WO2006137260A1 - Composition polymerisable, composition d'encre, procede de formation d'images, imprimante jet d'encre, et epoxyde alicyclique - Google Patents

Composition polymerisable, composition d'encre, procede de formation d'images, imprimante jet d'encre, et epoxyde alicyclique Download PDF

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Publication number
WO2006137260A1
WO2006137260A1 PCT/JP2006/311261 JP2006311261W WO2006137260A1 WO 2006137260 A1 WO2006137260 A1 WO 2006137260A1 JP 2006311261 W JP2006311261 W JP 2006311261W WO 2006137260 A1 WO2006137260 A1 WO 2006137260A1
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group
ink
general formula
alkyl group
polymerizable composition
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PCT/JP2006/311261
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English (en)
Japanese (ja)
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Takeshi Kurata
Kimihiko Ookubo
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Konica Minolta Medical & Graphic, Inc.
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Publication of WO2006137260A1 publication Critical patent/WO2006137260A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/44—Esterified with oxirane-containing hydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

Definitions

  • the present invention relates to a polymerizable composition, which cures with high sensitivity even under high temperature conditions, has excellent storage properties, and further, the formed cured film has adhesiveness, flexibility, storage stability,
  • the present invention relates to a polymerizable composition, an ink composition, an image forming method using the ink composition, an ink jet recording apparatus, and a specific alicyclic epoxide that are extremely excellent in resistance to environmental changes, particularly temperature change.
  • polymerizable compositions that are cured by active energy rays such as ultraviolet rays and electron beams, or heat, are paints such as plastic, paper, woodwork, and inorganic materials, adhesives, printing inks, printed circuit boards, and electrical insulation. It has been put to practical use in various applications such as relationships. In recent years, printing inks, paints, adhesives and the like have been desired to further improve weather resistance and adhesion.
  • an ink-jet ink system using these polymerized compositions there is an ultraviolet curable ink-jet ink that cures with ultraviolet rays.
  • the ink jet system using this ultraviolet curable ink has a relatively low odor and a high speed.
  • Ink using a radically polymerizable compound is subjected to an oxygen inhibition action, so that an ink droplet is used.
  • an ink droplet is used.
  • curing inhibition tends to occur.
  • inks using cationically polymerizable compounds are not affected by oxygen inhibition, but are susceptible to molecular water (humidity). There are two problems.
  • Patent Document 1 JP-A-6-200204
  • Patent Document 2 Japanese Translation of Special Publication 2000-504778
  • Patent Document 3 Japanese Patent Laid-Open No. 8-3493
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-220526
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-188025
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-317139
  • Patent Document 7 Japanese Patent Laid-Open No. 2003-55449
  • An object of the present invention is to cure with high sensitivity even under high temperature conditions and to have excellent storage stability. Further, the formed cured film has excellent adhesion, flexibility, storage stability, environmental resistance, especially temperature change.
  • a polymerizable composition, an ink composition, an image forming method using the ink composition, an ink jet recording apparatus, and a specific alicyclic epoxide (also known as an alicyclic alkylene oxide)! Is to provide.
  • a polymerizable composition comprising a compound represented by the following general formula (X) having a molecular weight of 180 to LOOO.
  • R 5 and R 6 each represent a hydrogen atom or an alkyl group
  • R 3 is a substituent bonded to any position of the saturated hydrocarbon ring to which the general formula (X) R 2 is bonded
  • n Is an integer from 0 to 7.
  • R 3 may be the same as or different from each other.
  • L is the general formula (X)
  • R 2 is a (p + 1) valent linking group or a simple bond bonded at any position to the saturated hydrocarbon ring to which p is bonded
  • p is an integer from 1 to 3
  • q is It is an integer from 1 to 3.
  • plural R 4 , R 5 and R 6 may be the same or different from each other.
  • q plural, plural L, R 4 , R 5 and R 6 are each They may be the same or different.
  • An image forming method in which the ink composition according to any one of the items 7 to 9 is jetted onto a recording material in an image-like manner from an inkjet recording head, and printing is performed on the recording material.
  • An image forming method comprising curing the ink composition through a step of heating after the ink composition has landed, or a step of irradiating an active ray for 0.001 seconds to 1.0 seconds. .
  • a compound having a molecular weight of 180 to 1000 represented by the following general formula (X—A):
  • R u , R 1, R 15 , R lb represent a hydrogen atom or an alkyl group, and R ′′ is bonded to an arbitrary position of the saturated hydrocarbon ring in the general formula (X—A).
  • M represents an integer from 0 to 7
  • R 14 represents a hydrogen atom or an alkyl group
  • L 2 represents an arbitrary position of the saturated hydrocarbon ring in the general formula (X—A)
  • the compound according to 14 above, wherein the general formula (X—A) is represented by the following general formula (X—B):
  • R 1 and R 2 each represents an alkyl group, represents a hydrogen atom or an alkyl group
  • L 3 represents an alkylene group, an oxygen atom, or a combination of the alkylene group and the oxygen atom.
  • the present invention cures with high sensitivity even under high-temperature conditions, has excellent storage stability, and the formed cured film has excellent adhesion, flexibility, storage stability, environmental resistance, especially durability against temperature changes. It was possible to provide an extremely excellent polymerizable composition, ink composition, image forming method using the ink composition, ink jet recording apparatus, and specific alicyclic epoxide. Brief Description of Drawings
  • FIG. 1 is a diagram showing a configuration of a main part of a recording apparatus used in the present invention.
  • FIG. 2 is a diagram showing a configuration of a main part of another recording apparatus used in the present invention.
  • the composition is cured with high sensitivity even under a high temperature condition, and the storage stability is improved.
  • the cured film thus formed was able to obtain a polymerizable composition having excellent adhesion, flexibility, storage stability, environmental resistance, especially resistance to temperature changes.
  • an ink composition containing the polymerizable composition, an image forming method using the ink composition, an ink jet recording apparatus, and the like can be obtained together, and further provide a specific alicyclic epoxide. did it.
  • the present inventor used a polymerizable composition containing a compound having an epoxide structure represented by the general formula (X) (also oxsilane structure).
  • X an epoxide structure represented by the general formula (X) (also oxsilane structure).
  • X an epoxide structure represented by the general formula (X) (also oxsilane structure).
  • a cured film that is strong without being affected by environmental humidity even with a low illuminance, retains sufficient hardness and flexibility before and after long-term storage, and has excellent resistance to temperature changes can be obtained. It has been found that, when the polymerizable composition is used as an ink composition and an image is formed, a high-quality image can be obtained, and the present invention has been achieved.
