one of 1 to 3 above.
　５．下記一般式（１）で表されるマレイミド誘導体。 5. A maleimide derivative represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　（式中、Ｒ１、Ｒ２は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表し、Ｒ１、Ｒ２はそれぞれ結合して環を形成してもよい。Ａ１、Ａ３は、それぞれ独立にアルキレン基を表し、Ａ２は不斉中心を有する炭化水素基を表す。Ｙは、カルボニルオキシ（－Ｃ＝Ｏ－Ｏ－）またはオキシカルボニル（－Ｏ－Ｃ＝Ｏ－）を表す。ｐは１または２を表す。Ｒ３はｐが１の場合は分子量１５～６００のアルキル基、アルキレンオキシ基、ｐが２の場合は、分子量１４～６００のアルキレン基、アルキレンオキシ基を表す。ｍは０または１、ｎは０または１を表す。）
　６．前記一般式（１）における、Ａ１、およびＡ３はメチレン基、Ａ２はＣＨＲ４、Ｒ３は炭素数４～１２のアルキル基、又はアルキレン基であり、Ｒ４は炭素数１～４のアルキル基を表すことを特徴とする前記５記載のマレイミド誘導体。 (Wherein R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring. A 1 , A 3 independently represents an alkylene group, A 2 represents a hydrocarbon group having an asymmetric center, and Y represents carbonyloxy (—C═O—O—) or oxycarbonyl (—O—C═O). P represents 1 or 2. R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2. Represents an oxy group, m represents 0 or 1, and n represents 0 or 1.)
6). In the general formula (1), A 1 and A 3 are methylene groups, A 2 is CHR 4 , R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group, and R 4 is 1 to 4 carbon atoms. 6. The maleimide derivative according to 5 above, which represents an alkyl group of
　７．前記一般式（１）が、下記一般式（２）、一般式（３）又は一般式（４）で表されることを特徴とする前記５又は６記載のマレイミド誘導体。 7. The maleimide derivative according to 5 or 6, wherein the general formula (1) is represented by the following general formula (2), general formula (3), or general formula (4).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　（式中、Ｒ４は、前記６記載のＲ４と同義の基を表し、ｐは一般式（１）のｐと同義である。Ｒ５は直鎖の炭素数４～１２のアルキル基、又はアルキレン基を表す。）
　８．前記５～７のいずれか１項記載のマレイミド誘導体を含有することを特徴とする光硬化性組成物。 (Wherein, R 4, the 6 represents R 4 group having the same meaning as described, p has the same meaning as p in the general formula (1) .R 5 is an alkyl group having 4 to 12 carbon atoms linear, Or represents an alkylene group.)
8). 8. A photocurable composition comprising the maleimide derivative according to any one of 5 to 7 above.
　本発明によれば、マレイミド誘導体に特定の構造を導入することにより、光硬化感度を落とすことなく、液体のマレイミド誘導体を与え、溶媒希釈せずともインクジェットヘッドで出射できるインクジェットインクを提供することができる。 According to the present invention, by introducing a specific structure into a maleimide derivative, a liquid maleimide derivative can be provided without reducing photocuring sensitivity, and an inkjet ink that can be emitted by an inkjet head without being diluted with a solvent can be provided. it can.
　以下本発明を実施するための最良の形態について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.
　本発明者らは、上記課題に鑑み鋭意検討を行った結果、マレイミド誘導体に不斉中心を有する３価の炭化水素基を導入することにより、光硬化感度を落とすことなく、液体で低粘度のマレイミド誘導体を与え、溶媒希釈せずともインクジェットヘッドで出射でき、優れた高画質の画像が得られるインクジェットインクを見出し、本発明に至った次第である。 As a result of intensive studies in view of the above problems, the present inventors have introduced a trivalent hydrocarbon group having an asymmetric center into a maleimide derivative, thereby reducing the photocuring sensitivity and reducing the viscosity of the liquid. As soon as the present invention has been found, an ink-jet ink which can be emitted by an ink-jet head without being diluted with a solvent and can be obtained with a maleimide derivative and which can provide an excellent high-quality image is obtained.
　＜液体になる理由＞
　本発明のマレイミドは、不斉中心を有する３価の炭化水素基によってＤ体Ｌ体の混合物になるとともに、マレイミド基の傍に導入することによって、マレイミドの結晶化が立体障害により妨げられることにより、比較的低い分子量でも、インク中で析出が起きず、良好な出射性が得られたと推察している。 <Reason for becoming liquid>
The maleimide of the present invention becomes a mixture of the D-form and L-form by a trivalent hydrocarbon group having an asymmetric center, and by introducing it near the maleimide group, the crystallization of maleimide is hindered by steric hindrance. It is presumed that, even with a relatively low molecular weight, no precipitation occurred in the ink, and good light emission was obtained.
　本発明で液体のマレイミド誘導体とは室温で液体（油状を含む）となっていることを意図する。 In the present invention, the liquid maleimide derivative is intended to be liquid (including oil) at room temperature.
　本発明のマレイミド誘導体は、好ましくはマレイミド環に対してαまたはβ位の位置に不斉中心の基を設ける。 The maleimide derivative of the present invention preferably has an asymmetric center group at the position of α or β position with respect to the maleimide ring.
　＜インクジェット吐出に適する理由＞
　更に、本発明の一般式（１）において、Ｒ３の分子量を１４～６００にすることで、同じ液体でＲ３が高分子のものよりも粘度を下げ、インクジェットヘッドから吐出するのに、適する粘度にすることができる。 <Reason for ink jet discharge>
Furthermore, in the general formula (1) of the present invention, by setting the molecular weight of R 3 to 14 to 600, the viscosity is lower than that of the same liquid and R 3 is a polymer, and it is suitable for discharging from the inkjet head. Can be a viscosity.
　更に好ましくは、Ｒ３の分子量は５６～１６８である。 More preferably, the molecular weight of R 3 is 56 to 168.
　更に好ましくは、Ｒ３が炭素数４～１２のアルキル基またはアルキレン基を表す。 More preferably, R 3 represents an alkyl group or alkylene group having 4 to 12 carbon atoms.
　＜光硬化感度が向上する理由＞
　キラル基を有するマレイミド化合物を用いると、キラル基を有しないマレイミド化合物を用いる場合に比べて、光硬化感度は高くなることは見いだされた。その理由としては、複数の光学異性体が系中に存在することで、結晶化しにくくなり、分子が自由に動けるようになるために、反応性が高まったものと考えている。 <Reason for improving photocuring sensitivity>
It has been found that when a maleimide compound having a chiral group is used, the photocuring sensitivity is higher than when a maleimide compound having no chiral group is used. The reason for this is that the presence of a plurality of optical isomers in the system makes it difficult to crystallize and the molecules can move freely.
　＜一般式（１）で表されるマレイミド誘導体＞
　一般式（１）において、Ｒ１及びＲ２で表されるアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基等を挙げることができる。またＲ１及びＲ２が結合して、シクロプロペン環、シクロブチレン環、シクロペンテン環、シクロヘキセン環等を形成しても良い。 <Maleimide derivative represented by general formula (1)>
In the general formula (1), examples of the alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. R 1 and R 2 may combine to form a cyclopropene ring, a cyclobutylene ring, a cyclopentene ring, a cyclohexene ring, or the like.
　Ａ１、Ａ３で表される２価の有機連結基としては、メチレン基、エチレン基、ブチレン基、ヘキシレン基エチレンオキシ基、ポリエチレンオキシ基、ブチレンオキシ基、ポリブチレンオキシ基、エチレンオキシカルボニル基、ヘキシレンオキシカルボニル基、メチレンエステル基、ヘキシレンエステル基、フェニレン基、メチルフェニレン基、オキシカルボニルフェニレンカルボニルオキシ基、カルボニルオキシフェニレンオキシカルボニル基が挙げられる。 Examples of the divalent organic linking group represented by A 1 or A 3 include a methylene group, an ethylene group, a butylene group, a hexylene group, an ethyleneoxy group, a polyethyleneoxy group, a butyleneoxy group, a polybutyleneoxy group, and an ethyleneoxycarbonyl group. Hexyleneoxycarbonyl group, methylene ester group, hexylene ester group, phenylene group, methylphenylene group, oxycarbonylphenylenecarbonyloxy group, and carbonyloxyphenyleneoxycarbonyl group.
　Ａ２は不斉炭素（キラル炭素）を有する基を表す。 A 2 represents a group having an asymmetric carbon (chiral carbon).
　具体的には、下記式が挙げられる。 Specifically, the following formula can be cited.
　　　－ＣＨＲ４－
　式中、好ましくは、Ｒ４は炭素数１～１２のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルキルオキシ基、炭素数１～１８のアルキルカルボニルオキシ基または水酸基を表す。更に好ましくは、炭素数１～４のアルキル基（メチル基、エチル基、プロピル基、イソブチル基等）が上げられる。 -CHR 4 -
In the formula, preferably R 4 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, an alkylcarbonyloxy group having 1 to 18 carbon atoms, or a hydroxyl group. To express. More preferred is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, isobutyl group, etc.).
　ｐが１の場合のＲ３で表される分子量１５～６００のアルキル基としては、好ましくは炭素数１～１８の分岐しても良いアルキル基を表し、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ネオペンチル基、ドデシレル基、２，２，４－オクチル基等を挙げることができる。 When p is 1, the alkyl group having a molecular weight of 15 to 600 represented by R 3 preferably represents an alkyl group having 1 to 18 carbon atoms which may be branched. Specifically, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, neopentyl group, dodecylyl group, 2,2,4-octyl group and the like.
　ｐが２の場合のＲ３で表される分子量１４～６００のアルキレン基としては、好ましくは炭素数１～１８の分岐しても良いアルキレン基を表し、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、ネオペンチレン基、ドデシレン基、２，２，４－オクチレン基等を挙げることができる。 The alkylene group having a molecular weight of 14 to 600 represented by R 3 when p is 2 preferably represents an alkylene group having 1 to 18 carbon atoms which may be branched, and specifically includes a methylene group, an ethylene group , Propylene group, butylene group, hexylene group, neopentylene group, dodecylene group, 2,2,4-octylene group, and the like.
　ｐが１の場合のＲ３で表されるアルキレンオキシ基としては、ヒドロキシまたはアルコキシポリエチレンオキシ基、ヒドロキシまたはアルコキシポリプロレンオキシ基、ヒドロキシまたはアルコキシポリブチレンオキシ基等が挙げられるが、これらに限定されるものではない。 Examples of the alkyleneoxy group represented by R 3 when p is 1 include, but are not limited to, a hydroxy or alkoxy polyethyleneoxy group, a hydroxy or alkoxypolyproleneoxy group, a hydroxy or alkoxypolybutyleneoxy group, and the like. It is not something.
　好ましいＲ３は、炭素数１～１８の分岐しても良いアルキレン基、炭素数１～１８の分岐しても良いアルキル基であり、さらに好ましくは、炭素数４～１２の分岐しても良いアルキレン基である。これらの基を用いることにより、さらにインクでの結晶化が発生せず、良好な光硬化性インクジェットインクを得ることが出来る。 R 3 is preferably an alkylene group having 1 to 18 carbon atoms which may be branched, or an alkyl group having 1 to 18 carbon atoms which may be branched, and more preferably a branched chain having 4 to 12 carbon atoms. An alkylene group; By using these groups, further crystallization in the ink does not occur, and a good photocurable inkjet ink can be obtained.
　さらに好ましいマレイミド誘導体としては、Ａ１、およびＡ３はメチレン、Ａ２は上述した、式　－ＣＨＲ４－　であり、Ｒ３は炭素数４～１２のアルキル基、又はアルキレン基である。 As more preferred maleimide derivatives, A 1 and A 3 are methylene, A 2 is the aforementioned formula —CHR 4 −, and R 3 is an alkyl group having 4 to 12 carbon atoms or an alkylene group.
　特に好ましくは、前記一般式（２）～（４）で表されるマレイミド誘導体を挙げることができる。 Particularly preferred are maleimide derivatives represented by the general formulas (2) to (4).
