WO2006137260A1 - Polymerizable composition, ink composition, image-forming method, inkjet recorder, and alicyclic epoxide - Google Patents

Polymerizable composition, ink composition, image-forming method, inkjet recorder, and alicyclic epoxide 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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French (fr)
Japanese (ja)
Inventor
Takeshi Kurata
Kimihiko Ookubo
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Konica Minolta Medical & Graphic, Inc.
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Priority to JP2007522232A priority Critical patent/JPWO2006137260A1/en
Publication of WO2006137260A1 publication Critical patent/WO2006137260A1/en

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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.

Abstract

Disclosed is a polymerizable composition having excellent storage stability which can be highly sensitively cured under high temperature conditions. This polymerizable composition enables to obtain a cured film which is extremely excellent in adhesion, flexibility, storage stability and environment resistance, especially durability against temperature changes. Also disclosed are a method for polymerizing a polymerizable composition, an ink composition, an image-forming method using an ink composition, an inkjet recorder and a specific alicyclic epoxy compound.

Description

明 細 書  Specification
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 び脂環式ェポキサイド  Polymerizable composition, ink composition, image forming method, ink jet recording apparatus, and alicyclic epoxide
技術分野  Technical field
[0001] 本発明は、重合性組成物に関するものであり、高温条件下でも高感度で硬化し、保 存性に優れ、更には形成された硬化膜は、密着性、柔軟性、保存性、耐環境性とり わけ温度変化への耐久性に極めて優れている重合性組成物、インク組成物、インク 組成物を用いる画像形成方法、インクジェット記録装置及び特定の脂環式ェポキサ イドに関する。  [0001] 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.
背景技術  Background art
[0002] 従来、紫外線や電子線などの活性エネルギー線または熱により硬化する重合性組 成物は、プラスチック、紙、木工及び無機質材等の塗料、接着剤、印刷インキ、印刷 回路基板及び電気絶縁関係等の種々の用途に実用化されている。近年、その中で も印刷インキ、塗料、接着剤等ではより一層の耐候性と付着性の改善が望まれている 。また、これらの重合組成物を使用したインクジェット用インクシステムとしては、紫外 線で硬化する紫外線硬化型インクジエトインクがある力 この紫外線硬化インクを用い たインクジェット方式は、比較的低臭気であり、速乾性、インク吸収性の無い記録媒 体への記録が出来る点で、近年注目されつつあり、紫外線硬化型インクジェットイン クが開示されて (例えば、特許文献 1、 2参照。）いる。この分野においては、低粘度で あることに加え、形成される膜がより強固であること及び柔軟であることが求められて いる。インクジェット用インクに可塑剤を添加することにより可塑性をもたせることがで きることが開示されて (例えば、特許文献 3参照。）いる。しかし、溶融型インクにおけ るものであり、溶剤型のインクを用いた紫外線硬化型インクジェットインクについての 記載は無い。  Conventionally, 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. In addition, as 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. In recent years, attention has been paid to the fact that recording on a recording medium having no dryness or ink absorption is possible, and ultraviolet curable ink jet inks have been disclosed (see, for example, Patent Documents 1 and 2). In this field, in addition to low viscosity, the formed film is required to be stronger and flexible. It has been disclosed that plasticity can be imparted by adding a plasticizer to ink-jet ink (see, for example, Patent Document 3). However, there is no description of ultraviolet curable ink-jet ink using solvent-type ink, which is in melt-type ink.
[0003] また、これらのインクを用いた場合、記録材料の種類や作業環境によって、硬化感 度が変動しやす 、と 、う問題がある。  In addition, when these inks are used, there is a problem that the curing sensitivity is likely to vary depending on the type of recording material and the working environment.
[0004] ラジカル重合性ィ匕合物を用いたインクは、酸素阻害作用を受けるため、インク液滴 量が少ない場合には硬化阻害が起こりやすい。また、カチオン重合性ィ匕合物を用い たインク (例えば、特許文献 4〜7参照。）は、酸素阻害作用をうけることはないが、分 子レベルの水分 (湿度）の影響を受けやす 、と 、つた問題がある。 [0004] Ink using a radically polymerizable compound is subjected to an oxygen inhibition action, so that an ink droplet is used. When the amount is small, curing inhibition tends to occur. Also, inks using cationically polymerizable compounds (see, for example, Patent Documents 4 to 7) are not affected by oxygen inhibition, but are susceptible to molecular water (humidity). There are two problems.
[0005] また重合性組成物をインクジェットインク等に実用化し、硬化膜を製品として使用す る際には硬化膜の耐環境性が必要とされるが、従来のェポキサイド、例えば、ミアセ ンジオキサイド（CAS： 63869— 17— 0)や ATOFINA社製ターピノレンジォキサイ ド、ダイセルィ匕学工業社製セロキサイド 3000、を用いた重合性組成物力も作製した 硬化膜では急激な温度変化に曝された場合に密着性、柔軟性が著しく低下すると ヽ う問題があった。 [0005] In addition, when a polymerizable composition is put into practical use for an inkjet ink or the like, and the cured film is used as a product, the environment resistance of the cured film is required. However, conventional epoxides such as mia CAS: 63869—17—0), terpinolene oxide manufactured by ATOFINA, and Celoxide 3000 manufactured by Daicel Engineering Co., Ltd. However, there was a problem that the adhesion and flexibility were significantly lowered.
特許文献 1：特開平 6— 200204号公報  Patent Document 1: JP-A-6-200204
特許文献 2：特表 2000 - 504778号公報  Patent Document 2: Japanese Translation of Special Publication 2000-504778
特許文献 3：特開平 8— 3493号公報  Patent Document 3: Japanese Patent Laid-Open No. 8-3493
特許文献 4：特開 2001— 220526号公報  Patent Document 4: Japanese Patent Laid-Open No. 2001-220526
特許文献 5 :特開 2002— 188025号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2002-188025
特許文献 6：特開 2002— 317139号公報  Patent Document 6: Japanese Patent Laid-Open No. 2002-317139
特許文献 7：特開 2003 - 55449号公報  Patent Document 7: Japanese Patent Laid-Open No. 2003-55449
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明の目的は、高温条件下でも高感度で硬化し、保存性に優れ、更には形成さ れた硬化膜は密着性、柔軟性、保存性、耐環境性とりわけ温度変化への耐久性に極 めて優れている重合性組成物、インク組成物、インク組成物を用いる画像形成方法 及びインクジェット記録装置及び特定の脂環式ェポキサイド (脂環式アルキレンォキ シドとも!/、う）を提供することである。 [0006] 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.
課題を解決するための手段  Means for solving the problem
[0007] 本発明の上記目的は、下記構成により達成された。 [0007] The above object of the present invention has been achieved by the following constitution.