  • R 1 and R 2 in the general formula (X) are hydrogen atoms or alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert butyl group, iso butyl group, sec Butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, etc.), which have further substituents.
  • alkyl groups for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert butyl group, iso butyl group, sec Butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, heptyl group, octy
  • substituent of the alkyl group having a substituent that may be substituted examples include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group). , Ethoxy group, n-propoxy group, iso propoxy group, n butoxy group, tert butoxy group, etc.), acyl group (for example, acetyl group, propiol group, trifluoroacetyl group, etc.), carbon number 1-20 Pieces of asyl Alkoxy group (e.g.
  • R 1 or R 2 is preferably an alkyl group and the other is a hydrogen atom.
  • R 1 or R 2 is an alkyl group
  • preferred as the alkyl group is an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms is more preferred and has 1 to 3 carbon atoms.
  • Most preferred is a methyl group, more preferably an alkyl group.
  • R 3 in the general formula (X) represents a substituent, and examples of the substituent include the above-described alkyl group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), a carbon number of 1 to 20 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl groups (for example, acetyl group, propiol group, A trifluoroacetyl group, etc.), an acyloxy group having 1 to 20 carbon atoms (eg, acetooxy group, propio-oxy group, trifluoroacetoxy group, etc.), an alkoxy carboxylic group having 1 to 20 carbon atoms ( Methoxycarbon group, ethoxycarbol group, tert-butoxycarbonyl group, etc.), alky
  • n in the general formula (X) is an integer of 0 to 7, and when n is plural, R 3 may be the same or different from each other.
  • R 4 to R 6 in the general formula (X) each represent a hydrogen atom or an alkyl group, and examples of the alkyl group include the same groups as the alkyl groups that can be R 1 and R 2 described above.
  • R 4 is a hydrogen atom
  • R 5 and R 6 are alkyl groups! /.
  • R 4 to R 6 are alkyl groups, each is an alkyl group having 1 to 20 carbon atoms. It is most preferable that the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • L in the general formula (X) is a (p + 1) -valent linking group or a simple bond
  • p is an integer from 1 to 3
  • q is an integer from 1 to 3
  • L is bonded at any position to a saturated hydrocarbon ring containing R 1 and R 2 .
  • q is preferably 1 or 2. More preferably, q is 1.
  • divalent linking groups include O group, S group, CO group, CS group, SO group, SO group, the following groups, and groups formed by combining these groups.
  • Furan 2,5 diyl bismethylene [2, 5-CH 2 -CH 2 O-CH 2-]
  • L is a trivalent or higher linking group
  • the above divalent linking basic power examples thereof include a linking group in which a primary atom is removed to form a bond.
  • Examples of the substituent which may have a substituent for L include a group having the same meaning as the above-mentioned R 3, and the connecting group between the main chain and the substituent is the above-mentioned 2 Examples of the valent linking group can be given.
  • substituents on the linking group are an alkyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a hydroxy group.
  • the substituent on the linking group may be a divalent or higher valent linking group by removing a necessary number of hydrogen atoms and using it as a bond, in which case the general formula (X)
  • the hydrogen atom bonded to any position in the inside may be removed and bonded at that position to form a ring, but the number of ring members should be 3-5, and 3-4 3 is the most preferred.
  • L may be added to at least one carbon atom in the chain as at least one carbon atom constituting the oxosilane ring.
  • L may be further added to the general formula (X).
  • the number of oxysilane rings formed is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
  • L is an oxygen atom, or an oxygen atom that is preferably a divalent linking group having 1 to 8 carbon atoms in the main chain, which may contain an oxygen atom in the main chain, or an oxygen atom in the main chain.
  • a divalent linking group having a carbon number of 5 to 5 in the main chain which may be contained is more preferable.
  • plural R 4 to R 6 may be the same or different from each other.
  • q is plural, plural L are the same or different from each other! / It ’s okay!
  • the molecular weight of the compound represented by the general formula (X) is preferably in the range of 180 to 1000, more preferably 200 to 700.
  • R u , R 12 , R 15 , and R 16 each represent a hydrogen atom or an alkyl group, and R 13 is saturated in the general formula (X—A).
  • Al bonded to any position of the hydrocarbon ring Represents a kill group, m represents an integer of 0 to 7, R 14 represents a hydrogen atom or an alkyl group, and L 2 is bonded to any position of the saturated hydrocarbon ring in the general formula (X—A).
  • Alkylene group e.g., methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, otatamethylene group, nonamethylene group, decamethylene group
  • the combination force represents a divalent linking group formed.
  • R 11 and R 12 is preferably an alkyl group and the other is a hydrogen atom
  • R 15 and R 16 are preferably an alkyl group.
  • Suitable alkyl groups for R u , R 12 , R 13 , R 15 and R 16 are as defined for the examples of R 1 and R 2 described above, preferably alkyl having 1 to 8 carbon atoms.
  • m is more preferably 0-5, more preferably 0-3. When m is plural, plural R 13 may be the same or different.
  • R 14 is an alkyl group
  • preferred alkyl groups have the same meanings as preferred alkyl groups for R u , R u , R 13 , R 15 and R 16 , but R 14 is most preferably a hydrogen atom.
  • R 14 is most preferably a hydrogen atom.
  • the alkylene group of L 2 an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is preferred.
  • This alkylene group may be substituted with a substituent having the same meaning as in the above-described examples of the substituent of L. Further, the substituent is substituted with a substituent having the same meaning as in the above-described example of the substituent of L. Also good.
  • L 2 Preferable as a substituent for the alkylene group of L 2 is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, or a substituent in which these are substituted with a halogen atom.
  • L 2 may have an ether bond by containing an oxygen atom in the main chain of the alkylene group or in the substituent.
  • the number of oxygen atoms is 1 to 5 preferably contained in L 2, 1 to 3 is more preferable.
  • a compound represented by the general formula (X—A) is particularly preferable.
  • R 25 and R 26 represent an alkyl group
  • R 24 represents a hydrogen atom or an alkyl group.
  • L 3 represents an alkylene group, an oxygen atom, or a divalent linking group formed of a combination thereof.
  • the alkyl group suitable for R 25 and R 26 has the same meaning as the alkyl group mentioned as the example of R 1 and R 2 described above, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably Is an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group.
  • R 24 is an alkyl group
  • preferred alkyl groups have the same meanings as preferred alkyl groups for R 25 and R 26 , but R 24 is most preferably a hydrogen atom.
  • an alkylene group having 1 to 10 carbon atoms more preferably an alkylene group having 1 to 20 carbon atoms, is more preferable.
  • This alkylene group is substituted with a substituent having the same meaning as in the above-mentioned examples of the substituent for L, and the substituent may be further substituted with the same substituent.