　一般式（１）～（４）でｐ＝２の場合、一般式（１）～（４）はＲ３に二つの同じ基が結合した対称型のマレイミド誘導体を表すが、本発明の光硬化性インクジェットインクおよび光硬化性組成物は、対称型のマレイミド誘導体と共に、Ｒ３に二つの異なる基が結合した非対称型のマレイミド誘導体を含んでも良い。 When p = 2 in the general formulas (1) to (4), the general formulas (1) to (4) represent symmetric maleimide derivatives in which two identical groups are bonded to R 3. The ink-jet ink and the photocurable composition may contain an asymmetric maleimide derivative in which two different groups are bonded to R 3 together with a symmetric maleimide derivative.
　以下に本発明の一般式（１）で表されるマレイミド誘導体の具体例を示すが、本発明はこの限りではない。 Specific examples of the maleimide derivative represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　（本発明の光硬化性組成物の好ましい形態）
　本発明で得られたマレイミド誘導体は、光硬化性組成物として、好適に用いることが出来る。光硬化性組成物は、マレイミド誘導体単独でも用いることは出来るが、多くの場合、ビニルエーテル化合物、（メタ）アクリロイル化合物、Ｎ－ビニル化合物などのエチレン性二重結合を有する他の重合性化合物とともに用いることが好ましい。 (Preferred form of the photocurable composition of the present invention)
The maleimide derivative obtained in the present invention can be suitably used as a photocurable composition. Although the photocurable composition can be used with a maleimide derivative alone, it is often used with other polymerizable compounds having an ethylenic double bond such as a vinyl ether compound, a (meth) acryloyl compound, and an N-vinyl compound. It is preferable.
　《ビニルエーテル化合物》
　本発明において、光硬化性組成物に加えてもよいビニルエーテル化合物として以下のものが挙げられる。 《Vinyl ether compound》
In this invention, the following are mentioned as a vinyl ether compound which may be added to a photocurable composition.
　（単官能のモノビニルエーテル化合物）
　単官能モノビニルエーテル化合物としては、例えば、ブチルビニルエーテル、ヘキシルビニルエーテル、エチルヘキシルビニルエーテル、フェニルビニルエーテル、ベンジルビニルエーテル、エチルエトキシビニルエーテル、アセチルエトキシエトキシビニルエーテル、シクロヘキシルビニルエーテル、アダマンチルビニルエーテル、等を挙げることができる。 (Monofunctional monovinyl ether compound)
Examples of the monofunctional monovinyl ether compound include butyl vinyl ether, hexyl vinyl ether, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether, and the like.
　（二官能のビニルエーテル化合物）
　二官能のビニルエーテル化合物としては、例えば、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールビニルエーテル、ブチレンジビニルエーテル、ジブチレングリコールジビニルエーテル、ネオペンチルグリコールジビニルエーテル、シクロヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ノルボルニルジメタノールジビニルエーテル、イソバイニルジビニルエーテル、ジビニルレゾルシン、ジビニルハイドロキノン等を挙げることができる。 (Bifunctional vinyl ether compound)
Examples of the bifunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, neopentyl glycol divinyl ether. And cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinyl resorcin, and divinyl hydroquinone.
　（三官能のビニルエーテル化合物）
　三官能のビニルエーテル化合物としては、例えば、グリセリントリビニルエーテル、グリセリンエチレンオキシド付加物トリビニルエーテル（エチレンオキシドの付加モル数６）、トリメチロールプロパントリビニルエーテル、トリビニルエーテルエチレンオキシド付加物トリビニルエーテル（エチレンオキシドの付加モル数３）等を挙げることができる。 (Trifunctional vinyl ether compound)
Examples of the trifunctional vinyl ether compound include glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition moles of ethylene oxide 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether (addition moles 3 of ethylene oxide). Etc.
　（四官能以上のビニルエーテル化合物）
　四官能以上のビニルエーテル化合物としては、例えば、ペンタエリスリトールトリビニルエーテル、ジトリメチロールプロパンヘキサビニルエーテル、それらのオキシエチレン付加物が挙げられる。 (Tetrafunctional or higher vinyl ether compounds)
Examples of the tetrafunctional or higher functional vinyl ether compound include pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether, and oxyethylene adducts thereof.
　上記各ビニルエーテル化合物のうち、より好ましくは二官能以上のビニルエーテル化合物である。二官能以上のビニルエーテル化合物を用いると、酸による重合反応が速やかに起こり、光硬化感度の点でより好ましい。 Of the above vinyl ether compounds, more preferred are bifunctional or higher vinyl ether compounds. When a bifunctional or higher vinyl ether compound is used, a polymerization reaction with an acid occurs rapidly, which is more preferable in terms of photocuring sensitivity.
　また、脂環式骨格を有するビニルエーテル化合物としては、単官能の場合、例えばシクロヘキシルビニルエーテル、アダマンチルビニルエーテル等を挙げることができる。二官能の場合はシクロヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ノルボルニルジメタノールジビニルエーテル、イソバイニルジビニルエーテルが例として挙げられる。 In addition, examples of the vinyl ether compound having an alicyclic skeleton include, for example, cyclohexyl vinyl ether and adamantyl vinyl ether in the case of monofunctionality. In the case of bifunctionality, cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, and isovinyl divinyl ether are listed as examples.
　《（メタ）アクリロイル化合物》
　本発明において、光硬化性組成物に加えても良いアクリルロイル化合物として以下のものが挙げられる。 << (Meth) acryloyl compound >>
In this invention, the following are mentioned as an acryloyl compound which may be added to a photocurable composition.
　イソアミルアクリレート、ステアリルアクリレート、ラウリルアクリレート、デシルアクリレート）、イソミルスチルアクリレート）、イソステアリルアクリレート、２－エチルヘキシルアクリレート、２－ヒドロキシブチルアクリレート、ブトキシエチルアクリレート、エトキシジエチレングリコールアクリレート、メトキシジエチレングリコールアクリレート、メトキシプロピレングリコールアクリレート、フェノキシエチルアクリレート、テトラヒドロフルフリルアクリレート、イソボルニルアクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、ｔ－ブチルシクロヘキシルアクリレート等の単官能モノマー、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、１，４－ブタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，９－ノナンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ウレタンアクリレート、ポリエステルアクリレート等の二官能モノマー、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレートジペンタエリスリトールヘキサアクリレート等の三以上の多官能モノマーが挙げられる。 Isoamyl acrylate, stearyl acrylate, lauryl acrylate, decyl acrylate), isomyristyl acrylate), isostearyl acrylate, 2-ethylhexyl acrylate, 2-hydroxybutyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxypropylene glycol acrylate Monofunctional monomers such as phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, t-butylcyclohexyl acrylate, triethylene Glycoldi Acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, urethane acrylate, Bifunctional monomers such as polyester acrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate dipentaerythritol hexaacrylate, and the like may be used.
　その他、本発明において、光硬化性組成物に加えても良い化合物として、Ｎ－ビニル化合物、例えば、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタムを挙げることができ、エチレン性二重結合を有する重合性化合物として、例えば、マレイン酸、マレイン酸エステル類、フマル酸、フマル酸エステル類を挙げることができる。 In the present invention, examples of compounds that may be added to the photocurable composition include N-vinyl compounds such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and N-vinylcaprolactam. Examples of the polymerizable compound having an ethylenic double bond include maleic acid, maleic acid esters, fumaric acid, and fumaric acid esters.
　《光開始剤》
　また、本発明係る光硬化性組成物は、本発明のマレイミド誘導体自身も光開始剤として働くが、より光硬化感度を高めるには、光開始剤を併用することが好ましい。併用してもよい他の光開始剤としては下記が挙げられる。 《Photoinitiator》
In the photocurable composition according to the present invention, the maleimide derivative of the present invention itself works as a photoinitiator. However, in order to further increase the photocuring sensitivity, it is preferable to use a photoinitiator in combination. The following is mentioned as another photoinitiator which may be used together.
　１）ベンゾフェノン、ヒドロキシベンゾフェノン、ビス－Ｎ，Ｎ－ジメチルアミノベンゾフェノン、ビス－Ｎ，Ｎ－ジエチルアミノベンゾフェノン、４－メトキシ－４′－ジメチルアミノベンゾフェノン等のベンゾフェノン類、及びそれらの塩
　２）チオキサントン、２，４－ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン、イソプロポキシクロロチオキサントン等のチオキサントン類、及びそれらの塩
　３）エチルアントラキノン、ベンズアントラキノン、アミノアントラキノン、クロロアントラキノン等のアントラキノン類
　４）アセトフェノン類
　５）ベンゾインメチルエーテル等のベンゾインエーテル類
　６）２，４，６－トリハロメチルトリアジン類
　７）１－ヒドロキシシクロヘキシルフェニルケトン、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メトキシフェニル）イミダゾール２量体、２－（ｏ－フルオロフェニル）－４，５－フェニルイミダゾール２量体、２－（ｏ－メトキシフェニル）－４，５－フェニルイミダゾール２量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、２，４－ジ（ｐ－メトキシフェニル）－５－フェニルイミダゾール２量体、２－（２，４－ジメトキシフェニル）－４，５－ジフェニルイミダゾール２量体、２，４，５－トリアリールイミダゾール２量体等のイミダゾール類
　８）ベンジルジメチルケタール、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－１－プロパノン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、フェナントレンキノン、９，１０－フェナンスレンキノン、メチルベンゾイン、エチルベンゾイン等のベンゾイン類
　９）９－フェニルアクリジン、１，７－ビス（９，９′－アクリジニル）ヘプタン等のアクリジン誘導体
　１０）ビスアシルフォスフィンオキサイド、ビスフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド
　１１）４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、及びこれらのエチレンオキシド付加物。 1) Benzophenones such as benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and salts thereof 2) Thioxanthone, 2 Thioxanthones such as 1,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, and salts thereof 3) anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone 4) acetophenones 5) benzoin methyl Benzoin ethers such as ether 6) 2,4,6-trihalomethyltriazines 7) 1-hydroxycyclohexyl phenyl ketone, -(O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl)- 4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-phenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, 4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer 8) Benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- Tyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenanthrenequinone, 9,10-phenanthrenequinone, benzoins such as methylbenzoin, ethylbenzoin 9) 9-phenylacridine, 1, Acridine derivatives such as 7-bis (9,9'-acridinyl) heptane 10) Bisacylphosphine oxide, bisphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 11) 4- (2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) Tons, and their ethylene oxide adducts.
　また、インクに加える形態は必要に応じて溶解物、または分散物として加えることができる。 Also, the form to be added to the ink can be added as a dissolved product or a dispersion as required.
　《光増感剤》
　本発明のインクジェットインクには、吸収波長を長波にする目的で、増感剤を用いることができる。光増感剤の例としては、ベンゾフェノン類、チオキサントン類、スチリルケトン類、クマリン類、ローダミン類、シアニン類、メロシアニン類などをあげることができる。また、特開２０１０－０１８７２８公報などに記載されているジヒドロベンゾチアイン－４－オン増感剤も用いても良い。光増感剤を加える場合の光増感剤の添加量は、光開始剤の添加量の０．１質量倍から２質量倍の範囲が好ましい。 <Photosensitizer>
In the inkjet ink of the present invention, a sensitizer can be used for the purpose of increasing the absorption wavelength. Examples of photosensitizers include benzophenones, thioxanthones, styryl ketones, coumarins, rhodamines, cyanines, merocyanines and the like. Further, dihydrobenzothiain-4-one sensitizers described in JP 2010-018728 A and the like may also be used. When the photosensitizer is added, the addition amount of the photosensitizer is preferably in the range of 0.1 to 2 times the addition amount of the photoinitiator.
　また、表面硬化性を高める目的で、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸アミル、トリエタノールアミンなどを加えても良い。 Also, for the purpose of enhancing the surface curability, ethyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, triethanolamine, etc. may be added.