[0008] 1.下記一般式 (X)で表される分子量が 180〜： LOOOである化合物を含有すること を特徴とする重合性組成物。  [0008] 1. A polymerizable composition comprising a compound represented by the following general formula (X) having a molecular weight of 180 to LOOO.
[0009] [化 1] [0009] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
[0010] (式中、
Figure imgf000004_0002
R5、 R6は、各々水素原子またはアルキル基を表し、 R3は一般式（ X) R2が結合している飽和炭化水素環の任意の位置で結合している置換基 であり、 nは 0から 7までの整数である。 nが複数の場合、 R3は互いに同じであっても異 なっていても良い。 Lは一般式 (X)
Figure imgf000004_0003
R2が結合している飽和炭化水素環と任 意の位置で結合している (p + 1)価の連結基または単なる結合手であり、 pは 1から 3 までの整数であり、 qは 1から 3までの整数である。 pが複数の場合、複数の R4、 R5、 R6 は各々互いに同じであっても異なっていても良ぐ qが複数の場合、複数の L、 R4、 R5 、 R6は各々互いに同じであっても異なっていても良い。 ) [0010] (where
Figure imgf000004_0002
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, and n Is an integer from 0 to 7. When n is plural, R 3 may be the same as or different from each other. L is the general formula (X)
Figure imgf000004_0003
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, and q is It is an integer from 1 to 3. When p is plural, plural R 4 , R 5 and R 6 may be the same or different from each other. When q is plural, plural L, R 4 , R 5 and R 6 are each They may be the same or different. )
2. R2の少なくとも一方がアルキル基であることを特徴とする前記 1に記載の重 合性組成物。 2. The polymerizable composition as described in 1 above, wherein at least one of R 2 is an alkyl group.
[0011] 3. R2のいずれか一方がアルキル基で、他方が水素原子であることを特徴とす る前記 1または 2に記載の重合性組成物。 [0011] 3. The polymerizable composition as described in 1 or 2 above, wherein one of R 2 is an alkyl group and the other is a hydrogen atom.
[0012] 4. R2の 、ずれか一方が炭素数 1から 3までのアルキル基で、他方が水素原子 であることを特徴とする前記 1〜3のいずれか 1項に記載の重合性組成物。 [0012] 4. The polymerizable composition as described in any one of 1 to 3 above, wherein one of R 2 is an alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom. object.
[0013] 5. R5及び R6力 各々アルキル基であることを特徴とする前記 1〜4のいずれ力 1項 に記載の重合性組成物。 [0013] 5. The polymerizable composition as described in any one of 1 to 4 above, wherein each of R 5 and R 6 is an alkyl group.
[0014] 6.酸発生剤を含有することを特徴とする前記 1〜5のいずれか 1項に記載の重合 性組成物。 [0014] 6. The polymerizable composition as described in any one of 1 to 5 above, which comprises an acid generator.
[0015] 7.前記 1〜6のいずれか 1項に記載の重合性組成物を含有することを特徴とするィ ンク組成物。  [0015] 7. An ink composition comprising the polymerizable composition as described in any one of 1 to 6 above.
[0016] 8. 25°Cにおける粘度が 7mPa' s〜40mPa' sであることを特徴とする前記 7に記載 のインク組成物。 [0016] 8. The viscosity according to 7, wherein the viscosity at 25 ° C is 7 mPa's to 40 mPa's. Ink composition.
[0017] 9.顔料を含有することを特徴とする前記 7または 8に記載のインク組成物。  [0017] 9. The ink composition as described in 7 or 8 above, which contains a pigment.
[0018] 10.インクジェット記録ヘッドより、前記 7〜9のいずれ力 1項に記載のインク組成物 を記録材料上に画像様に噴射し、該記録材料上に印刷を行う画像形成方法であつ て、該インク組成物が着弾した後、加熱する工程、または、 0. 001秒〜 1. 0秒間活 性光線を照射する工程を経て、前記インク組成物を硬化させることを特徴とする画像 形成方法。 [0018] 10. 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. .
[0019] 11.前記インクジェット記録ヘッドの各ノズルより吐出する最小インク液滴量力 2pl [0019] 11. Minimum ink droplet volume force ejected from each nozzle of the inkjet recording head 2pl
〜15plであることを特徴とする前記 10に記載の画像形成方法。 11. The image forming method as described in 10 above, wherein the image forming method is 15 pl.
[0020] 12.前記 10または 11に記載の画像形成方法に用いられるインクジェット記録装置 であって、記録ヘッドを 35°C〜100°Cに加熱した後、インク組成物を吐出することを 特徴とするインクジェット記録装置。 [0020] 12. An ink jet recording apparatus used in the image forming method according to 10 or 11, wherein the ink is ejected after the recording head is heated to 35 ° C to 100 ° C. Inkjet recording apparatus.
[0021] 13.前記 10または 11に記載の画像形成方法に用いられるインクジェット記録装置 であって、インク組成物を吐出する際、記録媒体を 35°C〜60°Cに加温することを特 徴とするインクジヱット記録装置。 [0021] 13. An ink jet recording apparatus used in the image forming method according to 10 or 11, wherein the recording medium is heated to 35 ° C to 60 ° C when the ink composition is ejected. Ink jet recording device.
[0022] 14.下記一般式 (X— A)で表される分子量が 180〜1000であることを特徴とする 化合物。 [0022] 14. A compound having a molecular weight of 180 to 1000 represented by the following general formula (X—A):
[0023] [化 2] [0023] [Chemical 2]
—般式 (X—A)
Figure imgf000005_0001
—General formula (X—A)
Figure imgf000005_0001
[0024] (式中、 Ru、 R , R15、 Rlbは水素原子またはアルキル基を表し、 R"は一般式 (X— A) 中の飽和炭化水素環の任意の位置に結合して 、るアルキル基を表し、 mは 0〜7ま での整数を表し、 R14は水素原子またはアルキル基を表し、 L2は一般式 (X— A)中の 飽和炭化水素環の任意の位置に結合しているアルキレン基、酸素原子または、該ァ ルキレン基と該酸素原子の組み合わせにより形成される二価の連結基を表す。 ) 15.前記一般式 (X— A)が下記一般式 (X— B)で表されることを特徴とする前記 1 4に記載の化合物。 [In the formula, 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, and L 2 represents an arbitrary position of the saturated hydrocarbon ring in the general formula (X—A) Represents an alkylene group bonded to the oxygen atom, an oxygen atom, or a divalent linking group formed by a combination of the alkylene group and the oxygen atom. 15. The compound according to 14 above, wherein the general formula (X—A) is represented by the following general formula (X—B):
[0025] [化 3]
Figure imgf000006_0001
[0025] [Chemical 3]
Figure imgf000006_0001
[0026] (式中、 R 、 R ま、各々アルキル基を表し、 は、水素原子またはアルキル基を表 し、 L3は、アルキレン基、酸素原子または、該アルキレン基と該酸素原子の組み合わ せにより形成される二価の連結基を表す。 ) (Wherein R 1 and R 2 each represents an alkyl group, represents a hydrogen atom or an alkyl group, and L 3 represents an alkylene group, an oxygen atom, or a combination of the alkylene group and the oxygen atom. Represents a divalent linking group formed by
発明の効果  The invention's effect
[0027] 本発明により、高温条件下でも高感度で硬化し、保存性に優れ、更には形成された 硬化膜は密着性、柔軟性、保存性、耐環境性とりわけ温度変化への耐久性に極めて 優れている重合性組成物、インク組成物、インク組成物を用いる画像形成方法及び インクジェット記録装置及び特定の脂環式ェポキサイドを提供することができた。 図面の簡単な説明  [0027] According to the present invention, it 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
[0028] [図 1]本発明に用いられる記録装置の要部の構成を示す図である。 FIG. 1 is a diagram showing a configuration of a main part of a recording apparatus used in the present invention.