  • a substituent for the alkylene group of L 3 is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, or a substituent in which these are substituted with a halogen atom.
  • L 3 may have an ether bond by containing an oxygen atom in the main chain of the alkylene group or in the substituent.
  • the number of oxygen atoms is 1 to 5 preferably contained in the L 3, 1 to 3 is more preferred.
  • Bisabolol 11.8 g and methylene chloride 120 ml were added to the reactor and stirred.
  • a solution prepared by dissolving 36 g of m-chloroperbenzoic acid (mCPBA) in 360 ml of methylene chloride was added dropwise to the stirring solution of bisabolol in methylene chloride at room temperature over 1 hour.
  • 100 ml of saturated sodium sulfite aqueous solution was added, the remaining excess mC PBA was deactivated, the organic layer was separated using a separatory funnel, and the aqueous layer was washed with 100 ml of methylene chloride. Organic matter was extracted from the cocoon.
  • the organic layers were mixed and washed twice with 100 ml saturated aqueous sodium bicarbonate solution, and then washed sequentially with 100 ml pure water and 100 ml saturated brine.
  • the obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 9 g of X-2.
  • the target product was confirmed by NMR and mass spectrum (parent peak 255).
  • the reactor was charged with 12 g of the following intermediate A and 90 ml of methylene chloride.
  • a solution prepared by dissolving 26.3 g of m-chloroperbenzoic acid (mCPBA) in 270 ml of methylene chloride was added dropwise to the stirring methylene chloride solution of intermediate A over 1 hour at room temperature.
  • 80 ml of saturated sodium sulfite aqueous solution was added to quench the remaining excess mCPBA, and the organic layer was separated using a separatory funnel, and 80 ml of methylene chloride was added to the aqueous layer. The organic matter was extracted.
  • the organic layers were mixed and washed twice with 80 ml of saturated aqueous sodium bicarbonate, and then washed successively with 80 ml of pure water and 80 ml of saturated saline.
  • the obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 12 g of X-4.
  • the target product was confirmed by 1 H-NMR and mass spectrum (parent peak 297).
  • a compound having an oxetane ring can be used in combination with the compound represented by the general formula (X). Any known oxetane compound described in 220526 and 2001-310937 can be used.
  • an oxetane containing only one oxetane ring may be used in order to obtain appropriate handling of the composition due to the viscosity and storage stability of the composition. It is preferable to use a compound in combination, for example, the following Alonoxetane OXT-101 (Exemplary Compound 1), ⁇ -212 (Exemplary Compound 2) manufactured by Toagosei Co., Ltd., and the like.
  • a compound having two oxetane rings is particularly preferable because the resulting composition has excellent adhesiveness, low viscosity, and excellent workability.
  • a compound represented by the general formula (102) described in paragraph No. 0094 (ii) of JP-A-2004-143135 is exemplified. It is done.
  • Examples of the compound having 3 to 4 oxetane rings include JP-A-2004-14313.
  • Examples include compounds represented by general formula (108) described in paragraph No. 0111 (Chemical Formula 24) of No. 5 publication.
  • examples of compounds having 1 to 4 oxetane rings other than those described above include those represented by the general formula (10) described in paragraph No. 0118 (Chemical Formula 27) of JP-A-2004-143135.
  • Preferable specific examples of the oxetane compound used in the present invention include JP-A-2004-143.
  • an alicyclic epoxide represented by the following general formula (A) (also referred to as alicyclic epoxide in the present specification): In the case where it is necessary to impart desired physical properties such as flexibility to the cured film, it is preferable to use these in combination.
  • R does not contain a reactive functional group that is cationically polymerizable or radically polymerizable.
  • MlO represents 1, 2, 3 or 4.
  • R represents a cationically polymerizable or radically polymerizable reactive group.
  • Examples of the substituent that represents a substituent that does not include a functional group include a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom), and an alkyl group having 1 to 20 carbon atoms (for example, a methyl group and an ethyl group).
  • a halogen atom for example, a chlorine atom, a bromine atom, and a fluorine atom
  • an alkyl group having 1 to 20 carbon atoms for example, a methyl group and an ethyl group
  • cycloalkyl group having 3 to 6 carbon atoms for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
  • An alkoxy group for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.
  • a C2-C20 acyl group for example, acetyl group, propionyl group) , Trifluoroacetyl group, etc.
  • an acyloxy group having 2 to 20 carbon atoms for example, acetooxy group, propio-loxy group, trifluoro group
  • Chloroacetoxy group etc.
  • a C2-C20 acyl acyl group for example, acetylylthio group, prop
  • alkylthiocarbol group having 2 to 20 carbon atoms for example, methylthiocarbol group, ethylthiocarbol group, tert-butylthiocarbole group) Group, etc.
  • These groups may further have a substituent.
  • substituents include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n propoxy group, iso propoxy group, n butoxy group).
  • C2-C20 acyl group for example, acetyl group, propionyl group, trifluoroacetyl group, etc.
  • C2-C20 acyl group for example, acetooxy group, propio-loxy group) Group, trifluoroacetoxy group, etc.
  • C2-C20 alkoxy group for example, methoxycarbol group, ethoxycarbonyl group, tertbutoxycarbonyl group, etc.
  • C2-C20 group Alkylthiocarbon groups for example, methylthio group, ethylthiocarbol group, tert-butylthiocarbon group, etc.
  • aryloxycarbon groups alkyl Sulfo - group, Arirusuruho - group, Shiano group, two Toro group is go up.
  • Preferable substituents are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarb
  • LV and alicyclic epoxide are compounds represented by the following general formula (AI), which are more preferable in that they produce a cured film with high hardness and further improve the adhesion of the cured film to the substrate. is there.
  • R represents a substituent
  • mi 1 represents 0, 1, 2, or 3.
  • 111 112 113 114 Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • Y and Y are it Each independently represents O or S, pl l represents 0, 1 or 2, ql l represents 0 or 1, rl l represents 0 or 1, and si 1 represents 0 or 1.
  • examples of the substituent represented by R include a halogen atom (for example,
  • Groups for example, methoxy group, ethoxy group, n-propoxy group, iso propoxy group, n butoxy group, tert butoxy group, etc.
  • acyl groups for example, acetyl group, propiool group, trifluoroacetyl group, etc.
  • a C1-C20 acyloxy group for example, acetooxy group, propio-loxy group, trifluoroacetoxy group, etc.
  • C1-C20 alkoxycarbonyl group for example, methoxycarbon group, ethoxy) Carbon group, tert-butoxycarbonyl group, etc.