　《色材》
　本発明の光硬化性組成物では、色材を用いて、有色の光硬化性組成物、或いは、光硬化性のインクジェットインクとして用いても良い。 《Coloring material》
In the photocurable composition of this invention, you may use as a colored photocurable composition or a photocurable inkjet ink using a coloring material.
　この場合、着色剤としては、染料、顔料いずれも用いることが出来るが、光硬化の特性上、光劣化しにくい顔料を色材として用いることが好ましい。用いられる顔料としては、カーボンブラック、酸化チタン、炭酸カルシウム等の無色無機顔料又は有色有機顔料を使用することができる。有機顔料としては、トルイジンレッド、トルイジンマルーン、ハンザイエロー、ベンジジンイエロー、ピラゾロンレッドなどの不溶性アゾ顔料、リトールレッド、ヘリオボルドー、ピグメントスカーレット、パーマネントレッド２Ｂ等の溶性アゾ顔料；アリザリン、インダントロン、チオインジゴマルーン等の建染染料からの誘導体；フタロシアニンブルー、フタロシアニングリーン等のフタロシアニン系有機顔料；キナクリドンレッド、キナクリドンマゼンタ等のキナクリドン系有機顔料；ペリレンレッド、ペリレンスカーレット等のペリレン系有機顔料；イソインドリノンイエロー、イソインドリノンオレンジ等のイソインドリノン系有機顔料；ピランスロンレッド、ピランスロンオレンジ等のピランスロン系有機顔料；チオインジゴ系有機顔料、縮合アゾ系有機顔料、ベンズイミダゾロン系有機顔料、キノフタロンイエロー等のキノフタロン系有機顔料；イソインドリンイエローなどのイソインドリン系有機顔料；その他の顔料として、フラバンスロンイエロー、アシルアミドイエロー、ニッケルアゾイエロー、銅アゾメチンイエロー、ペリノンオレンジ、アンスロンオレンジ、ジアンスラキノニルレッド、ジオキサジンバイオレット等が挙げられる。 In this case, both a dye and a pigment can be used as the colorant, but it is preferable to use a pigment that is not easily photodegraded as a coloring material because of the characteristics of photocuring. As the pigment to be used, colorless inorganic pigments or colored organic pigments such as carbon black, titanium oxide and calcium carbonate can be used. Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red, soluble azo pigments such as ritole red, heliobordeaux, pigment scarlet, and permanent red 2B; alizarin, indanthrone, thio Derivatives from vat dyes such as indigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; isoindolinone Isoindolinone organic pigments such as yellow and isoindolinone orange; Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange; Thioindigo Machine pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; other pigments such as flavanthron yellow, acylamide yellow, nickel Azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like can be mentioned.
　有機顔料をカラーインデックス（Ｃ．Ｉ．）Ｎｏ．で以下に例示する。 Organic pigment is color index (CI) No. This is illustrated below.
　Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１７、２０、２４、７４、８３、８６、９３、１０９、１１０、１１７、１２０、１２５、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１６６、１６８、１８０、１８５、
　Ｃ．Ｉ．ピグメントオレンジ１６、３６、４３、５１、５５、５９、６１、
　Ｃ．Ｉ．ピグメントレッド９、４８、４９、５２、５３、５７、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２０２、２０６、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２３８、２４０、
　Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９、３０、３７、４０、５０、
　Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：３、１５：４、１５：６、２２、６０、６４、
　Ｃ．Ｉ．ピグメントグリーン７、３６、
　Ｃ．Ｉ．ピグメントブラウン２３、２５、２６、
　上記顔料の中でも、キナクリドン系、フタロシアニン系、ベンズイミダゾロン系、イソインドリノン系、縮合アゾ系、キノフタロン系、イソインドリン系有機顔料等は耐光性が優れているため好ましい。 C. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185,
C. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61,
C. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240,
C. I. Pigment violet 19, 23, 29, 30, 37, 40, 50,
C. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64,
C. I. Pigment Green 7, 36,
C. I. Pigment brown 23, 25, 26,
Among the above pigments, quinacridone-based, phthalocyanine-based, benzimidazolone-based, isoindolinone-based, condensed azo-based, quinophthalone-based, and isoindoline-based organic pigments are preferable because of their excellent light resistance.
　有機顔料は、レーザ散乱による測定値でインクジェットインク中の平均粒径が１５～２５０ｎｍの微細粒子であることが好ましい。顔料の平均粒径が１５ｎｍ未満の場合は、粒径が小さくなることによる耐光性の低下が生じ、２５０ｎｍを超える場合は、粗大粒子が多く含まれるようになるために、インクジェットヘッドの目詰まりの原因になり、吐出安定性の低下や、サテライトと言われる微小のミストが発生する問題が起こる。ただし、酸化チタンの場合は白色度と隠蔽性を持たせるために平均粒径は１５０～３００ｎｍ、好ましくは１８０～２５０ｎｍとする。 The organic pigment is preferably fine particles having an average particle diameter in the inkjet ink of 15 to 250 nm as measured by laser scattering. When the average particle diameter of the pigment is less than 15 nm, the light resistance is reduced due to the small particle diameter. When the average particle diameter exceeds 250 nm, a large amount of coarse particles are contained, and therefore the inkjet head is clogged. This causes problems such as deterioration in ejection stability and generation of minute mist called satellite. However, in the case of titanium oxide, the average particle diameter is set to 150 to 300 nm, preferably 180 to 250 nm, in order to provide whiteness and concealment.
　またインクジェットインク中の顔料の最大粒径は、１μｍを越えないよう、十分に分散あるいは、ろ過により粗大粒子を除くことが好ましい。粗大粒子が存在すると、やはり吐出安定性が低下する。有機顔料の微細化は公知の分散方法を用いて行うことが出来る。 In addition, it is preferable that coarse particles are removed by sufficient dispersion or filtration so that the maximum particle size of the pigment in the inkjet ink does not exceed 1 μm. If coarse particles are present, the ejection stability is also lowered. Refinement of the organic pigment can be performed using a known dispersion method.
　また顔料はその表面に顔料分散剤との吸着を促進するために、酸性処理または塩基性処理、シナージスト、各種カップリング剤など、公知の技術により表面処理を行うことが分散安定性を確保するために好ましい。 In addition, in order to ensure the dispersion stability of the pigment, surface treatment by a known technique such as acidic treatment or basic treatment, synergist, various coupling agents in order to promote adsorption with the pigment dispersant on the surface thereof. Is preferred.
　顔料は、十分な濃度及び十分な耐光性を得るため、インクジェットインク中に白色を除く色の場合１．５～８質量％、酸化チタンを用いた白色インクの場合、１０～３０質量％の範囲で含まれることが好ましい。 In order to obtain a sufficient concentration and sufficient light resistance, the pigment ranges from 1.5 to 8% by mass in the case of colors other than white in the ink-jet ink, and from 10 to 30% by mass in the case of white ink using titanium oxide. It is preferable that it is contained.
　《顔料分散剤》
　用いる顔料を分散する顔料分散剤としては、水酸基含有カルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキル燐酸エステル、ポリオキシエチレンノニルフェニルエーテル、ステアリルアミンアセテート、顔料誘導体等を挙げることができる。 <Pigment dispersant>
Examples of the pigment dispersant for dispersing the pigment used include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, and a high molecular weight Unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester , Polyoxyethylene nonylphenyl ether, stearylamine acetate, pigment derivatives and the like.
　具体例としては、ＢＹＫ　Ｃｈｅｍｉｅ社製の「Ａｎｔｉ－Ｔｅｒｒａ－Ｕ（ポリアミノアマイド燐酸塩）」、「Ａｎｔｉ－Ｔｅｒｒａ－２０３／２０４（高分子量ポリカルボン酸塩）」、「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミノアマイド燐酸塩と酸エステル）、１０７（水酸基含有カルボン酸エステル）、１１０（酸基を含む共重合物）、１３０（ポリアマイド）、１６１、１６２、１６３、１６４、１６５、１６６、１７０（高分子共重合物）」、「４００」、「Ｂｙｋｕｍｅｎ」（高分子量不飽和酸エステル）、「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和酸ポリカルボン酸）」、「Ｐ１０４Ｓ、２４０Ｓ（高分子量不飽和酸ポリカルボン酸とシリコン系）」、「Ｌａｃｔｉｍｏｎ（長鎖アミンと不飽和酸ポリカルボン酸とシリコン）」、が挙げられる。 Specific examples include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” and “Disperbyk-101 (polyaminoamide phosphate) manufactured by BYK Chemie. Salt (acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ) "," 400 "," Bykumen "(high molecular weight unsaturated acid ester)," BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid) And silicon) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid and Recon) ", and the like.
　又、Ｅｆｋａ　ＣＨＥＭＩＣＡＬＳ社製の「エフカ４４、４６、４７、４８、４９、５４、６３、６４、６５、６６、７１、７０１、７６４、７６６」、「エフカポリマー１００（変性ポリアクリレート）、１５０（脂肪族系変性ポリマー）、４００、４０１、４０２、４０３、４５０、４５１、４５２、４５３（変性ポリアクリレート）、７４５（銅フタロシアニン系）」；共栄化学社製の「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「フローノンＳＨ－２９０、ＳＰ－１０００」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（（メタ）アクリル系共重合物）」；楠本化成社製の「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４（高分子分散剤）、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル型）」等が挙げられる。 In addition, “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150” (fat) manufactured by Efka CHEMICALS Group modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine)); “Floren TG-710 (urethane oligomer)” manufactured by Kyoei Chemical Co., Ltd. "Flownon SH-290, SP-1000", "Polyflow No. 50E, No. 300 ((meth) acrylic copolymer)"; "Disparon KS-860, 873SN, 874 (polymer) manufactured by Enomoto Kasei Co., Ltd. Dispersing agent), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester) ) ", And the like.
　更には、花王社製の「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン縮合物ナトリウム塩）、ＥＰ」、「ホモゲノールＬ－１８（ポリカルボン酸型高分子）」、「エマルゲン９２０、９３０、９３１、９３５、９５０、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン２４（ココナッツアミンアセテート）、８６（ステアリルアミンアセテート）」；ゼネカ社製の「ソルスパーズ５０００（フタロシアニンアンモニウム塩系）、１３２４０、１３９４０（ポリエステルアミン系）、１７０００（脂肪酸アミン系）、２４０００、３２０００、７０００」；日光ケミカル社製の「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）、Ｈｅｘａｇｌｉｎｅ４－０（ヘキサグリセリルテトラオレート）」、味の素ファインテクノ製のアジスパー８２１、８２２、８２４、ソルスパース２４０００ＧＲ（ルーブリゾール社製）等が挙げられる。 Furthermore, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18” manufactured by Kao Corporation. (Polycarboxylic acid type polymer) "," Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonyl phenyl ether) "," Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate) "; “Solspers 5000 (phthalocyanine ammonium salt type), 13240, 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000, 32000, 7000” manufactured by Zeneca Corporation; “Nikkor T106 (polyoxyethylenesorbitan) manufactured by Nikko Chemical Mo Oleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), Ajinomoto Fine Techno's Azisper 821, 822, 824, Solsperse 24000GR (manufactured by Lubrizol), etc. .
　これらの顔料分散剤は、顔料１００に対し５～７０質量％、好ましくは１０～５０質量％の範囲で含有させることが好ましい。５質量％より少ないと分散安定性が得られないし、７０質量％より多いと吐出安定性が劣化する。 These pigment dispersants are preferably contained in an amount of 5 to 70% by mass, preferably 10 to 50% by mass, based on the pigment 100. When the amount is less than 5% by mass, the dispersion stability cannot be obtained, and when it is more than 70% by mass, the ejection stability is deteriorated.
　更に、これらの顔料分散剤は、０℃における重合性化合物全体へ５質量％以上の溶解性があることが好ましい。溶解性が５質量％未満であると、インクジェットインクを低温保存したときに、好ましくないポリマーゲルまたは顔料の軟凝集体が発生し、インクジェットインクの保存安定性と吐出安定性とが劣化する。 Furthermore, these pigment dispersants preferably have a solubility of 5% by mass or more in the entire polymerizable compound at 0 ° C. When the solubility is less than 5% by mass, an undesirable polymer gel or pigment soft aggregate is generated when the inkjet ink is stored at a low temperature, and the storage stability and ejection stability of the inkjet ink are deteriorated.