[図 2]本発明に用いられる別の記録装置の要部の構成を示す図である。  FIG. 2 is a diagram showing a configuration of a main part of another recording apparatus used in the present invention.
符号の説明  Explanation of symbols
[0029] 1 記録装置 [0029] 1 Recording device
2 ヘッドキャリッジ  2 Head carriage
3 記録ヘッド  3 Recording head
4 照射手段  4 Irradiation means
5 プラテン部  5 Platen section
6 ガイド部材  6 Guide member
7 蛇腹構造  7 Bellows structure
P 記録材料  P Recording material
発明を実施するための最良の形態 [0030] 本発明の重合性組成物においては、請求の範囲第 1項〜第 6項のいずれか 1項に 規定する構成とすることにより、高温条件下でも高感度で硬化し、保存性に優れ、更 には形成された硬化膜は密着性、柔軟性、保存性、耐環境性とりわけ温度変化への 耐久性に極めて優れている重合性組成物を得ることができた。また、前記重合性組 成物を含有するインク組成物、前記インク組成物を用いる画像形成方法や、インクジ エツト記録装置等が併せて得られ、更に、特定の脂環式ェポキサイドを提供すること ができた。 BEST MODE FOR CARRYING OUT THE INVENTION [0030] In the polymerizable composition of the present invention, by adopting the constitution defined in any one of claims 1 to 6, the composition is cured with high sensitivity even under a high temperature condition, and the storage stability is improved. In addition, 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. In addition, 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.
[0031] 《重合性組成物》  [0031] << Polymerizable composition >>
本発明の重合性組成物につ！ヽて説明する。  For the polymerizable composition of the present invention! I will explain in a moment.
[0032] 本発明者は、上記課題に鑑みて鋭意検討を行った結果、一般式 (X)で表されるェ ポキサイド構造 (ォキシラン構造とも 、う）を有する化合物を含む重合性組成物を用い た場合に、低照度の光源でも環境湿度に影響を受けずに強固で、且つ長期間保存 前後で十分な硬さ及び柔軟性を保持し、温度変化への耐性に優れた硬化膜が得ら れることを見出し、前記重合性組成物をインク組成物として用い、画像を形成した場 合、高画質な画像が得られることを見いだし、本発明に至った次第である。  [0032] As a result of intensive studies in view of the above problems, the present inventor used a polymerizable composition containing a compound having an epoxide structure represented by the general formula (X) (also oxsilane structure). In such a case, 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.
[0033] 《一般式 (X)で表される化合物》  [0033] << Compound Represented by Formula (X) >>
本発明に係る一般式 (X)で表される化合物につ 、て説明する。  The compound represented by the general formula (X) according to the present invention will be described.
[0034] 一般式 (X)中の R1及び R2は水素原子またはアルキル基 (例えば、メチル基、ェチ ル基、プロピル基、イソプロピル基、ブチル基、 tert ブチル基、 iso ブチル基、 sec ブチル基、ペンチル基、へキシル基、シクロペンチル基、シクロへキシル基、ヘプ チル基、ォクチル基、 2—ェチルへキシル基、デシル基、ドデシル基等）を表し、これ らは更に置換基を有していても良ぐ置換基を有するアルキル基の置換基の例として は、ハロゲン原子 (例えば塩素原子、臭素原子、フッ素原子、等）、炭素数 1〜20個 のアルコキシ基（例えば、メトキシ基、エトキシ基、 n—プロポキシ基、 iso プロポキシ 基、 n ブトキシ基、 tert ブトキシ基、等）、ァシル基 (例えばァセチル基、プロピオ -ル基、トリフルォロアセチル基、等）、炭素数 1〜20個のァシルォキシ基 (例えばァ セトキシ基、プロピオニルォキシ基、トリフルォロアセトキシ基、等）、炭素数 1〜20個 のアルコキシカルボ-ル基（メトキシカルボ-ル基、エトキシカルボ-ル基、 tert ブト キシカルボニル基、等）、炭素数 2〜20のアルキルチオカルボニル基 (メチルチオ力 ルボニル基、ェチルチオカルボ-ル基、 tert—ブチルチオカルボ-ル基、等）、ァリ ールォキシカルボ-ル基、アルキルスルホ-ル基、ァリールスルホ-ル基、シァノ基、 ニトロ基、ヒドロキシ基等が挙げられる。 R1または R2はそのいずれか一方がアルキル 基であり、他方が水素原子であることが好ましい。 R1または R2がアルキル基の場合、 アルキル基として好ましいのは炭素数 1〜20個のアルキル基であり、炭素数 1〜10 個のアルキル基がより好ましぐ炭素数 1〜3個のアルキル基がさらに好ましぐメチル 基が最も好ましい。 [0034] 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. Examples of the substituent of the alkyl group having a substituent that may be substituted 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. § Setokishi group, a propionyloxy Ruo alkoxy group, triflate Ruo b acetoxy group, etc.), alcohol 1-20 carbon propoxycarbonyl - Le group (methoxycarbonyl - group, ethoxycarbonyl - group, tert-butoxide Xycarbonyl group, etc.), alkylthiocarbonyl groups having 2 to 20 carbon atoms (methylthio group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfol Group, arylsulfol group, cyano group, nitro group, hydroxy group and the like. Either R 1 or R 2 is preferably an alkyl group and the other is a hydrogen atom. When 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.