  • alkylthiocarbon group having 2 to 20 carbon atoms for example, methylthiocarbol group, ethylthiocarbol group, tert-butylthiocalyc group
  • Ball - Le group Ball - Le group
  • ⁇ reel O propoxycarbonyl - group, alkylsulfonyl -
  • R 1, R 2 and R 3 represent a hydrogen atom or a substituted or unsubstituted alkyl group.
  • Examples of the substituent of the alkyl group having a group include a halogen atom (for example, chlorine atom, fluorine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n —Propoxy group, iso propoxy group, n-butoxy group, tert butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), an acyloxy group having 1 to 20 carbon atoms (for example, Acetoxy group, propio-loxy group, trifluoroacetoxy group, etc.), an alkoxy carbo group having 1 to 20 carbon atoms (for example, a methoxy carbo ol group, an ethoxy carbo ol group, a tert butoxy carbo ol group, etc.), C2-C20 alkylthiocarbon group
  • pl l represents 0, 1 or 2
  • ql l, rl l, sl l represents 0 or 1;
  • An alicyclic epoxide particularly preferred in terms of producing a cured film with high hardness and further improving the substrate adhesion of the cured film is a compound represented by the following general formula (A-II). is there.
  • R represents a substituent
  • ml2 represents 0, 1 or 2.
  • 121 122 123 124 Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • pl2 represents 0, 1 or 2
  • ql2 represents 0 or 1
  • rl 2 represents 0 or 1
  • sl2 represents 0 or 1.
  • R is as defined above.
  • Y and Y represent ⁇ or S, ⁇ is preferred
  • ml2i represents 0-2, 0 or ⁇ or 1 power! / ⁇ . ⁇ 12 ⁇ to 0, 1 or ⁇ to 2, ql2, rl2, sl2 represents 0 or 1.
  • R 1, R 2 and R are synonymous with R 1, R 2 and R 3.
  • a more preferred alicyclic epoxide is a compound represented by the following general formula (A) in that the cured film having high curing sensitivity improves the substrate adhesion, and the hardness sensitivity is not easily affected by changes in the printing environment. — 111), a compound represented by general formula (A—IV) or general formula (A—V).
  • R represents a substituent
  • ml3 represents 0, 1 or 2.
  • R, R, R are each Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • pl3 represents 0, 1 or 2, ql3 or 0 or 1
  • R represents a substituent
  • ml4 represents 0, 1 or 2.
  • 141 142 143 144 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • pl4 represents 0, 1 or 2.
  • R represents a substituent
  • ml5 represents 0, 1 or 2.
  • R is a hydrogen atom or substituted
  • s 15 represents 0 or 1.
  • R 1, R 2 and R 3 have the same meanings as R. ml3, ml4, ml5 should be 0-2
  • R 1 Represents 0 or ⁇ or 1 power! / ⁇ . ⁇ 13, ⁇ 14 ⁇ up to 0, 1 or ⁇ up to 2, ql3, sl5i up to 0 or ⁇ up to 1 R 1, R 2, R 3, R 4, R 5, R 5, and R 5 have the same meanings as R 1, R 2, and R 3.
  • a particularly preferred alicyclic epoxide is the following general formula in that the cured film having a high curing sensitivity improves the adhesion of the base material of the cured film and the hardness of the cured film is not easily affected by changes in the printing environment.
  • R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example,
  • Preferred as alkyl groups are methyl group, ethyl group, Propyl group.
  • R 1, R 2 and R are synonymous with R 1, R 2 and R 3. ql
  • the content of the compound represented by the general formula (X) is not particularly limited, but is preferably in the range of 0.1 mass% force 60 mass%.
  • a compound represented by the general formula (X) an oxetane compound and a monofunctional epoxide represented by the general formula (A).
  • the difunctional alicyclic epoxide is preferably a polyfunctional epoxide represented by the following general formula (B).
  • R 1 and R 2 represent substituents
  • m20 and n20 represent 0, 1 or 2
  • 0 or 1 is preferred.
  • L is carbon which may contain an oxygen atom or a sulfur atom in the main chain
  • examples of the substituent represented by R 1 and R 2 include a halogen atom (for example, chlorine atom
  • Preferable substituents are an
  • linking group examples include the following groups and groups formed by combining these groups with a plurality of O groups, S groups, CO groups, and C S groups.
  • Furan 2,5 diyl bismethylene [2, 5-CH 2 -CH 2 O-CH 2-]
  • the trivalent or higher linking group includes a group formed by removing as many hydrogen atoms as desired from the divalent linking groups listed above as necessary, and an O group, S group, CO group, and CS group.
  • the group which can be combined together can be mentioned.
  • L may have a substituent.
  • substituents include halogen atoms (e.g. chlorine
  • Atoms, bromine atoms, fluorine atoms, etc. alkyl groups having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), alkoxy groups having 1 to 6 carbon atoms (for example, , Methoxy group, ethoxy group, n-propoxy group, iso propoxy group, n-butoxy group, tert butoxy group, etc.), acyl group (eg, acetyl group, propiool group, trifluoroacetyl group, etc.), acyloxy group ( For example, acetooxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxy carbo yl group (for example, methoxy carbo ol group, ethoxy carbo ol group, tert butoxy carbo ol group, etc.) It is done.
  • L is a divalent chain having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain.
  • Preferred is a divalent linking group having 1 to 5 carbon atoms in which the main chain preferred by the linking group is only carbon.
  • the alicyclic epoxide is particularly preferred in that it produces a hard film with high hardness and further improves the adhesion of the cured film to the substrate. ).
  • R 1 and R 2 represent a substituent
  • m21 and n21 represent 0, 1 or 2
  • 0 or 1 is preferred.
  • pl and ql represent 0 or 1, respectively.
  • rl represents 1-3.
  • L is oxygen source in the main chain
  • R 1 and R 2 represent a substituent
  • m22 and n22 represent 0, 1 or 2
  • 0 or 1 is preferred.
  • p2 and q2 each represents 0 or 1.
  • r2 represents 1-3.
  • L is oxygen source in the main chain
  • It may contain a hydrogen atom or a sulfur atom! It represents an r2 + monovalent linking group or single bond having 1 to 15 carbon atoms.
  • R 1, R 2, R 3 and R 4 have the same meaning as R in the general formula (A-1).
  • L a divalent valence of 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain represented by L
  • linking group examples are the same as those described in the description of L. L, as L
  • 0 1 2 is preferably a divalent linking group having 1 to 8 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain, and a divalent linking group having 1 to 5 carbon atoms in which the main chain only has carbon power. More preferred.
  • a particularly preferred alicyclic epoxide is represented by the following general formula (B-III) or (B-IV) in that the curing sensitivity is high and the curing sensitivity is not easily affected by changes in the printing environment. It is a compound.