　《重合禁止剤》
　本発明の光硬化性組成物においては、保存安定性を得るために、ラジカル重合禁止剤を添加することが好ましい。 <Polymerization inhibitor>
In the photocurable composition of the present invention, it is preferable to add a radical polymerization inhibitor in order to obtain storage stability.
　ラジカル重合禁止剤としては、メトキノン（ヒドロキノンモノメチルエーテル）、ハイドロキノン、４－メトキシ－１－ナフトール、ヒンダードアミン系酸化防止剤、含窒素複素環メルカプト系化合物、チオエーテル系酸化防止剤、ヒンダードフェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、チオシアン酸塩類、チオ尿素誘導体、各種糖類、リン酸系酸化防止剤、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体、ニトロシルラジカル類、ジシアンジアミドとポリアルキレンポリアミンの重縮合物などが挙げられる。特に、ニトロシルラジカル類が好ましい。 As radical polymerization inhibitors, methoquinone (hydroquinone monomethyl ether), hydroquinone, 4-methoxy-1-naphthol, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants Agents, ascorbic acids, zinc sulfate, thiocyanates, thiourea derivatives, various sugars, phosphate antioxidants, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, nitrosyl radicals, dicyandiamide and polyalkylene polyamines Examples include polycondensates. In particular, nitrosyl radicals are preferred.
　ラジカル重合禁止剤の添加量は１０～５０００ｐｐｍであることが好ましい。１０ｐｐｍ未満では保存安定性が得られず、インクの増粘やインクジェットノズルに対する撥液性が得られなくなるなど吐出安定性を損なう。５０００ｐｐｍより多いと光硬化感度が低下してしまう。 The addition amount of the radical polymerization inhibitor is preferably 10 to 5000 ppm. If it is less than 10 ppm, the storage stability cannot be obtained, and the ejection stability is impaired, for example, the viscosity of the ink cannot be increased or the liquid repellency with respect to the inkjet nozzle cannot be obtained. If it exceeds 5000 ppm, the photocuring sensitivity is lowered.
　《その他の添加剤》
　本発明の光硬化性組成物には、必要に応じて界面活性剤、滑剤、充填剤、防錆剤、消泡剤、増粘剤、ゲル化剤、ポリマー類など各種の添加剤を含有させることが出来る。 《Other additives》
The photocurable composition of the present invention contains various additives such as a surfactant, a lubricant, a filler, a rust inhibitor, an antifoaming agent, a thickener, a gelling agent, and polymers as necessary. I can do it.
　また、必要に応じてエステル系溶剤、エーテル系溶剤、エーテルエステル系溶剤、ケトン系溶剤、芳香族炭化水素溶剤、含窒素系有機溶剤など少量の溶剤を添加することも出来る。 If necessary, a small amount of solvent such as an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a nitrogen-containing organic solvent can be added.
　（光硬化させる方法）
　本発明の光硬化性組成物は、基材に塗布後、紫外線を照射して硬化させるのが好ましい。光照射の方法の照射装置は、例えば紫外線ＬＥＤ、紫外線レーザ、水銀アークランプ、キセノンアークランプ、低圧水銀灯、螢光ランプ、炭素アークランプ、タングステン－ハロゲン複写ランプ及び太陽光を使用することができる。 (Method of photocuring)
The photocurable composition of the present invention is preferably cured by irradiating with ultraviolet rays after being applied to a substrate. As an irradiation apparatus of the light irradiation method, for example, an ultraviolet LED, an ultraviolet laser, a mercury arc lamp, a xenon arc lamp, a low-pressure mercury lamp, a fluorescent lamp, a carbon arc lamp, a tungsten-halogen copying lamp, and sunlight can be used.
　（インクジェットインクとしての使用方法及びその物性）
　本発明の光硬化性組成物は、インクジェットインクとして用いることが、より好ましい。インクジェットインクは、細いミクロンオーダーのインクジェットヘッドノズルから吐出されるために、粘度は２５℃において５～１００ｍＰａ・ｓで、シェアレート依存性が出来るだけ小さく、表面張力は２５℃において２２～３５ｍＮ／ｍの範囲にあること、顔料以外に１μｍを超えるようなゲル状物質が無いこと、電導度は１０μＳ／ｃｍ以下の電導度とし、ヘッド内部での電気的な腐食のないインクジェットインクとすることが好ましい。コンティニュアスタイプにおいては、電解質による電導度の調整が必要であり、この場合には０．５ｍＳ／ｃｍ以上の電導度に調整する必要がある。 (How to use as inkjet ink and its physical properties)
The photocurable composition of the present invention is more preferably used as an inkjet ink. Since inkjet ink is ejected from a thin micron-order inkjet head nozzle, the viscosity is 5 to 100 mPa · s at 25 ° C, and the shear rate dependence is as small as possible, and the surface tension is 22 to 35 mN / m at 25 ° C. It is preferable that the inkjet ink has no gel-like substance exceeding 1 μm other than the pigment, has an electric conductivity of 10 μS / cm or less, and has no electrical corrosion inside the head. . In the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.
　（インクジェットでの光照射方法）
　インクジェットでの光照射の方法は、上記、紫外線を付与する照射装置を具備したインクジェットプリンターで、インクジェットインクを重ねて硬化する多数回パス方式のシリアル記録方法、または、１回のパスで記録するライン記録方法いずれでも使用可能である。具体的には、インクジェットインクを基材上に付与し、基材上のインクジェットインクに紫外線を照射してインクジェットインクを硬化または半硬化状態とし、この上にフレッシュなインクジェットインクを付与し、活性エネルギー線によりインクジェットインクを硬化させる工程を含むものである。 (Light irradiation method with inkjet)
The method of light irradiation by inkjet is the above-described multi-pass serial recording method in which inkjet ink is overlaid and cured by an inkjet printer equipped with an irradiation device that applies ultraviolet rays, or a line for recording in one pass. Any recording method can be used. Specifically, the inkjet ink is applied onto the substrate, and the inkjet ink on the substrate is irradiated with ultraviolet rays so that the inkjet ink is cured or semi-cured. It includes a step of curing the ink-jet ink with lines.
　本発明の記録方法に用いる基材としては、従来、各種の用途で使用されている広汎な合成樹脂が全て対象となり、具体的には、例えばポリエステル、ポリ塩化ビニル、ポリエチレン、ポリウレタン、ポリプロピレン、（メタ）アクリル樹脂、ポリカーボネート、ポリスチレン、アクリロニトリル・ブタジエン・スチレン共重合体、ポリエチレンテレフタレート、ポリブタジエンテレフタレート等が挙げられ、これらの合成樹脂基材の厚みや形状は何ら限定されない。この他にも金属類、ガラス、印刷用紙なども使用できる。 As a base material used in the recording method of the present invention, a wide range of conventional synthetic resins used in various applications are all targeted. Specifically, for example, polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, ( Examples thereof include (meth) acrylic resin, polycarbonate, polystyrene, acrylonitrile / butadiene / styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like, and the thickness and shape of these synthetic resin substrates are not limited. In addition, metals, glass, printing paper, etc. can be used.
　以下実施例により本発明を説明するが本発明はこれにより限定されるものではない。なお、実施例において「部」あるいは「％」の表示を用いるが、特に断りがない限り「質量部」あるいは「質量％」を表す。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.
　合成例１（本発明のマレイミド誘導体１－１の合成）
　攪拌機、減圧装置およびトラップを備えた３００ｍｌナス型フラスコに、文献「有機合成化学協会誌第２３巻第２号（１９６５）」に記載の方法で合成したＮ－β－オキシイソプロピルマレイミド５．０ｇ、アゼライン酸２．８２ｇ、ｐ－トルエンスルホン酸一水和物０．７ｇ、２，６－ｔｅｒｔ－ブチル－ｐ－クレゾール０．０５ｇおよびトルエン２０ｍｌを順次仕込み、減圧下、生成する水とトルエンを共沸留去しながら、反応温度８０℃の条件で１２時間攪拌し反応終了とした。反応液を室温まで冷却し、酢酸エチル３００ｍｌに溶解させ、飽和炭酸水素ナトリウム水溶液１００ｍｌで３回、飽和食塩水１００ｍｌで１回洗浄した。有機層を硫酸マグネシウムにて乾燥後、濃縮して本発明のマレイミド誘導体１－１を３．２ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７４（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），
５．１１－５．１５（ｍ，２Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ－），
３．６４－３．６８（ｍ，４Ｈ，Ｎ－ＣＨ２－），
２．２３（ｔ，４Ｈ，－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－），
１．５５（ｂｒｓ，４Ｈ，－ＣＨ２－），１．２４－１．２７（ｍ，６Ｈ，－ＣＨ２－），
１．２４（ｄ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１７３．１［－（Ｃ＝Ｏ）－Ｏ－］，１７０．４［Ｎ－（Ｃ＝Ｏ）］，
１３４．０（－ＣＨ＝ＣＨ－），６７．９［－（Ｃ＝Ｏ）－Ｏ－ＣＨ－］，
４１．８（－Ｎ－ＣＨ２－），３４．１［－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－］，
２８．７（２Ｃ）（－ＣＨ２－），２４．５（－ＣＨ２－），
１７．５（－ＣＨ３）．で確認した。 Synthesis Example 1 (Synthesis of maleimide derivative 1-1 of the present invention)
Into a 300 ml eggplant type flask equipped with a stirrer, a decompression device and a trap, 5.0 g of N-β-oxyisopropylmaleimide synthesized by the method described in the literature “Organic Synthetic Chemistry Association Vol. 23, No. 2 (1965)” 2.82 g of azelaic acid, 0.7 g of p-toluenesulfonic acid monohydrate, 0.05 g of 2,6-tert-butyl-p-cresol and 20 ml of toluene were sequentially added, and the resulting water and toluene were combined under reduced pressure. While boiling off, the reaction was terminated by stirring for 12 hours under the condition of a reaction temperature of 80 ° C. The reaction solution was cooled to room temperature, dissolved in 300 ml of ethyl acetate, and washed 3 times with 100 ml of saturated aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine. The organic layer was dried over magnesium sulfate and concentrated to obtain 3.2 g of maleimide derivative 1-1 of the present invention. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.74 (s, 4H, -CH = CH-),
5.11-5.15 (m, 2H,-(C = O) -O-CH-),
3.64-3.68 (m, 4H, N—CH 2 —),
2.23 (t, 4H, —O— (C═O) —CH 2 —),
1.55 (brs, 4H, —CH 2 —), 1.24 to 1.27 (m, 6H, —CH 2 —),
1.24 (d, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
173.1 [— (C═O) —O—], 170.4 [N— (C═O)],
134.0 (—CH═CH—), 67.9 [— (C═O) —O—CH—],
41.8 (—N—CH 2 —), 34.1 [—O— (C═O) —CH 2 —],
28.7 (2C) (—CH 2 —), 24.5 (—CH 2 —),
17.5 (—CH 3 ). Confirmed with.