[0035] 一般式 (X)中の R3は置換基を表し、置換基の例としては上述のアルキル基、ハロ ゲン原子 (例えば塩素原子、臭素原子、フッ素原子、等）、炭素数 1〜20個のアルコ キシ基（例えば、メトキシ基、エトキシ基、 n—プロポキシ基、 iso—プロポキシ基、 n— ブトキシ基、 tert—ブトキシ基、等）、ァシル基 (例えばァセチル基、プロピオ-ル基、 トリフルォロアセチル基、等）、炭素数 1〜20個のァシルォキシ基 (例えばァセトキシ 基、プロピオ-ルォキシ基、トリフルォロアセトキシ基、等）、炭素数 1〜20個のアルコ キシカルボ-ル基（メトキシカルボ-ル基、エトキシカルボ-ル基、 tert—ブトキシカ ルボニル基、等）、炭素数 2〜20のアルキルチオカルボ-ル基（メチルチオカルボ- ル基、ェチルチオカルボ-ル基、 tert—ブチルチオカルボ-ル基、等）、ァリールォ キシカルボ-ル基、アルキルスルホ-ル基、ァリール基、ァリールスルホ-ル基、シァ ノ基、ニトロ基、ァシルァミノ基、ァリールォキシァミノ基、アミノ基、ウレイド基、ウレタン 基、ヒドロキシ基、等が挙げられ、これらの置換基はさらに同義の置換基によって置換 されていてもよい。置換基として好ましいのは、アルキル基、アルコキシ基、ァシルォ キシ基、アルコキシカルボ-ル基である。 [0035] 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.), alkylthiocarbon group having 2 to 20 carbon atoms (methylthiocarbol group, ethylthiocarbol group, tert-butylthiocarbol group) Le group Etc.), aryloxycarbonyl group, alkylsulfol group, arylyl group, arylylsulfonyl group, cyano group, nitro group, acylamino group, aryloxyamino group, amino group, ureido group, urethane group, A hydroxy group, and the like, and these substituents may be further substituted with the same substituents. Preferred as a substituent are an alkyl group, an alkoxy group, an acyl group, and an alkoxy carbo group.
[0036] 一般式 (X)中の nは 0〜7の整数であり、 nが複数の場合、 R3は互いに同じであって も異なっていても良い。 [0036] 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.
[0037] 一般式 (X)中の R4〜R6は各々水素原子またはアルキル基を表し、アルキル基の例 としては上述した R1及び R2となりうるアルキル基と同義の基が挙げられる。 R4〜R6の 組み合わせとしては、 R4が水素原子であり、且つ R5及び R6がアルキル基であることが 好まし!/、。 R4〜R6がアルキル基の場合はそれぞれ炭素数 1〜20個のアルキル基で あることが好ましぐ炭素数 1〜10個のアルキル基であることがより好ましぐ炭素数 1 〜3個のアルキル基であることがさらに好ましぐメチル基であることが最も好ましい。 [0037] 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. As a combination of R 4 to R 6 , it is preferable that R 4 is a hydrogen atom, and R 5 and R 6 are alkyl groups! /. When 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.
[0038] 一般式 (X)中の Lは (p + 1)価の連結基または単なる結合手であり、 pは 1〜3まで の整数であり、 qは 1〜3までの整数であり、 Lは R1及び R2を含む飽和炭化水素環と任 意の位置で結合している。 qは 1または 2であることが好ましぐ 1であることがより好ま しい。 2価の連結基の例としては、 O 基、 S 基、 CO 基、 CS 基、 S O 基、 SO—基及び以下の基、及びこれらの基を複数組み合わせてできる基を [0038] 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. Examples of 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.
2  2
挙げることができる。  Can be mentioned.
[0039] メチレン基 [ CH—] [0039] Methylene group [CH—]
2  2
ェチリデン基 [ >CHCH ]  Ethylidene group [> CHCH]
3  Three
ノ ' 3 2  No '3 2
1, 2—エチレン基 [ CH CH -]  1, 2-ethylene group [CH CH-]
2 2  twenty two
1. 2—プロピレン基 [― CH (CH ) CH -]  1. 2-Propylene group [-CH (CH) CH-]
3 2  3 2
1. 3 プロパンジィル基 [ CH CH CH— ]  1. 3 Propandyl group [CH CH CH-]
2 2 2  2 2 2
2, 2 ジメチル— 1, 3 プロパンジィル基 [― CH C (CH ) CH -]  2, 2 Dimethyl— 1, 3 Propanedyl group [— CH C (CH) CH-]
2 3 2 2  2 3 2 2
2, 2 ジメトキシ— 1, 3 プロパンジィル基 [― CH C (OCH ) CH -]  2, 2 Dimethoxy— 1, 3 Propanedyl group [— CH C (OCH) CH-]
2 3 2 2  2 3 2 2
2, 2 ジメトキシメチル— 1, 3 プロパンジィル基 [― CH C (CH OCH ) CH -]  2, 2 Dimethoxymethyl— 1, 3 Propanedyl group [— CH C (CH OCH) CH-]
2 2 3 2 2 2 2 3 2 2
1—メチル― 1, 3 プロパンジィル基 [― CH (CH ) CH CH -] 1-methyl-1,3 propanediyl group [-CH (CH) CH CH-]
3 2 2  3 2 2
1. 4 ブタンジィル基 [ CH CH CH CH― ]  1. 4 Butanediyl group [CH CH CH CH-]
2 2 2 2  2 2 2 2
1. 5 ペンタンジィル基 [ CH CH CH CH CH― ]  1.5 Pentandyl group [CH CH CH CH CH-]
2 2 2 2 2  2 2 2 2 2
ォキシジエチレン基 [一 CH CH OCH CH一]  Oxydiethylene group [One CH CH OCH CH One]
2 2 2 2  2 2 2 2
チオジェチレン基 [ CH CH SCH CH -]  Thioethylene [CH CH SCH CH-]
2 2 2 2  2 2 2 2
3—ォキソチオジェチレン基 [ CH CH SOCH CH -]  3-Oxothiojetylene group [CH CH SOCH CH-]
2 2 2 2  2 2 2 2
3, 3—ジォキソチオジェチレン基 [ CH CH SO CH CH—]  3, 3-Dioxothiojetylene group [CH CH SO CH CH—]
2 2 2 2 2  2 2 2 2 2
1. 4 ジメチル - 3-ォキサ—1, 5 ペンタンジィル基 [― CH (CH ) CH OCH (  1. 4 Dimethyl-3-oxa-1,5-pentandyl [-CH (CH) CH OCH (
3 2 3 2
CH ) CH一] CH) CH 1]
3 2  3 2
3—ォキソペンタンジィル基 [ CH CH COCH CH -]  3-Oxopentanediol [CH CH COCH CH-]
2 2 2 2  2 2 2 2
1. 5 ジォキソ一 3—ォキサペンタンジィル基 [ COCH OCH CO— ] 4—ォキサ 1, 7 ヘプタンジィル基 [ CH CH CH OCH CH CH -] 1.5 Dioxo 1-Oxapentanediol [COCH OCH CO-] 4-Oxa 1, 7 heptaneyl group [CH CH CH OCH CH CH-]
2 2 2 2 2 2  2 2 2 2 2 2