  • R 1 and R 2 represent a substituent
  • m23 and n23 each represents 0 or 1.
  • r3 represents 1-3.
  • L represents a carbon number which may contain an oxygen atom or a sulfur atom in the main chain] '15 and represents an r3 + 1 monovalent linking group or a single bond.
  • R 1 and R 2 represent a substituent
  • m24 and n24 represent 0 or 1.
  • L contains oxygen or sulfur atoms in the main chain
  • R 1, R 2, R 3 and R 4 have the same meaning as R in the general formula (A-1). .
  • L a divalent valence of 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain represented by L
  • linking group are the same as those described in the description of L.
  • the addition amount of these epoxides is 10 mass% to from the viewpoint of improving the stability of the curability depending on the curing environment (temperature, humidity) and keeping the film properties after curing appropriate.
  • the content is preferably 40% by mass, and more preferably in the range of 20% by mass to 40% by mass.
  • one type of polyfunctional epoxide may be used alone, or two or more types may be used in appropriate combination.
  • a conventionally known polymerization initiator can be used.
  • the polymerization initiator is used as an ink composition that is preferably an acid generator, a photoacid generator is used. Preferably there is.
  • the polymerizable composition of the present invention can be polymerized by covering with actinic rays or heat, or both.
  • the polymerizable composition of the present invention is converted into an ink composition (ink composition). The product will be described in detail later.)
  • it is preferable to polymerize by irradiating with actinic rays it is more preferable to polymerize by irradiating with ultraviolet rays.
  • the photoacid generator used in the cationic polymerization type ink using the polymerizable composition of the present invention for example, a chemical amplification type photoresist or a compound used for photopower thione polymerization is used (organic electronic material). Study Group, “Organic Materials for Imaging”, Bunshin Edition (1993), pages 187-192). Examples of compounds suitable for the present invention are listed below.
  • sulfonates such as CF 2 SO—salts. Borate as a match
  • sulfone compounds that generate sulfonic acid can be mentioned.
  • Specific examples thereof include compounds described in JP-A-2004-143135, paragraph No. 0151 (Chemical Formula 32). Can be mentioned.
  • a halide that generates halogenated hydrogen can also be used.
  • compounds described in JP-A-2004-143135, paragraph No. 0152 are used. Can be mentioned.
  • an iron allene complex can be mentioned, and specific examples thereof include, for example, JP-A-2004-14.
  • Examples of the light-power thione polymerization initiator used in the present invention include aryl chloride salt derivatives (for example, Cyracure UVI-6990 manufactured by Union Carbide, Cyracure UVI 6974, Adekatop manufactured by Asahi Denka Kogyo Co., Ltd.) MER SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172), Aryododom salt derivative (for example, RP-2074 made by Rhodia), Allen — Acid generators such as ion complex derivatives (for example, Irgacure 261 manufactured by Ciba Geigy Co., Ltd.), diazo-um salt derivatives, triazine initiators and other halogenated compounds.
  • the cationic polymerization initiator is preferably contained in a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass
  • Preferable photoacid generators used in the present invention are onium salts such as sulfonium salts, iodine salts, ammonium salts, phosphonium salts, and the like.
  • a chloride is preferred.
  • a sulfo represented by the general formulas (1-1), (1-2) (I3) described in claim 8 of JP-A-2004-143135 Nium salt can be mentioned.
  • Examples of the photopolymerization accelerator include anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), and phenothiazine derivatives (for example, 10-methylphenol).
  • anthracene for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.
  • phenothiazine 10H-phenothiazine
  • phenothiazine derivatives for example, 10-methylphenol
  • the viscosity is preferably 0. ImPa's ⁇ : LOOOmPa's It should be 0. lmPa's ⁇ 500mPa's. More preferred 0. More preferred to be lmPa's to 300 mPa's, Most preferred to be 0.1 mPa ⁇ s to 150 mPa ⁇ s! / ⁇ .
  • the ink composition of the present invention may be a composition containing the polymerizable composition of the present invention and a coloring material, or may contain various other additives.
  • the color material used in the ink composition using the polymerizable composition of the present invention can be used without limitation as long as it is a color material that can be dissolved or dispersed in the main component of the polymerizable compound, and may be an oil-soluble dye. Pigment is preferred, and pigment is preferred from the viewpoint of weather resistance and light resistance.
  • Pigments that can be preferably used in the present invention are listed below.
  • a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like can be used.
  • a dispersing agent it is encouraging to use a polymer dispersing agent, and as the polymer dispersing agent, there is Avecia's Solsperse series.
  • a synergist according to various pigments can be used as a dispersion aid.
  • the dispersant and dispersion aid are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
  • the dispersion medium is a solvent or a polymerizable compound.
  • the ink composition used in the present invention is preferably solvent-free because it is reacted and cured immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC problem of the remaining solvent occurs. Therefore, the dispersion medium is not a solvent but a polymerizable compound. Among them, it is preferable to select a monomer having the lowest viscosity in view of dispersibility.
  • the average particle size of the pigment particles is 0.08 ⁇ m to 0.5 ⁇ m.
  • the maximum particle size is 0.3 111 to 10 111, preferably 0.3 /
  • the pigment, dispersant, dispersion medium, dispersion conditions, and filtration conditions are appropriately set so that ⁇ -3 / ⁇ .
  • the colorant concentration is preferably 1% by mass to 10% by mass of the whole ink! /.
  • a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.
  • the thermal base generator for example, a salt of an organic acid and a base that decomposes by decarboxylation by heating, an intramolecular nucleophilic substitution reaction, a Rossen rearrangement, a Beckmann rearrangement, or the like decomposes to release amines.
  • a compound that releases a base by causing some kind of reaction upon heating is preferably used.
  • a salt of triclonal acetic acid described in British Patent No. 998, 949, a salt of alphasulfoacetic acid described in US Pat. No. 4,060,420, JP-A-59-157637 Propylic acid salts, 2-carboxycarboxamide derivatives described in Japanese Patent Publication No.
  • JP-A-59-168440 and alkali bases and alkaline earth metals in addition to organic bases. Salts with acids, hydroxam force rubamates utilizing the Lossen rearrangement described in JP-A-59-180537, aldoxime force rubamates described in JP-A-59-195237, which produces -tolyl by heating, etc. All I can get lost.
  • British Patent No. 998,945 U.S. Pat.No.
  • specific examples include chlorodiacetate guanidine, trichlorodiethyl acetate darzine, trichlorodiethyl acetate potassium, phenolsulfol acetate guanidine, p-cyclodiethylsulfol-sulfone.
  • the thermal base generator can be used in a wide range.