　合成例２（本発明のマレイミド誘導体１－２の合成）
　合成例１で用いたアゼライン酸２．８２ｇの代わりに、セバシン酸３．０３ｇを用いた以外は、合成例１の条件と同様に合成を行うことで、本発明のマレイミド誘導体１－２を３．３ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７２（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），
５．１２－５．１４（ｍ，２Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ－），
３．５８－３．７１（ｍ，４Ｈ，Ｎ－ＣＨ２－），
２．２２（ｔ，４Ｈ，－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－），
１．５４（ｂｒｓ，４Ｈ，－ＣＨ２－），
１．２２－１．４２（ｍ，８Ｈ，－ＣＨ２－），
１．２４（ｄ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１７３．３［－（Ｃ＝Ｏ）－Ｏ－］，１７０．５［Ｎ－（Ｃ＝Ｏ）］，
１３４．１（－ＣＨ＝ＣＨ－），６８．０［－（Ｃ＝Ｏ）－Ｏ－ＣＨ－］，
４１．９（－Ｎ－ＣＨ２－），３４．２［－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－］，
２９．０（－ＣＨ２－），２８．９（－ＣＨ２－），２４．６（－ＣＨ２－），１７．６（－ＣＨ３）．で確認した。 Synthesis Example 2 (Synthesis of maleimide derivative 1-2 of the present invention)
By synthesizing under the same conditions as in Synthesis Example 1 except that 3.03 g of sebacic acid was used instead of 2.82 g of azelaic acid used in Synthesis Example 1, 3 of the maleimide derivative 1-2 of the present invention was obtained. .3 g was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.72 (s, 4H, —CH═CH—),
5.12-5.14 (m, 2H,-(C = O) -O-CH-),
3.58-3.71 (m, 4H, N—CH 2 —),
2.22 (t, 4H, —O— (C═O) —CH 2 —),
1.54 (brs, 4H, —CH 2 —),
1.22-1.42 (m, 8H, —CH 2 —),
1.24 (d, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
173.3 [— (C═O) —O—], 170.5 [N— (C═O)],
134.1 (—CH═CH—), 68.0 [— (C═O) —O—CH—],
41.9 (—N—CH 2 —), 34.2 [—O— (C═O) —CH 2 —],
29.0 (—CH 2 —), 28.9 (—CH 2 —), 24.6 (—CH 2 —), 17.6 (—CH 3 ). Confirmed with.
　合成例３（比較例のマレイミド誘導体２－１の合成）
　合成例１で用いたＮ－β－オキシイソプロピルマレイミド５．０ｇの代わりに、文献「有機合成化学協会誌第２３巻第２号（１９６５）」に記載の方法で合成したＮ－β－オキシエチルマレイミド４．５５ｇを用いた以外は、合成例１の条件と同様に合成を行うことで、比較例のマレイミド誘導体２－１を３．３ｇ得た。得られた合成物は室温で固体であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７３（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），
４．２３（ｔ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
３．７９（ｔ，４Ｈ，Ｎ－ＣＨ２－），
２．２６（ｔ，４Ｈ，－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－），
１．５７（ｔ，４Ｈ，－ＣＨ２－），１．２７（ｓ，８Ｈ，－ＣＨ２－），及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１７３．５［－（Ｃ＝Ｏ）－Ｏ－］，１７０．４［Ｎ－（Ｃ＝Ｏ）］，
１３４．２（－ＣＨ＝ＣＨ－），６１．１［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，３６．９（－Ｎ－ＣＨ２－），３３．９［－Ｏ－（Ｃ＝Ｏ）－ＣＨ２－］，２８．９（２Ｃ）（－ＣＨ２－），２４．６（－ＣＨ２－）．で確認した。 Synthesis Example 3 (Synthesis of Maleimide Derivative 2-1 of Comparative Example)
In place of 5.0 g of N-β-oxyisopropylmaleimide used in Synthesis Example 1, N-β-oxyethyl synthesized by the method described in the document “Organic Synthetic Chemistry, Vol. 23, No. 2 (1965)” By synthesizing under the same conditions as in Synthesis Example 1, except that 4.55 g of maleimide was used, 3.3 g of maleimide derivative 2-1 of Comparative Example was obtained. The resulting composite was a solid at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.73 (s, 4H, -CH = CH-),
4.23 (t, 4H, — (C═O) —O—CH 2 —),
3.79 (t, 4H, N—CH 2 —),
2.26 (t, 4H, —O— (C═O) —CH 2 —),
1.57 (t, 4H, —CH 2 —), 1.27 (s, 8H, —CH 2 —), and
13 C NMR (100 MHz, CDCl 3 ):
173.5 [— (C═O) —O—], 170.4 [N— (C═O)],
134.2 (—CH═CH—), 61.1 [— (C═O) —O—CH 2 —], 36.9 (—N—CH 2 —), 33.9 [—O— (C = O) —CH 2 —], 28.9 (2C) (—CH 2 —), 24.6 (—CH 2 —). Confirmed with.
　合成例４（本発明のマレイミド誘導体１－３の合成）
　攪拌機、減圧装置およびトラップを備えた３００ｍｌナス型フラスコに、特許文献「第３５９９１６０号」に記載の方法で合成した２－マレイミド－２－メチル酢酸３３．８ｇ、ジエチレングリコール１０．２ｇ、ｐ－トルエンスルホン酸一水和物４．４７ｇ、２，６－ｔｅｒｔ－ブチル－ｐ－クレゾール０．３５ｇおよびトルエン２０ｍｌを順次仕込み、減圧下、生成する水とトルエンを共沸留去しながら、反応温度８０℃の条件で５時間攪拌し反応終了とした。反応液を室温まで冷却し、酢酸エチル３００ｍｌに溶解させ、飽和炭酸水素ナトリウム水溶液１００ｍｌで３回、飽和食塩水１００ｍｌで１回洗浄した。有機層を硫酸マグネシウムにて乾燥後、濃縮して本発明のマレイミド誘導体１－３を２４．７ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．８２（ｑ，２Ｈ，Ｎ－ＣＨ－），４．２０－４．３２（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
３．５８－３．６７（ｍ，４Ｈ，－ＣＨ２－Ｏ－），
１．５９（ｄ，２Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．７［Ｎ－（Ｃ＝Ｏ）］，１６９．５［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６８．７［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，６４．６（－ＣＨ２－Ｏ－），４７．４（－ＣＨ－），１５．１（－ＣＨ３）．で確認した。 Synthesis Example 4 (Synthesis of maleimide derivative 1-3 of the present invention)
In a 300 ml eggplant-shaped flask equipped with a stirrer, a decompression device and a trap, 33.8 g of 2-maleimido-2-methylacetic acid synthesized by the method described in Patent Document “3599160”, 10.2 g of diethylene glycol, p-toluenesulfone Acid monohydrate (4.47 g), 2,6-tert-butyl-p-cresol (0.35 g), and toluene (20 ml) were sequentially added. The reaction was terminated by stirring for 5 hours under the conditions described above. The reaction solution was cooled to room temperature, dissolved in 300 ml of ethyl acetate, and washed 3 times with 100 ml of saturated aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine. The organic layer was dried over magnesium sulfate and concentrated to obtain 24.7 g of maleimide derivative 1-3 of the present invention. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 4H, —CH═CH—), 4.82 (q, 2H, N—CH—), 4.20-4.32 (m, 4H, — (C═O) —O— CH 2- ),
3.58-3.67 (m, 4H, —CH 2 —O—),
1.59 (d, 2H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.7 [N— (C═O)], 169.5 [— (C═O) —O—],
134.3 (—CH═CH—), 68.7 [— (C═O) —O—CH 2 —], 64.6 (—CH 2 —O—), 47.4 (—CH—), 15.1 (—CH 3 ). Confirmed with.
　合成例５（本発明のマレイミド誘導体１－４の合成）
　合成例４で用いた、２－マレイミド－２－メチル酢酸３３．８ｇの代わりに、特許文献「第３５９９１６０号」に記載の方法で合成した２－マレイミド－２－イソブチリル酢酸を３９．４ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－４を２８．１ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．４１（ｄ，２Ｈ，Ｎ－ＣＨ－），４．２３（ｑ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
３．５８（ｔ，４Ｈ，－ＣＨ２－Ｏ－），
２．６２－２．７０［ｍ，２Ｈ，ＣＨ３－ＣＨ（ＣＨ３）－］，
１．０８（ｄ，６Ｈ，－ＣＨ３），０．８８（ｄ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１７０．１［Ｎ－（Ｃ＝Ｏ）］，１６８．６［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．１（－ＣＨ＝ＣＨ－），６８．６［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，６４．２（－ＣＨ２－Ｏ－），５７．６（Ｎ－ＣＨ－），
２８．５［ＣＨ３－ＣＨ（ＣＨ３）－］，２０．６（－ＣＨ３），
１９．３（－ＣＨ３）．で確認した。 Synthesis Example 5 (Synthesis of maleimide derivative 1-4 of the present invention)
Instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4, 39.4 g of 2-maleimido-2-isobutyrylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used. Was synthesized under the same conditions as in Synthesis Example 4 to obtain 28.1 g of maleimide derivative 1-4 of the present invention. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 4H, —CH═CH—), 4.41 (d, 2H, N—CH—), 4.23 (q, 4H, — (C═O) —O—CH 2 —) ,
3.58 (t, 4H, —CH 2 —O—),
2.62-2.70 [m, 2H, CH 3 —CH (CH 3 ) —],
1.08 (d, 6H, —CH 3 ), 0.88 (d, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
170.1 [N— (C═O)], 168.6 [— (C═O) —O—],
134.1 (—CH═CH—), 68.6 [— (C═O) —O—CH 2 —], 64.2 (—CH 2 —O—), 57.6 (N—CH—) ,
28.5 [CH 3 —CH (CH 3 ) —], 20.6 (—CH 3 ),
19.3 (—CH 3 ). Confirmed with.
　合成例６（本発明のマレイミド誘導体１－５の合成）
　合成例４で用いた、２－マレイミド－２－メチル酢酸３３．８ｇの代わりに、特許文献「第３５９９１６０号」に記載の方法で合成した２－マレイミド－２－イソバレリル酢酸を４２．２ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－５を２８．８ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７４（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．４８（ｄｄ，２Ｈ，Ｎ－ＣＨ－），４．１８－４．３０（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
３．６０－３．６４（ｍ，４Ｈ，－ＣＨ２－Ｏ－），
２．２２（ｄｄｄ，２Ｈ，Ｎ－ＣＨ－ＣＨ２－），
１．８８（ｄｄｄ，２Ｈ，Ｎ－ＣＨ－ＣＨ２－），
１．４０－１．５０［ｍ，２Ｈ，ＣＨ３－ＣＨ（ＣＨ３）－］，
０．９３（ｄ，６Ｈ，－ＣＨ３），０．９１（ｄ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１７０．１［Ｎ－（Ｃ＝Ｏ）］，１６９．６［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．２（－ＣＨ＝ＣＨ－），６８．７［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，６４．６（－ＣＨ２－Ｏ－），５０．６（Ｎ－ＣＨ－），３７．０（－ＣＨ２－），
２５．０［ＣＨ３－ＣＨ（ＣＨ３）－］，２３．０（－ＣＨ３），
２０．９（－ＣＨ３）．で確認した。 Synthesis Example 6 (Synthesis of maleimide derivative 1-5 of the present invention)
Instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4, 42.2 g of 2-maleimido-2-isovalerylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used. Was synthesized under the same conditions as in Synthesis Example 4 to obtain 28.8 g of maleimide derivative 1-5 of the present invention. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.74 (s, 4H, —CH═CH—), 4.48 (dd, 2H, N—CH—), 4.18-4.30 (m, 4H, — (C═O) —O— CH 2- ),
3.60-3.64 (m, 4H, —CH 2 —O—),
2.22 (ddd, 2H, N—CH—CH 2 —),
1.88 (ddd, 2H, N—CH—CH 2 —),
1.40-1.50 [m, 2H, CH 3 —CH (CH 3 ) —],
0.93 (d, 6H, —CH 3 ), 0.91 (d, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
170.1 [N— (C═O)], 169.6 [— (C═O) —O—],
134.2 (—CH═CH—), 68.7 [— (C═O) —O—CH 2 —], 64.6 (—CH 2 —O—), 50.6 (N—CH—) , 37.0 (—CH 2 —),
25.0 [CH 3 —CH (CH 3 ) —], 23.0 (—CH 3 ),
20.9 (—CH 3 ). Confirmed with.