3, 6 ジォキサ一 1, 8—オクタンジィル基 [ CH CH OCH CH OCH CH -]  3, 6 Dioxa-1, 1,8-octanediyl group [CH CH OCH CH OCH CH-]
2 2 2 2 2 2 2 2 2 2 2 2
1, 4, 7 トリメチルー 3, 6 ジォキサ一 1, 8—オクタンジィル基 [― CH (CH ) CH 1, 4, 7 Trimethyl-3, 6 Dioxa 1,8-octanediyl [-CH (CH) CH
3 Three
OCH (CH ) CH OCH (CH ) CH -] OCH (CH) CH OCH (CH) CH-]
2 3 2 3 2  2 3 2 3 2
5, 5 ジメチル— 3, 7 ジォキサ— 1, 9 ノナンジィル基 [ CH CH OCH C (C  5, 5 Dimethyl— 3, 7 Dioxa— 1, 9 Nonandyl group [CH CH OCH C (C
2 2 2 2 2 2
H ) CH OCH CH一] H) CH OCH CH
3 2 2 2 2  3 2 2 2 2
5, 5 ジメトキシ一 3, 7 ジォキサ一 1, 9 ノナンジィル基 [ CH CH OCH C (  5,5 Dimethoxy-1,3,7 Dioxa-1,9 Nonaneyl [CH CH OCH C (
2 2 2 2 2 2
OCH ) CH OCH CH -] OCH) CH OCH CH-]
3 2 2 2 2  3 2 2 2 2
5, 5 ジメトキシメチル一 3, 7 ジォキサ一 1, 9 ノナンジィル基 [― CH CH OC  5, 5 Dimethoxymethyl 1, 3, 7 Dioxa 1, 9, Nonanediyl [-CH CH OC
2 2 twenty two
H C (CH OCH ) CH OCH CH -] H C (CH OCH) CH OCH CH-]
2 2 3 2 2 2 2  2 2 3 2 2 2 2
4, 7 ジォキソ— 3, 8 ジォキサ— 1, 10 デカンジィル基 [― CH CH O— CO  4, 7 Dioxo-3, 8 Dioxa-1, 10 Decandyl [-CH CH O- CO
2 2  twenty two
CH CH CO -OCH CH -]  CH CH CO -OCH CH-]
2 2 2 2  2 2 2 2
3, 8 ジォキソ— 4, 7 ジォキサ— 1, 10 デカンジィル基 [― CH CH CO— O  3, 8 Dioxo— 4, 7 Dioxa— 1, 10 Decandyl group [— CH CH CO— O
2 2  twenty two
CH CH O-COCH CH -]  CH CH O-COCH CH-]
2 2 2 2  2 2 2 2
1, 3 シクロペンタンジィル基 [ 1, 3 -C H -]  1, 3 cyclopentandyl group [1, 3 -C H-]
5 8  5 8
1. 2—シクロへキサンジィル基 [— 1, 2-C H -]  1. 2-Cyclohexanyl group [— 1, 2-C H-]
6 10  6 10
1. 3 シクロへキサンジィル基 [ 1, 3— C H -]  1. 3 Cyclohexanediyl group [1, 3— C H-]
6 10  6 10
1. 4 シクロへキサンジィル基 [ 1, 4— C H -]  1. 4 Cyclohexanediyl [1, 4-— C H-]
6 10  6 10
2, 5—テトラヒドロフランジィル基 [2, 5— C H O— ]  2,5-tetrahydrofuranyl group [2, 5— C H O—]
4 6  4 6
p—フエ二レン基 [—p— C H—]  p—Phenylene group [—p— C H—]
6 4  6 4
m—フエ二レン基 [—m—C H—]  m—Phenylene group [—m—C H—]
6 4  6 4
α , α ' ο キシリレン基 [ ο— CH— C H CH—]  α, α 'ο Xylylene group [ο— CH— C H CH—]
2 6 4 2  2 6 4 2
α , α ' m キシリレン基 [ m— CH— C H CH—]  α, α 'm Xylylene group [m— CH— C H CH—]
2 6 4 2  2 6 4 2
α , α '—ρ キシリレン基 [ p— CH― C H― CH -]  α, α '—ρ Xylylene group [p— CH— C H— CH-]
2 6 4 2  2 6 4 2
フラン一 2, 5 ジィル一ビスメチレン基 [2, 5-CH -C H O-CH -]  Furan 2,5 diyl bismethylene [2, 5-CH 2 -CH 2 O-CH 2-]
2 4 2 2  2 4 2 2
チォフェン一 2, 5 ジィル一ビスメチレン基 [2, 5-CH -C H S-CH -]  Thiophene 1,5 diyl bismethylene [2, 5-CH -C H S-CH-]
2 4 2 2 イソプロピリデンビス一 p フエ二レン基 [ p— C H -C (CH ) —p— C H—]  2 4 2 2 Isopropylidenebis- 1 p phenylene group [p— C H -C (CH) —p— C H—]
6 4 3 2 6 4 6 4 3 2 6 4
Lが 3価以上の連結基となる場合、例えば上記の 2価の連結基力 必要な数だけ水 素原子を取り除いて結合手とした連結基が挙げられる。 When L is a trivalent or higher linking group, for example, the above divalent linking basic power Examples thereof include a linking group in which a primary atom is removed to form a bond.
[0040] Lは置換基を有していても良ぐ置換基の例としては上述の R3と同義の基が挙げら れ、主鎖と置換基の間に連結基としては、上述した 2価の連結基の例を挙げることが できる。 [0040] 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.
[0041] 連結基上の置換基として好ましいのはアルキル基、アルコキシ基、ァシルォキシ基 、アルコキシカルボ-ル基、ヒドロキシ基である。  [0041] Preferable substituents on the linking group are an alkyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a hydroxy group.
[0042] さらに連結基上の置換基はその任意の位置力 必要な数だけ水素原子を取り除き 結合手とすることで 2価以上の連結基となっていても良ぐその場合一般式 (X)中の 任意の位置に結合している水素原子を取り除き、その位置で結合して環を形成して いても良いが、伹しその環員数は 3〜5であり、 3〜4であることがより好ましぐ 3であ ることがもっとも好まし 、。  [0042] Further, 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.
[0043] 特に Lは鎖中の炭素原子の少なくとも一つが、さらにォキシラン環を構成する炭素 原子の少なくとも一つとして共有されていても良ぐその場合一般式 (X)中にさらに追 加して形成されるォキシラン環の数は 1〜5個であることが好ましぐ 1〜3個であるこ とがより好ましぐ 1〜2個であることがさらに好ましい。  [0043] In particular, L may be added to at least one carbon atom in the chain as at least one carbon atom constituting the oxosilane ring. In that case, 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.
[0044] Lとしては酸素原子、または主鎖に酸素原子を含んでいても良い主鎖の炭素数が 1 〜8の 2価の連結基が好ましぐ酸素原子、または主鎖に酸素原子を含んでいても良 い主鎖の炭素数力^〜 5の 2価の連結基がより好ましい。 pまたは qが複数の場合、複 数の R4〜R6はそれぞれ互いに同じであっても異なっていても良ぐ qが複数の場合、 複数の Lは互いに同じであっても異なって!/ヽても良!、。 [0044] 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. When p or q is plural, plural R 4 to R 6 may be the same or different from each other. When q is plural, plural L are the same or different from each other! / It ’s okay!