  • the ink composition of the present invention is a new acid composition produced by an acid generated by actinic ray irradiation, which is already known, such as those disclosed in JP-A-8-248561 and JP-A-9-34106. It is also possible to contain an acid proliferating agent that generates.
  • the ink composition of the present invention is produced by well dispersing a pigment together with a polymerizable composition and a pigment dispersant using a normal dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with a polymerizable composition. Sufficient dispersion is possible even with dispersion using a normal disperser, so that excessive dispersion energy is not used and a large amount of dispersion time is not required, so it is difficult to cause deterioration during dispersion of ink components. An ink with excellent properties is prepared. The ink is preferably filtered through a filter having a pore size of 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the ink composition of the present invention has a viscosity of 5 mPa's at 25 ° C from the viewpoint of preventing a decrease in the followability of the discharge and improving the stability of the discharge in a high-frequency head. It is preferable to adjust so that it exceeds 40 mPa's. Further, the viscosity at 25 ° C. is preferably adjusted to 7 mPa ⁇ s to 80 mPa ⁇ s, more preferably 7 mPa ⁇ s to 40 mPa ⁇ s. Inks with a viscosity of 7111?
  • &'5-40111?&' 5 at 25 ° ⁇ are especially normal 4kHz ⁇ : LO Even from a head with a frequency of kHz to a head with a high frequency of 10 to 50 KHz, it shows stable ejection characteristics.
  • the ink composition of the present invention preferably has an electric conductivity of 10 ⁇ SZcm or less in a piezo head and does not cause electrical corrosion inside the head.
  • the conductivity In the case of the container-type, it is necessary to adjust the conductivity with the electrolyte. In this case, the conductivity must be adjusted to 0.5 mSZcm or more.
  • ink ejection also referred to as ejection
  • light irradiation heating, and the like
  • uniform dot diameters are provided for various supports.
  • Force required to be obtained the surface tension of ink at 25 ° C is 25 mNZn from the viewpoint of stable emission (also called ejection) and obtaining a desired dot diameter.
  • ⁇ / Preferably in the range of 40mNZm!
  • a surfactant may be added as necessary.
  • the surfactant preferably used in the ink composition of the present invention include, for example, diionic sulfosuccinates, alkylnaphthalene sulfonates, fatty acid salts and the like surfactants such as polyoxyethylene alkyl ethers.
  • Nonionic surfactants such as polyoxyethylene alkyl aryl ethers, acetylene glycols, polyoxyethylene 'polyoxypropylene block copolymers, alkylamine salts, cations such as quaternary ammonia salts And surface active compounds having a polymerizable group.
  • silicone-modified acrylate fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, fluorine-modified oxetane, etc. Active compounds are preferred.
  • additives other than those described above can be used in the ink composition of the present invention.
  • leveling additives, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes to adjust film properties should be added.
  • it is also effective to add a trace amount of organic solvent.
  • it is effective to add in the range where solvent resistance and VOC problems do not occur, and the amount used is in the range of 0.1% to 5% by mass, preferably 0%. 1% by mass to 3% by mass.
  • the ink composition of the present invention is ejected and drawn on a recording material by an ink jet recording method, and then the ink is irradiated by actinic rays such as ultraviolet rays or by heating.
  • the composition (also referred to simply as ink) is cured.
  • the ink jet nozzles during ink ejection (also referred to as ejection) to lower the viscosity of the ink liquid.
  • the heating temperature is 35 ° C to 100 ° C, preferably 35 ° C to 60 ° C.
  • the current force is that the total ink film thickness exceeds 20 / zm.
  • the recording material is often a thin plastic material.
  • the curl of the material can not be used because there is a problem that the texture of the entire printed matter changes just because of the wrinkle problem.
  • the amount of liquid droplets discharged from each nozzle is preferably 2 to 15 pl.
  • the irradiation timing is as early as possible.
  • the viscosity or water content of the ink is preferable. It is preferable to start the light irradiation at the following timing.
  • a basic method of actinic ray irradiation is disclosed in JP-A-60-132767. According to this, a light source is provided on both sides of the recording head unit, and the recording head and the light source are scanned by the shuttle method. Irradiation may occur after a certain period of time after ink landing. It becomes. Further, the curing is completed by another light source that is not driven.
  • a method using an optical fiber or a collimated light source is applied to a mirror surface provided on the side of a recording head unit, and the recording unit is irradiated with UV light. How to do it is disclosed. Any of these irradiation methods can be used in the image forming method of the present invention.
  • irradiation with actinic rays is divided into two stages.
  • actinic rays are irradiated in the above-described manner between 0.001 seconds and 1.0 seconds after ink landing, and after all printing is completed, further actinic rays are emitted.
  • the irradiation method is also one of the preferred embodiments. By dividing the actinic ray irradiation into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.
  • Examples of light sources used for actinic ray irradiation include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten halogen copying lamps, high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, Examples include, but are not limited to, UV lasers, xenon flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, LEDs, etc. Among them, fluorescent tubes are preferred because of their low energy and low cost.
  • the light source wavelength is 250 nm to 370 nm, preferably 270 ⁇ ! It is preferable in terms of light source power sensitivity with a peak of emission wavelength at ⁇ 320 nm.
  • the illuminance is lmWZcm 2 to 3000 mWZc, preferably lmWZcm 2 to 200 mWZcm 2 .
  • an irradiation dose of 1 to 5 Mrad, which is usually cured with an electron beam with an energy of 300 eV or less.
  • the ink composition of the present invention is used to perform image printing on a recording medium (both of the base materials).
  • a recording medium a wide variety of conventional synthetic resins have been used. More specifically, for example, polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile butadiene styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate
  • the thickness and shape of these synthetic resin substrates are not limited at all.
  • a non-absorbent support can be used in addition to a normal non-coated paper, a coated paper, etc. Among them, a non-absorbent support can be used as the base material. Is preferably used.
  • various non-absorbable plastics and films thereof can be used as the non-absorbent support. Examples of the various plastic films include PET film, OPS film, OPP film, ONy Film, PVC film, PE film, TAc film. Other plastics include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubber. It can also be applied to metals and glasses.
  • the structure of the present invention is effective particularly when an image is formed on a PET film, OPS film, OPP film, ONy film, or PVC film that can be shrunk by heat.
  • These substrates are hard to follow the shrinkage of the substrate if the film is easily curled or deformed due to ink curing shrinkage and heat generation during the curing reaction.
  • the wetting index force is S40mN / m to 60mN Zm as a force base material including OPP film with low surface energy, OPS film and relatively large surface energy, up to PET! / ,.