　合成例７（比較例のマレイミド誘導体２－２の合成）
　合成例４で用いた、２－マレイミド－２－メチル酢酸３３．８ｇの代わりに、特許文献「第３５９９１６０号」に記載の方法で合成したマレイミド酢酸を３１．２ｇ用いた以外は合成例４と同様の条件で合成することにより、比較例のマレイミド誘導体２－２を３０．２ｇ得た。得られた合成物は室温で固体であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．８０（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．３４（ｓ，４Ｈ，Ｎ－ＣＨ２－），４．２７（ｔ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
３．６９（ｔ，４Ｈ，－ＣＨ２－Ｏ－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．７［Ｎ－（Ｃ＝Ｏ）］，１６７．２［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．５（－ＣＨ＝ＣＨ－），６８．７［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，６４．６（－ＣＨ２－Ｏ－），３８．６（Ｎ－ＣＨ２－）．で確認した。 Synthesis Example 7 (Synthesis of Maleimide Derivative 2-2 of Comparative Example)
Synthetic Example 4 except that 31.2 g of maleimidoacetic acid synthesized by the method described in Patent Document “No. 3599160” was used instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthetic Example 4. By synthesizing under the same conditions, 30.2 g of maleimide derivative 2-2 of Comparative Example was obtained. The resulting composite was a solid at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.80 (s, 4H, —CH═CH—), 4.34 (s, 4H, N—CH 2 —), 4.27 (t, 4H, — (C═O) —O—CH 2 — ),
3.69 (t, 4H, —CH 2 —O—). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.7 [N— (C═O)], 167.2 [— (C═O) —O—],
134.5 (—CH═CH—), 68.7 [— (C═O) —O—CH 2 —], 64.6 (—CH 2 —O—), 38.6 (N—CH 2 —) ). Confirmed with.
　合成例８（本発明のマレイミド誘導体１－６の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、１，６－ヘキサンジオールを１１．４ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－６を２５．４ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．７７（ｑ，２Ｈ，Ｎ－ＣＨ－），４．０７－４．１７（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．６３（ｄ，６Ｈ，－ＣＨ３），１．５８－１．６３（ｍ，４Ｈ，－ＣＨ２－），１．２４－１．３３（ｍ，４Ｈ，－ＣＨ２－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．８［Ｎ－（Ｃ＝Ｏ）］，１６９．５［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．２（－ＣＨ＝ＣＨ－），６５．５［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４７．４（Ｎ－ＣＨ－），２８．１（－ＣＨ２－），２５．１（－ＣＨ２－），１５．０（－ＣＨ３）．で確認した。 Synthesis Example 8 (Synthesis of maleimide derivative 1-6 of the present invention)
The maleimide derivative 1-6 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 11.4 g of 1,6-hexanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 25.4g was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 4H, —CH═CH—), 4.77 (q, 2H, N—CH—), 4.07-4.17 (m, 4H, — (C═O) —O— CH 2- ),
1.63 (d, 6H, —CH 3 ), 1.58-1.63 (m, 4H, —CH 2 —), 1.24—1.33 (m, 4H, —CH 2 —). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.8 [N— (C═O)], 169.5 [— (C═O) —O—],
134.2 (—CH═CH—), 65.5 [— (C═O) —O—CH 2 —], 47.4 (N—CH—), 28.1 (—CH 2 —), 25 .1 (—CH 2 —), 15.0 (—CH 3 ). Confirmed with.
　合成例９（本発明のマレイミド誘導体１－７の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、１，９－ノナンジオールを１５．４ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－７を２２．３ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７４（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．７８（ｑ，２Ｈ，Ｎ－ＣＨ－），４．０８－４．１８（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．５８－１．６５（ｍ，１０Ｈ，－ＣＨ２－，－ＣＨ３），
１．２４－１．２８（ｍ，１０Ｈ，－ＣＨ２－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．８［Ｎ－（Ｃ＝Ｏ）］，１６９．６［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６５．８［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４７．５（Ｎ－ＣＨ－），２９．２（－ＣＨ２－），２８．９（－ＣＨ２－），２８．３（－ＣＨ２－），２５．６（－ＣＨ２－），１５．１（－ＣＨ３）．で確認した。 Synthesis Example 9 (Synthesis of maleimide derivative 1-7 of the present invention)
The maleimide derivative 1-7 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 15.4 g of 1,9-nonanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 22.3 g was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.74 (s, 4H, —CH═CH—), 4.78 (q, 2H, N—CH—), 4.08-4.18 (m, 4H, — (C═O) —O— CH 2- ),
1.58-1.65 (m, 10H, —CH 2 —, —CH 3 ),
1.24-1.28 (m, 10H, —CH 2 —). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.8 [N— (C═O)], 169.6 [— (C═O) —O—],
134.3 (—CH═CH—), 65.8 [— (C═O) —O—CH 2 —], 47.5 (N—CH—), 29.2 (—CH 2 —), 28 .9 (—CH 2 —), 28.3 (—CH 2 —), 25.6 (—CH 2 —), 15.1 (—CH 3 ). Confirmed with.
　合成例１０（本発明のマレイミド誘導体１－８の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、１，１６－ヘキサデカンジオールを２４．８ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－８を３２．５ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．７２（ｑ，２Ｈ，Ｎ－ＣＨ－），４．０７－４．１７（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．５２－１．７０（ｍ，１０Ｈ，－ＣＨ２－，－ＣＨ３），
１．１５－１．３９（ｍ，２４Ｈ，－ＣＨ２－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．７［Ｎ－（Ｃ＝Ｏ）］，１６９．４［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６６．０［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４７．２（Ｎ－ＣＨ－），２９．２（－ＣＨ２－），２８．９（－ＣＨ２－），２８．３（－ＣＨ２－），２７．８（－ＣＨ２－），２７．４（－ＣＨ２－），２６．７（－ＣＨ２－），２５．６（－ＣＨ２－），１４．９（－ＣＨ３）．で確認した。 Synthesis Example 10 (Synthesis of maleimide derivative 1-8 of the present invention)
The maleimide derivative 1-8 of the present invention was synthesized under the same conditions as in Synthesis Example 4 except that 24.8 g of 1,16-hexadecanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 32.5 g was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 4H, —CH═CH—), 4.72 (q, 2H, N—CH—), 4.07-4.17 (m, 4H, — (C═O) —O— CH 2- ),
1.52-1.70 (m, 10H, —CH 2 —, —CH 3 ),
1.15-1.39 (m, 24H, —CH 2 —). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.7 [N— (C═O)], 169.4 [— (C═O) —O—],
134.3 (—CH═CH—), 66.0 [— (C═O) —O—CH 2 —], 47.2 (N—CH—), 29.2 (—CH 2 —), 28 .9 (—CH 2 —), 28.3 (—CH 2 —), 27.8 (—CH 2 —), 27.4 (—CH 2 —), 26.7 (—CH 2 —), 25 .6 (—CH 2 —), 14.9 (—CH 3 ). Confirmed with.
　合成例１１（本発明のマレイミド誘導体１－９の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、２－ブチル－２－エチル－１，３－プロパンジオールを１５．４ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－９を２６．２ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７４（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．８０（ｑ，２Ｈ，Ｎ－ＣＨ－），３．８０－３．９４（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．１５－１．２８（ｍ，８Ｈ，－ＣＨ２－），０．８４（ｄ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．８［Ｎ－（Ｃ＝Ｏ）］，１６９．３［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６６．９［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４７．４（－ＣＨ－），３９．４（－ＣＨ２－），３０．４（－ＣＨ２－），２４．６（－ＣＨ２－），２３．７（－ＣＨ２－），２３．３（－ＣＨ２－），１５．１（－ＣＨ３），１３．９（－ＣＨ３），７．０（－ＣＨ３）．で確認した。 Synthesis Example 11 (Synthesis of maleimide derivative 1-9 of the present invention)
By synthesizing under the same conditions as in Synthesis Example 4 except that 15.4 g of 2-butyl-2-ethyl-1,3-propanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 26.2 g of maleimide derivative 1-9 of the present invention was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.74 (s, 4H, —CH═CH—), 4.80 (q, 2H, N—CH—), 3.80-3.94 (m, 4H, — (C═O) —O— CH 2- ),
1.15-1.28 (m, 8H, —CH 2 —), 0.84 (d, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.8 [N— (C═O)], 169.3 [— (C═O) —O—],
134.3 (—CH═CH—), 66.9 [— (C═O) —O—CH 2 —], 47.4 (—CH—), 39.4 (—CH 2 —), 30. 4 (—CH 2 —), 24.6 (—CH 2 —), 23.7 (—CH 2 —), 23.3 (—CH 2 —), 15.1 (—CH 3 ), 13.9 (—CH 3 ), 7.0 (—CH 3 ). Confirmed with.
　合成例１２（本発明のマレイミド誘導体１－１０の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、２，４－ジエチル－１，５－ペンタンジオールを１５．４ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－１０を２７．８ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，４Ｈ，－ＣＨ＝ＣＨ－），４．７９（ｑ，２Ｈ，Ｎ－ＣＨ－），３．９５－４．１２（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．６３（ｄ，６Ｈ，－ＣＨ３），１．５９－１．６８（ｍ，２Ｈ，－ＣＨ２－），１．２１－１．３７（ｍ，４Ｈ，－ＣＨ２－），
１．１２－１．２０（ｍ，２Ｈ，－ＣＨ－），
０．８３－０．９１（ｍ，６Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．８［Ｎ－（Ｃ＝Ｏ）］，１６９．６［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６７．９［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４７．５（Ｎ－ＣＨ－），３６．０（－ＣＨ２－），３２．３（－ＣＨ２－），２４．０（－ＣＨ２－），１５．１（－ＣＨ３），１０．８（－ＣＨ３）．で確認した。 Synthesis Example 12 (Synthesis of maleimide derivative 1-10 of the present invention)
Synthesis was performed under the same conditions as in Synthesis Example 4 except that 15.4 g of 2,4-diethyl-1,5-pentanediol was used instead of 10.2 g of diethylene glycol used in Synthesis Example 4. 27.8 g of the maleimide derivative 1-10 was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 4H, —CH═CH—), 4.79 (q, 2H, N—CH—), 3.95-4.12 (m, 4H, — (C═O) —O— CH 2- ),
1.63 (d, 6H, —CH 3 ), 1.59-1.68 (m, 2H, —CH 2 —), 1.21-1.37 (m, 4H, —CH 2 —),
1.12-1.20 (m, 2H, —CH—),
0.83-0.91 (m, 6H, —CH 3 ). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.8 [N— (C═O)], 169.6 [— (C═O) —O—],
134.3 (—CH═CH—), 67.9 [— (C═O) —O—CH 2 —], 47.5 (N—CH—), 36.0 (—CH 2 —), 32 .3 (—CH 2 —), 24.0 (—CH 2 —), 15.1 (—CH 3 ), 10.8 (—CH 3 ). Confirmed with.
　合成例１３（本発明のマレイミド誘導体１－１１の合成）
　合成例４で用いた、２－マレイミド－２－メチル酢酸３３．８ｇの代わりに、特許文献「第３５９９１６０号」に記載の方法で合成した２－（３－マレイミド）－２－メチル酢酸を３６．６ｇ用いた以外は合成例２０と同様の条件で合成することにより、本発明のマレイミド誘導体１－１１を３１．２ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７５（ｓ，２Ｈ，－ＣＨ＝Ｃ－），４．６７（ｑ，２Ｈ，Ｎ－ＣＨ－），４．０５－４．１６（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．９３（ｓ，６Ｈ，－ＣＨ３），１．６３（ｄ，６Ｈ，－ＣＨ３），
１．５８－１．６３（ｍ，４Ｈ，－ＣＨ２－），
１．２４－１．３３（ｍ，２Ｈ，－ＣＨ２－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．６［Ｎ－（Ｃ＝Ｏ）］，１６９．２［－（Ｃ＝Ｏ）－Ｏ－］，
１３８．２（－ＣＨ＝Ｃ－），１３４．２（－ＣＨ＝Ｃ－），
６４．５［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４６．８（Ｎ－ＣＨ－），
２６．９（－ＣＨ２－），２２．１（－ＣＨ２－），
１５．０（－ＣＨ３），１１．８（－ＣＨ３）．で確認した。 Synthesis Example 13 (Synthesis of maleimide derivative 1-11 of the present invention)
Instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4, 36 mg of 2- (3-maleimido) -2-methylacetic acid synthesized by the method described in Patent Document “No. 3599160” was used. 31.2 g of maleimide derivative 1-11 of the present invention was obtained by synthesis under the same conditions as in Synthesis Example 20 except that 0.6 g was used. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.75 (s, 2H, —CH═C—), 4.67 (q, 2H, N—CH—), 4.05-4.16 (m, 4H, — (C═O) —O— CH 2- ),
1.93 (s, 6H, —CH 3 ), 1.63 (d, 6H, —CH 3 ),
1.58-1.63 (m, 4H, —CH 2 —),
1.24-1.33 (m, 2H, —CH 2 —). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.6 [N— (C═O)], 169.2 [— (C═O) —O—],
138.2 (—CH═C—), 134.2 (—CH═C—),
64.5 [— (C═O) —O—CH 2 —], 46.8 (N—CH—),
26.9 (—CH 2 —), 22.1 (—CH 2 —),
15.0 (—CH 3 ), 11.8 (—CH 3 ). Confirmed with.