[0045] 一般式 (X)で表される化合物の分子量は 180〜1000の範囲が好ましぐ更に好ま しくは、 200〜700である。  [0045] 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.
[0046] 《一般式 (X— A)で表される化合物》  [0046] << Compound represented by the general formula (X-A) >>
本発明に係る異一般式 (X— A)で表される化合物につ 、て説明する。  The compound represented by the different general formula (XA) according to the present invention will be described.
[0047] 一般式 (X)で表される化合物の中で、より好ましいのは一般式 (X—A)で表される 化合物である。  [0047] Among the compounds represented by the general formula (X), a compound represented by the general formula (X-A) is more preferable.
[0048] 一般式 (X— A)にお 、て、 Ru、 R12、 R15、 R16は、各々水素原子またはアルキル基を 表し、 R13は一般式 (X— A)中の飽和炭化水素環の任意の位置に結合しているアル キル基を表し、 mは 0〜7までの整数を表し、 R14は水素原子またはアルキル基を表し 、 L2は一般式 (X— A)中の飽和炭化水素環の任意の位置に結合しているアルキレン 基 (例えばメチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、 ペンタメチレン基、へキサメチレン基、ヘプタメチレン基、オタタメチレン基、ノナメチレ ン基、デカメチレン基等)または酸素原子、あるいはその組み合わせ力 形成される 二価の連結基を表す。 [0048] In the general formula (X—A), 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) or oxygen atom, or The combination force represents a divalent linking group formed.
[0049] R11及び R12の 、ずれか一方はアルキル基で他方が水素原子であることが好ましく、 R15及び R16はアルキル基であることが好ましい。 Ru、 R12、 R13、 R15、 R16に適している アルキル基は前述の R1及び R2の例として挙げたアルキル基と同義であり、好ましくは 炭素数 1から 8までのアルキル基であり、より好ましくは炭素数 1〜3までのアルキル基 であり、特に好ましくはメチル基またはェチル基である。 mは 0〜5がより好ましぐ 0〜 3がより好ましい。 mが複数の場合、複数の R13は同じでも異なっていても良い。 R14が アルキル基の場合、好ましいアルキル基は Ru、 Ru、 R13、 R15、 R16として好ましいアル キル基と同義であるが、 R14として最も好ましいのは水素原子である。 L2のアルキレン 基としては、炭素数 1〜20のアルキレン基が好ましぐ炭素数 1〜10のアルキレン基 力 り好まし 、。このアルキレン基は上述の Lの置換基の例と同義の置換基によって 置 換されていても良ぐさらに置換基は上述の Lの置換基の例と同義の置換基によ つて置換されていても良い。 L2のアルキレン基の置換基として好ましいのは、アルキ ル基、アルコキシ基、アルコキシカルボ-ル基、ァシルォキシ基、ヒドロキシ基あるい はこれらがハロゲン原子によって置換された置換基である。また L2はアルキレン基の 主鎖、または置換基中に酸素原子を含むことでエーテル結合を備えて 、ても良 、。 [0049] Either one of R 11 and R 12 is preferably an alkyl group and the other is a hydrogen atom, and 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. Group, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. m is more preferably 0-5, more preferably 0-3. When m is plural, plural R 13 may be the same or different. When 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. As 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. 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.
[0050] L2中に酸素原子が含まれる場合、 L2中に含まれる酸素原子の数は 1〜5が好ましく 、 1〜3がより好ましい。 [0050] If the oxygen atoms contained in L 2, the number of oxygen atoms is 1 to 5 preferably contained in L 2, 1 to 3 is more preferable.
[0051] 《一般式 (X— B)で表される化合物》  [0051] << Compound Represented by General Formula (X-B) >>
本発明に係る一般式 (X— B)で表される化合物につ 、て説明する。  The compound represented by the general formula (X—B) according to the present invention will be described.
[0052] 一般式 (X— A)で表される化合物の中で、特に好ましいのは一般式 (X— B)で表さ れる化合物である。  Among the compounds represented by the general formula (X—A), a compound represented by the general formula (X—B) is particularly preferable.
[0053] 一般式 (X— B)にお 、て、 R25、 R26はアルキル基を表し、 R24は水素原子またはアル キル基を表し、 L3はアルキレン基または酸素原子、あるいはその組み合わせによって なる二価の連結基を表す。 [0053] In the general formula (X—B), R 25 and R 26 represent an alkyl group, and R 24 represents a hydrogen atom or an alkyl group. Represents a kill group, and L 3 represents an alkylene group, an oxygen atom, or a divalent linking group formed of a combination thereof.
[0054] R25、 R26に適しているアルキル基は前述の R1及び R2の例として挙げたアルキル基と 同義であり、好ましくは炭素数 1から 8までのアルキル基であり、より好ましくは炭素数 1〜3までのアルキル基であり、特に好ましくはメチル基またはェチル基である。 R24が アルキル基の場合、好ましいアルキル基は R25、 R26として好ましいアルキル基と同義 であるが、 R24として最も好ましいのは水素原子である。 L3のアルキレン基としては、炭 素数 1〜20のアルキレン基が好ましぐ炭素数 1〜10のアルキレン基がより好ましい 。このアルキレン基は上述の Lの置換基の例と同義の置換基によって置換されて!、て も良ぐさらに置換基は同義の置換基によって置換されていても良い。 L3のアルキレ ン基の置換基として好ましいのは、アルキル基、アルコキシ基、アルコキシカルボ- ル基、ァシルォキシ基、ヒドロキシ基あるいはこれらがハロゲン原子によって置換され た置換基である。また L3はアルキレン基の主鎖、または置換基中に酸素原子を含む ことでエーテル結合を備えて 、ても良 、。 [0054] 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. When 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. As the alkylene group of L 3, 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. Preferable as 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.
[0055] L3中に酸素原子が含まれる場合、 L3中に含まれる酸素原子の数は 1〜5が好ましく 、 1〜3がより好ましい。 [0055] If the oxygen atoms contained in the L 3, the number of oxygen atoms is 1 to 5 preferably contained in the L 3, 1 to 3 is more preferred.
[0056] 以下に、一般式 (X)で表される化合物の具体例を示すが、本発明はこれらに限定 されない。  [0056] Specific examples of the compound represented by the general formula (X) are shown below, but the present invention is not limited thereto.