  • a long (web) recording material is used in terms of the cost of recording materials such as packaging costs and production costs, print production efficiency, and compatibility with various size prints. Is more advantageous.
  • Fig. 1 is a front view showing a configuration of a main part of the ink jet recording apparatus of the present invention.
  • the recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like.
  • a platen unit 5 is installed under the recording material P.
  • the platen section 5 has a function of absorbing ultraviolet rays and absorbs extra ultraviolet rays that have passed through the recording material P. As a result, a high-definition image can be reproduced very stably.
  • the recording material P is guided by the guide member 6 and moves from the near side to the far side in Fig. 1 by the operation of the conveying means (not shown).
  • Head scanning means (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.
  • the head carriage 2 is installed on the upper side of the recording material P, and a plurality of recording heads 3 to be described later are arranged in accordance with the number of colors used for image printing on the recording material P, and the discharge ports are arranged on the lower side.
  • the head carriage 2 is installed on the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.
  • the head carriage 2 houses the recording head 3 of white (W), yellow (Y), magenta (M), sheen (C), black (K), and white (W).
  • the number of colors of the recording head 3 housed in the head carriage 2 is appropriately determined.
  • the recording head 3 has an ink composition (for example, ultraviolet curable ink) supplied by an ink supply means (not shown) by the operation of a discharge means (not shown) provided in the interior thereof.
  • the discharge roller is also discharged toward the recording material P.
  • the ultraviolet hard ink ejected by the recording head 3 is composed of a coloring material, a polymerizable monomer, an initiator, and the like, and the initiator acts as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by monomer crosslinking and polymerization reactions.
  • the recording head 3 moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. UV curable ink is ejected as ink droplets onto the possible region), and the ink droplets are landed on the landable region.
  • the recording material P is appropriately moved from the front to the back in FIG. While performing the scanning by the head scanning means, the recording head 3 discharges the ultraviolet curable ink to the next landable area adjacent in the depth direction in FIG. [0231] By repeating the above-described operation and discharging the ultraviolet curable ink from the recording head 3 in conjunction with the head scanning means and the conveying means, an image composed of an aggregate of ultraviolet curable ink droplets is formed on the recording material P.
  • the irradiation means 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength.
  • ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy
  • a filter that transmits ultraviolet light of a specific wavelength.
  • Cold cathode tube, mercury lamp tube or black light is preferred.
  • a cold cathode tube and a black light emitting ultraviolet light having a wavelength of 365 nm are preferable because they can prevent bleeding, control the dot diameter efficiently, and reduce wrinkles during curing.
  • black light as the radiation source of the irradiation means 4
  • the irradiation means 4 for curing the ultraviolet curable ink can be produced at low cost.
  • Irradiation means 4 can be set by a recording device (ultraviolet curable ink jet printer) 1 among the landable areas where the recording head 3 ejects ultraviolet ray curable ink by a single scan driven by the head scanning means. It has almost the same shape as the largest or larger than the landable area.
  • the irradiation means 4 is installed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.
  • the recording head is determined by the distance hi between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the ink ejection part 31 and the recording material P in Fig. 3 (hl ⁇ h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). is there. Further, it is more preferable that the space between the recording head 3 and the irradiation means 4 is a bellows structure 7.
  • the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be appropriately changed by replacing the ultraviolet lamp or filter provided in the irradiation means 4.
  • FIG. 2 is a diagram showing another example of the configuration of the main part of the ink jet recording apparatus.
  • the ink jet recording apparatus shown in FIG. 2 is called a line head system, and the ink jet recording head 3 of each color is covered with the head carriage 2 so as to cover the entire width of the recording material P. A plurality of them are fixedly arranged. The head carriage 2 is shielded from light.
  • an irradiation means 4 arranged so as to cover the entire width of the recording material P and cover the entire ink printing surface.
  • the ultraviolet lamp used for the illumination means 4 can be the same as described in FIG.
  • the head carriage 2 and the irradiation means 4 are fixed, and only the recording material P is transported to perform image formation by ejecting and curing ink.
  • a polymerizable compound and a polymerization initiator were added as shown in Tables 1 and 2, and dissolved in 50 parts by mass of methylene chloride to prepare a polymerizable composition.
  • the prepared polymerizable composition was polymerized by applying actinic rays or heat as shown in Table 2.
  • Actinic rays were irradiated for 20 minutes from a high-pressure mercury lamp placed on a container containing the polymerizable composition.
  • the polymerizable composition was placed in a container equipped with a refluxer and heated to reflux for 20 minutes.
  • Reaction fluidity After the polymer was collected by filtration and dried, the mass of the polymer obtained was measured to calculate the yield, and the polymerizability of the polymerizable composition was evaluated accordingly.
  • the polymerizable composition is polymerized in an atmosphere of 80% humidity, and the residue is washed with a solvent and rinsed. After drying, the mass of the obtained polymer was measured to calculate the yield, and the polymerizability of the polymerizable composition under high humidity conditions was evaluated.
  • the composition was shaken if necessary, and the coloration and thickening of the composition were visually evaluated as follows.
  • Tables 1 and 2 show the evaluation results of the polymerizable compositions.
  • UVI 6992 Dow Chemical Propion carbonate solution
  • WPI-113 Propion carbonate solution manufactured by Wako Pure Chemical Industries
  • the molecular weight of the compound represented by the general formula (X) according to the present invention used is as follows: X-1: 252.35, X—3: 338.48, X—5: 282.42
  • a polymerizable compound, an acid generator and a basic compound were dissolved as shown in Tables 3 and 4 to prepare a polymerizable composition.
  • Epolyide GT403 (manufactured by Daicel Chemical Industries)
  • the hardness of each cured film was measured according to JIS K 5400.
  • the hardness rank is (soft) 6B to B, HB, F, H to 9H (hard), 6B is the softest, and 9H is the hardest.
  • Adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) is pasted to the cured composition sample obtained in the cross-cut test of JIS K 5400, and then pressed once with a 2kg roller. The number of eye-shaped samples was investigated.
  • the obtained cured film was evaluated according to the method for evaluating bending resistance defined in JIS K 5600.
  • ® a composition having a viscosity at 25 ° C of 150 mPa ⁇ s or less
  • X a composition of 500 mPa's or more
  • the cured composition obtained was stored in a high-temperature and high-humidity environment at 85 ° C and 90% RH for one month, and the pencil pulling force test and flexibility evaluation of the cured composition were the same as described above. Then, the rank was evaluated as follows.
  • the obtained cured film is stored at 85 ° C for 30 minutes and then stored at 40 ° C for 30 minutes, and then the cured film surface is scratched to test whether the cured film peels off. ) was evaluated as follows.