　合成例１４（本発明のマレイミド誘導体１－１２の合成）
　合成例４用いた、２－マレイミド－２－メチル酢酸３３．８ｇの代わりに、特許文献「第３５９９１６０号」に記載の方法で合成した２－（３，４，５，６－テトラヒドロ－フタロイミド）－２－メチル酢酸を４４．６ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－１２を３５．４ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
４．６０（ｑ，２Ｈ，Ｎ－ＣＨ－），
４．０８－４．１７（ｍ，４Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），
１．９６－２．１２（ｍ，８Ｈ，－ＣＨ２－），１．８９（ｓ，６Ｈ，－ＣＨ３），１．６３－１．７８（ｍ，８Ｈ，－ＣＨ３），
１．５８－１．６２（ｍ，４Ｈ，－ＣＨ２－），
１．２０－１．３１（ｍ，２Ｈ，－ＣＨ２－）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．８［Ｎ－（Ｃ＝Ｏ）］，１６９．３［－（Ｃ＝Ｏ）－Ｏ－］，
１４５．０（－Ｃ＝Ｃ－），６５．８［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，
４７．２（Ｎ－ＣＨ－），２９．０（－ＣＨ２－），２８．６（－ＣＨ２－），２４．６（－ＣＨ２－），２２．１（－ＣＨ２－），１５．９（－ＣＨ３）．で確認した。 Synthesis Example 14 (Synthesis of maleimide derivative 1-12 of the present invention)
2- (3,4,5,6-tetrahydro-phthaloimide) synthesized by the method described in Patent Document “No. 3599160” instead of 33.8 g of 2-maleimido-2-methylacetic acid used in Synthesis Example 4 By synthesizing under the same conditions as in Synthesis Example 4 except that 44.6 g of -2-methylacetic acid was used, 35.4 g of maleimide derivative 1-12 of the present invention was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
4.60 (q, 2H, N—CH—),
4.08-4.17 (m, 4H, — (C═O) —O—CH 2 —),
1.96-2.12 (m, 8H, —CH 2 —), 1.89 (s, 6H, —CH 3 ), 1.63-1.78 (m, 8H, —CH 3 ),
1.58-1.62 (m, 4H, —CH 2 —),
1.20-1.31 (m, 2H, —CH 2 —). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.8 [N— (C═O)], 169.3 [— (C═O) —O—],
145.0 (—C═C—), 65.8 [— (C═O) —O—CH 2 —],
47.2 (N—CH—), 29.0 (—CH 2 —), 28.6 (—CH 2 —), 24.6 (—CH 2 —), 22.1 (—CH 2 —), 15.9 (—CH 3 ). Confirmed with.
　合成例１５（本発明のマレイミド誘導体１－１３の合成）
　合成例４で用いた、ジエチレングリコール１０．２ｇの代わりに、１－ブタノールを１４．２ｇ用いた以外は合成例４と同様の条件で合成することにより、本発明のマレイミド誘導体１－１３を３６．５ｇ得た。得られた合成物は室温で油状であった。
１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：
６．７２（ｓ，２Ｈ，－ＣＨ＝ＣＨ－），４．７９（ｑ，１Ｈ，Ｎ－ＣＨ－），
４．１２（ｑ，２Ｈ，－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－），１．６３（ｄ，６Ｈ，－ＣＨ３），１．２３－１．３９（ｍ，４Ｈ，－ＣＨ２－），０．９０（ｍ，３Ｈ，－ＣＨ３）．及び、
１３Ｃ　ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ３）：
１６９．７［Ｎ－（Ｃ＝Ｏ）］，１６９．４［－（Ｃ＝Ｏ）－Ｏ－］，
１３４．３（－ＣＨ＝ＣＨ－），６６．２［－（Ｃ＝Ｏ）－Ｏ－ＣＨ２－］，４６．５（Ｎ－ＣＨ－），２５．９（－ＣＨ２－），２４．０（－ＣＨ２－），１５．３（－ＣＨ３），９．８（－ＣＨ３）．で確認した。 Synthesis Example 15 (Synthesis of maleimide derivative 1-13 of the present invention)
By synthesizing under the same conditions as in Synthesis Example 4 except that 14.2 g of 1-butanol was used in place of 10.2 g of diethylene glycol used in Synthesis Example 4, 36. 5 g was obtained. The resulting composition was oily at room temperature.
1 H NMR (400 MHz, CDCl 3 ):
6.72 (s, 2H, —CH═CH—), 4.79 (q, 1H, N—CH—),
4.12 (q, 2H, — (C═O) —O—CH 2 —), 1.63 (d, 6H, —CH 3 ), 1.23-1.39 (m, 4H, —CH 2 -), 0.90 (m, 3H , -CH 3). as well as,
13 C NMR (100 MHz, CDCl 3 ):
169.7 [N— (C═O)], 169.4 [— (C═O) —O—],
134.3 (—CH═CH—), 66.2 [— (C═O) —O—CH 2 —], 46.5 (N—CH—), 25.9 (—CH 2 —), 24 0.0 (—CH 2 —), 15.3 (—CH 3 ), 9.8 (—CH 3 ). Confirmed with.
　実施例１（マレイミド誘導体単独での実施対応）
　（光硬化性組成物１の作製）
　以下の組成の光硬化性組成物１を作製し、出射性と光硬化感度の測定に用いた。 Example 1 (Compatibility with maleimide derivative alone)
(Preparation of photocurable composition 1)
A photocurable composition 1 having the following composition was prepared and used for measurement of light emission and photocuring sensitivity.
　光硬化性組成物組成
　本発明のマレイミド誘導体１－１　　　　　　　　　　　９７．９質量％
　光開始剤（ＢＡＳＦ社製Ｄａｒｏｃｕｒｅ１１７３）　　　２．０質量％
　ＴＥＭＰＯ（２，２，６，６－テトラメチルピペリジニル－Ｎ－オキシル）　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１質量％
　（光硬化性組成物２～１７の作製）
　光硬化性組成物１の作製において、本発明のマレイミド誘導体１－１を、表１～４記載のマレイミド誘導体に変更した以外は光硬化性組成物１と同様にして光硬化性組成物２～１７を作製した。 Photocurable Composition Composition Maleimide Derivative 1-1 of the Present Invention 97.9 mass%
Photoinitiator (Darocur 1173 manufactured by BASF) 2.0% by mass
TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) 0.1% by mass
(Preparation of photocurable compositions 2 to 17)
In the preparation of the photocurable composition 1, the photocurable compositions 2 to 2 were prepared in the same manner as the photocurable composition 1 except that the maleimide derivative 1-1 of the present invention was changed to the maleimide derivatives shown in Tables 1 to 4. 17 was produced.
　《光硬化性組成物の評価》
　作製した光硬化性組成物１～１７について、以下の方法で評価した。評価結果を表１～４に示す。 << Evaluation of Photocurable Composition >>
The produced photocurable compositions 1 to 17 were evaluated by the following methods. The evaluation results are shown in Tables 1 to 4.
　（出射性）
　コニカミノルタＩＪ社製のピエゾヘッド５１２Ｌを用いて、ヘッド温度を９０℃以下でインク粘度１０ｍＰａ・ｓになる温度、または９０℃でも１０ｍＰａ・ｓより大きい場合はヘッド温度を９０℃に設定した、４２ｐｌの液滴サイズを８ｋＨｚの周波数で１Ｌ相当の各インクを１０分間連続吐出し、欠ノズルの数を調べ、下記基準で評価した。 (Outgoing properties)
Using a piezo head 512L manufactured by Konica Minolta IJ, the temperature at which the head temperature is 90 ° C. or lower and the ink viscosity becomes 10 mPa · s, or the head temperature is set to 90 ° C. when 90 ° C. is greater than 10 mPa · s, 42 pl Each droplet corresponding to 1 L at a frequency of 8 kHz was continuously ejected for 10 minutes, the number of missing nozzles was examined, and evaluated according to the following criteria.
　◎：欠のノズルは認められなかった
　○：欠ノズルが１個以上全体の３％未満発生した
　△：欠ノズルが全体の全体の３％以上、１０％未満発生した
　×：欠ノズルが全体の１０％以上発生した。 ◎: No missing nozzles were recognized. ○: One or more missing nozzles occurred in less than 3% of the whole. △: Missing nozzles occurred in 3% or more and less than 10% of the whole. More than 10% occurred.
　（光硬化感度）
　ピエゾヘッドＫＭ５１２Ｌを搭載したシリアル方式のＵＶ硬化型プリンターを用いて、画像解像度７２０×７２０ｄｐｉ（ｄｐｉとは１インチ、即ち２．５４ｃｍ当たりのドット数を表す）で、ＰＥＴ上にベタ画像を作製後、高圧水銀灯の出力を調整し、１０、３０、及び１００ｍＪ／ｃｍ２の光量になるように調整し、ＵＶ照射した。ＵＶ照射されたベタ画像から、触診により硬化の有無を調べ、下記基準で評価した。 (Photocuring sensitivity)
After producing a solid image on PET with an image resolution of 720 x 720 dpi (dpi represents 1 inch, that is, the number of dots per 2.54 cm) using a serial UV curable printer equipped with a piezo head KM512L The output of the high-pressure mercury lamp was adjusted to adjust the light amount to 10, 30, and 100 mJ / cm 2 , and UV irradiation was performed. From the solid image irradiated with UV, the presence or absence of curing was examined by palpation and evaluated according to the following criteria.
　◎：光量１０ｍＪ／ｃｍ２で硬化していた
　○：光量１０ｍＪ／ｃｍ２で硬化しなかったが、光量３０ｍＪ／ｃｍ２では硬化した
　△：光量３０ｍＪ／ｃｍ２で硬化しなかったが、光量１００ｍＪ／ｃｍ２で硬化した
　×：光量１００ｍＪ／ｃｍ２で硬化しなかった。 ◎: ○ was cured at a light volume 10mJ / cm 2: but did not cure in the amount of light 10mJ / cm 2, the amount of light 30mJ / cm 2 was cured in △: but did not cure in the amount of light 30mJ / cm 2, the amount of light 100mJ Cured at / cm 2 ×: Not cured at 100 mJ / cm 2 .
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　表１～４から、本発明のマレイミド誘導体を用いた光硬化性組成物は、インクジェット出射性が良好であり、光硬化感度が高いことがわかる。 From Tables 1 to 4, it can be seen that the photocurable composition using the maleimide derivative of the present invention has good ink jetting properties and high photocuring sensitivity.