[0057] [化 4] [0057] [Chemical 4]
Figure imgf000014_0001
Figure imgf000014_0001
[0058] [化 5] [0058] [Chemical 5]
Figure imgf000015_0001
Figure imgf000015_0001
[0059] [ィ匕 6] [0059] [6]
Figure imgf000016_0001
Figure imgf000016_0001
[0060] [化 7] [0060] [Chemical 7]
Figure imgf000017_0001
Figure imgf000017_0001
[0061] [ィ匕 8] [0061] [Yi 8]
Figure imgf000018_0001
Figure imgf000018_0001
[0062] [ィ匕 9]
Figure imgf000019_0001
[0062] [Yi 9]
Figure imgf000019_0001
[0063] [化 10] [0063] [Chemical 10]
Figure imgf000020_0001
Figure imgf000020_0001
[0064] [化 11]
Figure imgf000021_0001
これらの一般式 (X)で表される化合物は、その製法は問わないが、例えば、 J. Org . Chem. , 33, 1656 (1968) .、J. Org. Chem. , 42, 1197 (1977) .、J. Org. Chem. , 62, 3748 (1997) .、 Tetrahedron Lett. , 29, 4177 (1988) .、丸善 KK出版、第四版実験化学講座 20有機合成 II、 213〜、平成 4年、 Ed. by Alfred Hasfner, The cnemistry oi heterocyclic compounds― Small Ring H eterocycles part 3 Oxiranes, John & Wiley and Sons, An Interscienc e Publication, New York, 1985、吉村、接着、 29卷 12号、 32、 1985、吉村、 接着、 30卷 5号、 42, 1986,吉村、接着、 30卷 7号、 42, 1986,特開平 11— 1003 78号公報、特開平 4 36263号公報、特開平 4 69360号公報等の文献を参考に して合成でさる。 [0066] 以下、本発明に係る一般式 (X)で表される化合物の合成例を示すが、本発明はこ れらに限定されない。 [0064] [Chemical 11]
Figure imgf000021_0001
These compounds represented by the general formula (X) may be produced by any method, for example, J. Org. Chem., 33, 1656 (1968)., J. Org. Chem., 42, 1197 (1977). ), J. Org. Chem., 62, 3748 (1997)., Tetrahedron Lett., 29, 4177 (1988), Maruzen KK Publishing, 4th edition, Experimental Chemistry Course 20 Organic Synthesis II, 213-, Heisei 4 Ed. By Alfred Hasfner, The cnemistry oi cyclic compounds― Small Ring Heterocycles part 3 Oxiranes, John & Wiley and Sons, An Interscienc e Publication, New York, 1985, Yoshimura, Adhesion, 29 卷 12, 32, 1985 , Yoshimura, Adhesion, 30-5, 42, 1986, Yoshimura, Adhesion, 30-7, 42, 1986, JP-A-11-100378, JP-A-4-36263, JP-A-469360, etc. Refer to the above literature for synthesis. [0066] Hereinafter, synthesis examples of the compound represented by the general formula (X) according to the present invention will be shown, but the present invention is not limited thereto.
[0067] 《合成例 1 : X—2の合成》  [0067] << Synthesis Example 1: Synthesis of X-2 >>
反応器にビサボロール 11. 8gと塩化メチレン 120mlを入れ、攪拌した。次に m—ク ロロ過安息香酸 (mCPBA) 36gを塩化メチレン 360mlに溶解させた液を、攪拌して いるビサボロールの塩化メチレン溶液へ、室温で一時間かけて滴下した。さらに 2時 間攪拌した後に、 100mlの飽和亜硫酸ナトリウム水溶液をカ卩え、残存する過剰の mC PBAを失活させ、分液漏斗を用いて有機層を分取し、 100mlの塩化メチレンで水層 カゝら有機物を抽出した。有機層を混合し、 100mlの飽和重炭酸ソーダ水溶液で 2回 洗浄した後、 100mlの純水、 100mlの飽和食塩水で順次洗浄を行った。得られた有 機層を無水硫酸マグネシウム上で乾燥し、濾過、濃縮後、混合物をシリカゲルクロマ トグラフィ一によつて分離し、 9gの X— 2を得た。 NMRおよびマススペクトル（親 ピーク 255)にて目的物を確認した。  Bisabolol 11.8 g and methylene chloride 120 ml were added to the reactor and stirred. Next, 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. After further stirring for 2 hours, 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).
[0068] 'H-NMRCCDCl ) δ (ppm)：  [0068] 'H-NMRCCDCl) δ (ppm):
3  Three
1. 0- 2. 2 (m, 24H、メチル、メチレン、シクロへキサン環メチレン、メチン、ヒドロキ シ基）、 2. 9- 3. l (m, 1H、エポキシ根元）、 3. 6— 3. 8 (m, 1H,エポキシ根元） 《合成例 2 :X— 4の合成》  1. 0- 2.2 (m, 24H, methyl, methylene, cyclohexane ring methylene, methine, hydroxy group), 2. 9- 3. l (m, 1H, epoxy root), 3.6-6 8 (m, 1H, epoxy base) << Synthesis Example 2: Synthesis of X-4 >>
反応器に 12gの下記中間体 Aと塩化メチレン 90mlを入れ、攪拌した。次に m—クロ 口過安息香酸 (mCPBA) 26. 3gを塩化メチレン 270mlに溶解させた液を、攪拌して いる中間体 Aの塩化メチレン溶液へ、室温で一時間かけて滴下した。さらに 2時間攪 拌した後に、 80mlの飽和亜硫酸ナトリウム水溶液をカ卩え、残存する過剰の mCPBA を失活させ、分液漏斗を用いて有機層を分取し、 80mlの塩化メチレンで水層から有 機物を抽出した。有機層を混合し、 80mlの飽和重炭酸ソーダ水溶液で 2回洗浄した 後、 80mlの純水、 80mlの飽和食塩水で順次洗浄を行った。得られた有機層を無水 硫酸マグネシウム上で乾燥し、濾過、濃縮後、混合物をシリカゲルクロマトグラフィー によって分離し、 12gの X— 4を得た。 H—NMRおよびマススペクトル（親ピーク 297 )にて目的物を確認した。  The reactor was charged with 12 g of the following intermediate A and 90 ml of methylene chloride. Next, 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. After further stirring for 2 hours, 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).