  • the resulting cured film is stored at 85 ° C for 30 minutes, and after storage at -40 ° C for 30 minutes, the cured film is bent and tested for cracks in the cured film to withstand temperature changes. (Bend resistance) was evaluated. Repeatedly evaluated the rank as follows, until the cracking force reached the cured film, or until 10 cycles were reached without cracking.
  • Example 3 From Table 5, the sample of the present invention has sufficient adhesion and hardness, and cured film i: maintains hardness and flexibility even after long-term storage, has almost no deterioration, and has excellent durability against temperature change. It turns out that it is also excellent. [0275] Example 3
  • W Titanium oxide (anatase type: particle size 0.2 ⁇ )
  • the compounds used are as follows.
  • R100 Halitac R100 (Rosin-modified maleic acid rosin Harima Chemical Co., Ltd.)
  • Halitak 145P (Rosin-modified maleic acid resin, Harima Chemical Co., Ltd.) 3 ⁇ 4027
  • the ink supply system consists of an ink tank, supply pipe, front chamber ink tank just before the head, pipe with filter, and piezo head force.
  • the front chamber tank force was also insulated to the head and heated to 50 ° C.
  • the head is cooled according to the viscosity of each cured yarn and composite ink, and multi-sized dots with a droplet volume of 2 pl to 15 pl are applied to 720 x 720 dpi (1 dpi, that is, 2.54 cm per 2.54 cm).
  • the ink composition described above was continuously ejected by driving so that it could be ejected at a resolution of (the number of dots). Also recording material was heated to 50 ° C with a surface heater.
  • irradiation light source A High pressure mercury lamp VZero085 (manufactured by INTEGRATION TECHNOLOGY) or irradiation light source B: Metal halide lamp (manufactured by Nippon Battery Co., Ltd.
  • MAL400NL power 3kW'hr 120W / cm) After less than 0.4 seconds).
  • the total ink film thickness was measured after image recording, it was in the range of 2.3 m to 13 m.
  • the ink-jet image was printed in an environment of 27 ° C, 85% RH, 25 ° C, and 25% RH.
  • the integrated illuminance at 254 nm was measured using UVPF-A1 manufactured by Iwasaki Electric Co., Ltd.
  • Synthetic paper Synthetic paper made by YUPO Corporation YUPO FGS
  • PVC polyvinyl chloride
  • ® Ink having a viscosity in the range of 7 mPa ⁇ s to 40 mPa ⁇ s at 25 ° C,
  • ⁇ and ⁇ are levels that have no practical problem.
  • ⁇ Visible but can be distinguished as characters and can be used at the last minute
  • ⁇ and ⁇ are levels that have no practical problem.
  • Y, M, C, and K colors are printed so that one dot is adjacent to each other, each adjacent color dot is enlarged with a rule, and the appearance of bleeding and wrinkles is visually observed and mixed according to the following criteria. Was evaluated.
  • Adjacent dots are slightly blurred and the dot shape is slightly broken.
  • Adjacent dots are blurred and mixed, and there are wrinkles in the overlapping area.
  • the physical properties of the cured film produced by printing by the above-described inkjet image forming method using magenta ink in which a magenta pigment was dispersed were evaluated by the following tests.
  • Lead Writing brush test The hardness of each cured film was measured according to JIS 5400. The hardness rank is (soft) 6B to B, HB, F, H to 9H (hard), 6B is the softest, and 9H is the hardest.
  • Evaluation of flexibility After ink was applied by injection onto PVC so that the film thickness was 3 ⁇ m, 800 mi Zcm 2 ultraviolet rays were irradiated with a metal halide lamp within 1 second to obtain a cured film. The obtained cured film was evaluated in accordance with the method of bending resistance evaluation of JIS K 5600.
  • test for misalignment is any one selected from ink viscosity, ink ejection properties, ink jet recording image evaluation, color mixing, cured film hardness, and cured film bending resistance evaluation. One test is shown.
  • the obtained ink-curing composition was stored in a high-temperature and high-humidity environment at 85 ° C and 90% RH for 1 month, and the pencil pulling force test and the evaluation of flexibility of the cured composition were the same as described above. It was evaluated in a test.
  • the obtained ink cured film was stored at 85 ° C for 30 minutes. After storing at 40 ° C for 30 minutes, the cured film surface was rubbed to test whether the cured film could be peeled off. Adhesion) was evaluated. This was repeated until the cured film peeled off or reached 10 cycles without peeling off, and rank evaluation was performed as follows.
  • the obtained ink cured film was stored at 85 ° C for 30 minutes. After storing at 40 ° C for 30 minutes, the cured film was bent and tested for cracks in the cured film. Evaluation of flex resistance. This was repeated until the cracking force was applied to the cured film or until 10 cycles were reached without cracking, and the rank evaluation was performed as follows.
  • the sample of the present invention has good injection properties and improved image quality. It can be seen that the sample of the present invention exhibits good curability regardless of the environmental difference. It can be seen that the sample of the present invention maintains various properties and physical properties even after long-term storage. Invented sample Shows excellent durability against temperature changes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Epoxy Resins (AREA)
  • Ink Jet (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne une composition polymérisable présentant une excellente stabilité au stockage, pouvant être durcie de manière hautement sensible dans des conditions de température élevée. Cette composition polymérisable permet d'obtenir un film durci présentant d'excellentes propriétés d'adhésion, de flexibilité, de stabilité au stockage et de résistance à l'environnement, en particulier de résistance aux changements de température. L'invention concerne également un procédé de polymérisation d'une composition polymérisable, une composition d'encre, un procédé de formation d'images utilisant une composition d'encre, une imprimante jet d'encre, et un composé spécifique d'époxy alicyclique.
PCT/JP2006/311261 2005-06-20 2006-06-06 Composition polymerisable, composition d'encre, procede de formation d'images, imprimante jet d'encre, et epoxyde alicyclique WO2006137260A1 (fr)

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JP2007522232A JPWO2006137260A1 (ja) 2005-06-20 2006-06-06 重合性組成物、インク組成物、画像形成方法、インクジェット記録装置及び脂環式エポキサイド

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JP2005179076 2005-06-20
JP2005-179076 2005-06-20

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JP2002317139A (ja) * 2001-04-19 2002-10-31 Riso Kagaku Corp 活性エネルギー線硬化型インキ
WO2003099947A1 (fr) * 2002-05-24 2003-12-04 Huntsman Advanced Materials (Switzerland) Gmbh Compositions se pretant a la formation de jets
JP2005041893A (ja) * 2003-07-22 2005-02-17 Konica Minolta Medical & Graphic Inc 活性光線硬化型組成物、それを用いた画像形成方法及びインクジェット記録装置
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