　実施例２（インクジェットインクにした時の実施対応）
　《インクジェットインクの作製》
　（インクジェットインク１の作製）
　ＴＥＧＤＶＥ（トリエチレングリコールジビニルエーテル）　３３．４ｇ
　マレイミド誘導体１－１　　　　　　　　　　　　　　　　　５５．５ｇ
　カーボンブラック　　　　　　　　　　　　　　　　　　　　　２．０ｇ
　スルスパース２４０００ＧＲ（ルーブリゾール社製）　　　　　１．０ｇ
　ＴＥＭＰＯ（２，２，６，６－テトラメチルピペリジニル－Ｎ－オキシル）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１ｇを混合し、粒径０．５ｍｍのジルコニアビーズとともにペイントシェーカーで６時間分散混合した液に
　ＤＡＲＯＣＵＲＥ　ＴＰＯ（ホスフィンオキシド系光開始剤　ＢＡＳＦ製）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　５．０ｇ
　Ｑｕａｎｔａｃｕｒｅ　ＩＴＸ（チオキサントン系光増感剤　Ａｃｅｔｏ　Ｃｈｅｍｉｃａｌ製）　　　　　　　　　　　　　　　　　　　３．０ｇを混合溶解させて、インクジェットインク１を作製した。このインクのビニルエーテルとマレイミド誘導体１－１の当量比は５０／５０である。 Example 2 (Implementation when using inkjet ink)
<Production of inkjet ink>
(Preparation of inkjet ink 1)
TEGDVE (triethylene glycol divinyl ether) 33.4 g
Maleimide derivative 1-1 55.5g
Carbon black 2.0g
Sulsperse 24000GR (made by Lubrizol) 1.0g
TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) 0.1 g was mixed and dispersed with a zirconia bead having a particle size of 0.5 mm for 6 hours using a paint shaker. DAROCURE TPO (phosphine) Oxide photoinitiator BASF) 5.0g
Quantacure ITX (manufactured by thioxanthone photosensitizer manufactured by Aceto Chemical) 3.0 g was mixed and dissolved to prepare inkjet ink 1. The equivalent ratio of vinyl ether to maleimide derivative 1-1 in this ink is 50/50.
　（インクジェットインク２～１７の作製）
　インクジェットインク１の作製の際、マレイミド誘導体１－１の代わりに表５に示すマレイミド誘導体を用いて当量比５０／５０になるように調製した他は、インクジェットインク１と同様にして、インクジェットインク２～１７を作製した。 (Preparation of inkjet inks 2 to 17)
Ink jet ink 1 was prepared in the same manner as ink jet ink 1 except that the maleimide derivative shown in Table 5 was used instead of maleimide derivative 1-1 and the equivalent ratio was 50/50. To 17 were produced.
　《インクジェットインクの評価》
　作製したインクジェットインク１～１７について、以下の方法で評価した。評価結果を表５に示す。 <Evaluation of inkjet ink>
The produced inkjet inks 1 to 17 were evaluated by the following methods. The evaluation results are shown in Table 5.
　（出射性）
　コニカミノルタＩＪ社製のピエゾヘッド５１２Ｌを用いて、ヘッド温度を７５℃以下でインク粘度１０ｍＰａ・ｓになる温度、または７５℃でも１０ｍＰａ・ｓより大きい場合はヘッド温度を７５℃に設定した、４２ｐｌの液滴サイズを８ｋＨｚの周波数で１Ｌ相当の各インクを１０分間連続吐出し、欠ノズルの数を調べ、下記基準で評価した。 (Outgoing properties)
Using a piezo head 512L manufactured by Konica Minolta IJ, the temperature at which the head temperature is 75 ° C. or lower and the ink viscosity is 10 mPa · s, or the head temperature is set to 75 ° C. when 75 ° C. is higher than 10 mPa · s, 42 pl Each droplet corresponding to 1 L at a frequency of 8 kHz was continuously ejected for 10 minutes, the number of missing nozzles was examined, and evaluated according to the following criteria.
　◎：欠のノズルは認められなかった。 ◎: No missing nozzle was found.
　○：欠ノズルが１個以上全体の３％未満発生した。 ○: One or more missing nozzles occurred in less than 3% of the total.
　△：欠ノズルが全体の全体の３％以上、１０％未満発生した。 △: Missing nozzles occurred 3% or more and less than 10% of the whole.
　×：欠ノズルが全体の１０％以上発生した。 X: 10% or more of missing nozzles occurred.
　（光硬化感度）
　ピエゾヘッドＫＭ５１２Ｌを搭載したシリアル方式のＵＶ硬化型プリンターを用いて、画像解像度７２０×７２０ｄｐｉで、ＰＥＴ上にベタ画像を作製後、高圧水銀灯の出力を調整し、１０、３０、及び１００ｍＪ／ｃｍ２の光量になるように調整し、ＵＶ照射した。ＵＶ照射されたベタ画像から、触診により硬化の有無を調べ、下記基準で評価した。 (Photocuring sensitivity)
Using a serial UV curable printer equipped with a piezo head KM512L, a solid image was produced on PET with an image resolution of 720 × 720 dpi, and the output of the high-pressure mercury lamp was adjusted to 10, 30, and 100 mJ / cm 2. It adjusted so that it might become the light quantity of, and UV irradiation was carried out. From the solid image irradiated with UV, the presence or absence of curing was examined by palpation and evaluated according to the following criteria.
　◎：光量１０ｍＪ／ｃｍ２で硬化していた。 A: Cured with a light amount of 10 mJ / cm 2 .
　○：光量１０ｍＪ／ｃｍ２で硬化しなかったが、光量３０ｍＪ／ｃｍ２では硬化した。 ○: Although not cured with light intensity 10 mJ / cm 2, and curing the quantity of light 30 mJ / cm 2.
　△：光量３０ｍＪ／ｃｍ２で硬化しなかったが、光量１００ｍＪ／ｃｍ２で硬化した。 △: but did not cure in the amount of light 30mJ / cm 2, it was cured in light intensity 100mJ / cm 2.
　×：光量１００ｍＪ／ｃｍ２で硬化しなかった。 X: It did not harden | cure by light quantity 100mJ / cm < 2 >.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　表５から、本発明のマレイミド誘導体を用いたインクジェットインクは、インクジェット出射性が良好であり、光硬化感度が高いことがわかる。 From Table 5, it can be seen that the ink jet ink using the maleimide derivative of the present invention has good ink jetting properties and high photocuring sensitivity.

Claims (8)

  1. 　下記一般式（１）で表されるマレイミド誘導体を含有することを特徴とする光硬化性インクジェットインク。
    Figure JPOXMLDOC01-appb-C000001
    　（式中、Ｒ１、Ｒ２は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表し、Ｒ１、Ｒ２はそれぞれ結合して環を形成してもよい。Ａ１、Ａ３は、それぞれ独立にアルキレン基を表し、Ａ２は不斉中心を有する炭化水素基を表す。Ｙは、カルボニルオキシ（－Ｃ＝Ｏ－Ｏ－）またはオキシカルボニル（－Ｏ－Ｃ＝Ｏ－）を表す。ｐは１または２を表す。Ｒ３はｐが１の場合は分子量１５～６００のアルキル基、アルキレンオキシ基、ｐが２の場合は、分子量１４～６００のアルキレン基、アルキレンオキシ基を表す。ｍは０または１、ｎは０または１を表す。）     A photocurable inkjet ink comprising a maleimide derivative represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001
    (Wherein R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring. A 1 , A 3 independently represents an alkylene group, A 2 represents a hydrocarbon group having an asymmetric center, and Y represents carbonyloxy (—C═O—O—) or oxycarbonyl (—O—C═O). P represents 1 or 2. R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2. Represents an oxy group, m represents 0 or 1, and n represents 0 or 1.)
  2. 　前記一般式（１）における、Ａ１、およびＡ３はメチレン基、Ａ２はＣＨＲ４、Ｒ３は炭素数４～１２のアルキル基、又はアルキレン基であり、Ｒ４は炭素数１～４のアルキル基を表すことを特徴とする請求項１記載の光硬化性インクジェットインク。 In the general formula (1), A 1 and A 3 are methylene groups, A 2 is CHR 4 , R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group, and R 4 is 1 to 4 carbon atoms. The photocurable inkjet ink according to claim 1, which represents an alkyl group of
  3. 　前記一般式（１）が、下記一般式（２）、一般式（３）又は一般式（４）で表されることを特徴とする請求項１又は２記載の光硬化性インクジェットインク。
    Figure JPOXMLDOC01-appb-C000002
    　（式中、Ｒ４は、請求項２記載のＲ４と同義の基を表し、ｐは一般式（１）のｐと同義である。Ｒ５は直鎖の炭素数４～１２のアルキル基、又はアルキレン基を表す。）     The photocurable inkjet ink according to claim 1 or 2, wherein the general formula (1) is represented by the following general formula (2), general formula (3), or general formula (4).
    Figure JPOXMLDOC01-appb-C000002
    (Wherein R 4 represents a group having the same meaning as R 4 in claim 2, and p has the same meaning as p in formula (1). R 5 is a linear alkyl group having 4 to 12 carbon atoms. Or represents an alkylene group.)
  4. 　請求項１～３のいずれか１項記載の光硬化性インクジェットインクを用いることを特徴とする画像形成方法。 An image forming method comprising using the photocurable inkjet ink according to any one of claims 1 to 3.
  5. 　下記一般式（１）で表されるマレイミド誘導体。
    Figure JPOXMLDOC01-appb-C000003
     　（式中、Ｒ１、Ｒ２は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表し、Ｒ１、Ｒ２はそれぞれ結合して環を形成してもよい。Ａ１、Ａ３は、それぞれ独立にアルキレン基を表し、Ａ２は不斉中心を有する炭化水素基を表す。Ｙは、カルボニルオキシ（－Ｃ＝Ｏ－Ｏ－）またはオキシカルボニル（－Ｏ－Ｃ＝Ｏ－）を表す。ｐは１または２を表す。Ｒ３はｐが１の場合は分子量１５～６００のアルキル基、アルキレンオキシ基、ｐが２の場合は、分子量１４～６００のアルキレン基、アルキレンオキシ基を表す。ｍは０または１、ｎは０または１を表す。）     A maleimide derivative represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring. A 1 , A 3 independently represents an alkylene group, A 2 represents a hydrocarbon group having an asymmetric center, and Y represents carbonyloxy (—C═O—O—) or oxycarbonyl (—O—C═O). P represents 1 or 2. R 3 represents an alkyl group or alkyleneoxy group having a molecular weight of 15 to 600 when p is 1, and an alkylene group or alkylene group having a molecular weight of 14 to 600 when p is 2. Represents an oxy group, m represents 0 or 1, and n represents 0 or 1.)
  6. 　前記一般式（１）における、Ａ１、およびＡ３はメチレン基、Ａ２はＣＨＲ４、Ｒ３は炭素数４～１２のアルキル基、又はアルキレン基であり、Ｒ４は炭素数１～４のアルキル基を表すことを特徴とする請求項５記載のマレイミド誘導体。 In the general formula (1), A 1 and A 3 are methylene groups, A 2 is CHR 4 , R 3 is an alkyl group having 4 to 12 carbon atoms, or an alkylene group, and R 4 is 1 to 4 carbon atoms. The maleimide derivative according to claim 5, which represents an alkyl group of
  7. 　前記一般式（１）が、下記一般式（２）、一般式（３）又は一般式（４）で表されることを特徴とする請求項５又は６記載のマレイミド誘導体。
    Figure JPOXMLDOC01-appb-C000004
     　（式中、Ｒ４は、請求項６記載のＲ４と同義の基を表し、ｐは一般式（１）のｐと同義である。Ｒ５は直鎖の炭素数４～１２のアルキル基、又はアルキレン基を表す。）     The maleimide derivative according to claim 5 or 6, wherein the general formula (1) is represented by the following general formula (2), general formula (3), or general formula (4).
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 4 represents a group having the same meaning as R 4 in claim 6, and p has the same meaning as p in formula (1). R 5 is a linear alkyl group having 4 to 12 carbon atoms. Or represents an alkylene group.)
  8. 　請求項５～７のいずれか１項記載のマレイミド誘導体を含有することを特徴とする光硬化性組成物。 A photocurable composition comprising the maleimide derivative according to any one of claims 5 to 7.
PCT/JP2011/061395 2010-06-16 2011-05-18 Photocurable ink jet ink, method for forming image, maleimide derivative and photocurable composition WO2011158593A1 (en)

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