[0069] 'H -NMR CCDCI ) δ (ppm) : 1. 2— 2. 2 (m, 26H、メチル、メチレン、シクロへ キサン環メチレン、メチン、ヒドロキシ基）、 2. 6- 2. 8 (m, 1H、エポキシ根元）、 2. 9 - 3. 2 (m, 1H,エポキシ根元） [0069] 'H -NMR CCDCI) δ (ppm): 1. 2— 2. 2 (m, 26H, methyl, methylene, cycloto Xylene ring methylene, methine, hydroxy group), 2. 6- 2. 8 (m, 1H, epoxy root), 2. 9-3.2 (m, 1H, epoxy root)
[0070] [化 12]  [0070] [Chemical 12]
Figure imgf000023_0001
Figure imgf000023_0001
[0071] 《合成例 3 : X— 6の合成》 [0071] << Synthesis Example 3: Synthesis of X-6 >>
反応器に 6. 6gの下記中間体 Bと塩化メチレン 40mlを入れ、攪拌した。次に m—ク ロロ過安息香酸 (mCPBA) l lgを塩化メチレン 120mlに溶解させた液を、攪拌して いる中間体 Bの塩化メチレン溶液へ、室温で一時間かけて滴下した。さらに 2時間攪 拌した後に、 40mlの飽和亜硫酸ナトリウム水溶液をカ卩え、残存する過剰の mCPBA を失活させ、分液漏斗を用いて有機層を分取し、 40mlの塩化メチレンで水層から有 機物を抽出した。有機層を混合し、 40mlの飽和重炭酸ソーダ水溶液で 2回洗浄した 後、 40mlの純水、 40mlの飽和食塩水で順次洗浄を行った。得られた有機層を無水 硫酸マグネシウム上で乾燥し、濾過、濃縮後、混合物をシリカゲルクロマトグラフィー によって分離し、 4. 5gの X— 6を得た。丄！！ー NMRおよびマススペクトル（親ピーク 35 1)にて目的物を確認した。  Into the reactor, 6.6 g of the following intermediate B and 40 ml of methylene chloride were added and stirred. Next, a solution prepared by dissolving m-chloroperbenzoic acid (mCPBA) 1 lg in 120 ml of methylene chloride was added dropwise to the stirring solution of intermediate B in methylene chloride at room temperature over 1 hour. After stirring for another 2 hours, 40 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 40 ml of methylene chloride was added to the aqueous layer. The organic matter was extracted. The organic layers were mixed, washed twice with 40 ml saturated aqueous sodium bicarbonate solution, and then washed successively with 40 ml pure water and 40 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 4.5 g of X-6.丄! ! -The target product was confirmed by NMR and mass spectrum (parent peak 351).
[0072] 'H-NMRCCDCl ) δ (ppm) : 1. 1— 2. 2 (m, 23H、メチル、メチレン、シクロへ  [0072] 'H-NMRCCDCl) δ (ppm): 1. 1— 2. 2 (m, 23H, methyl, methylene, cycloto
3  Three
キサン環メチレン、メチン、ヒドロキシ基）、 2. 6- 2. 8 (m, 1H、エポキシ根元）、 2. 9 - 3. 2 (m, 1H,エポキシ根元）  Xylene ring methylene, methine, hydroxy group), 2. 6- 2. 8 (m, 1H, epoxy root), 2. 9-3.2 (m, 1H, epoxy root)
[0073] [化 13] 中間体 B
Figure imgf000023_0002
[0074] 《合成例 4： X— 5の合成》 [0073] [Chemical 13] Intermediate B
Figure imgf000023_0002
[0074] << Synthesis Example 4: Synthesis of X-5 >>
反応器に 13gの下記中間体 Cと塩化メチレン 80mlを入れ、攪拌した。次に m—クロ 口過安息香酸 (mCPBA) 22gを塩化メチレン 240mlに溶解させた液を、攪拌してい る中間体 Cの塩化メチレン溶液へ、室温で一時間かけて滴下した。さらに 2時間攪拌 した後に、 80mlの飽和亜硫酸ナトリウム水溶液をカ卩え、残存する過剰の mCPBAを 失活させ、分液漏斗を用いて有機層を分取し、 80mlの塩化メチレンで水層から有機 物を抽出した。有機層を混合し、 80mlの飽和重炭酸ソーダ水溶液で 2回洗浄した後 、 80mlの純水、 80mlの飽和食塩水で順次洗浄を行った。得られた有機層を無水硫 酸マグネシウム上で乾燥し、濾過、濃縮後、混合物をシリカゲルクロマトグラフィーに よって分離し、 10gの X— 5を得た。 H—NMRおよびマススペクトル（親ピーク 283) にて目的物を確認した。  13 g of the following intermediate C and 80 ml of methylene chloride were placed in the reactor and stirred. Next, a solution prepared by dissolving 22 g of m-chloroperbenzoic acid (mCPBA) in 240 ml of methylene chloride was added dropwise to the stirring solution of Intermediate C in methylene chloride at room temperature over 1 hour. After further stirring for 2 hours, 80 ml of saturated sodium sulfite aqueous solution was added to quench the remaining excess mCPBA, the organic layer was separated using a separatory funnel, and the organic layer was separated from the aqueous layer with 80 ml of methylene chloride. The product was extracted. The organic layers were mixed, washed twice with 80 ml saturated aqueous sodium bicarbonate solution, and then washed successively with 80 ml pure water and 80 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 10 g of X-5. The target product was confirmed by 1 H-NMR and mass spectrum (parent peak 283).
[0075] ^Η— NMR(CDC1 ) δ (ppm) : 1. 2— 2. 2 (m, 26H,メチル、メチレン、シクロへ  [0075] ^ Η—NMR (CDC1) δ (ppm): 1. 2— 2. 2 (m, 26H, methyl, methylene, cycloto
3  Three
キサン環メチレン、メチン、ヒドロキシ基）、 2. 6- 2. 8 (m, 1H、エポキシ根元）、 2. 9 - 3. 2 (m, 1H,エポキシ根元）、 3. 2— 3. 4 (m, 2H,エトキシ基メチレン）  Xylene ring methylene, methine, hydroxy group), 2. 6- 2. 8 (m, 1H, epoxy root), 2. 9-3.2 (m, 1H, epoxy root), 3.2-2. m, 2H, ethoxy group methylene)
[0076] [化 14] 中間体 C[0076] [Chemical 14] Intermediate C
Figure imgf000024_0001
Figure imgf000024_0001
[0077] 《合成例 5〜7》 [0077] Synthesis examples 5 to 7
下式に示す通り、上記の合成例 1〜4と同様の方法により X— 21、 X— 28、 X— 39 を得た。構造は1 H—NMR及びマススペクトル（それぞれの親ピークは、 227、 241 及び 325)にて確認した。 As shown in the following formula, X-21, X-28, and X-39 were obtained in the same manner as in Synthesis Examples 1 to 4 described above. The structure was confirmed by 1 H-NMR and mass spectrum (respective parent peaks were 227, 241 and 325).
[0078] [化 15] 合成例 5 [0078] [Chemical 15] Synthesis example 5
Figure imgf000025_0001
Figure imgf000025_0001
中間体 E(11g> X-28(10g) 合成例 7
Figure imgf000025_0002
Intermediate E (11g> X-28 (10g) Synthesis Example 7
Figure imgf000025_0002
中間体 F(4g) X-39(4g)  Intermediate F (4g) X-39 (4g)
[0079] 本発明の重合性組成物においては、一般式 (X)で表される化合物とともに、ォキセ タン環を有する化合物を併用することができ、ォキセタン環を有する化合物としては、 特開 2001— 220526号公報、同 2001— 310937号公報に記載の公知のあらゆる ォキセタンィ匕合物を使用できる。 [0079] In the polymerizable composition of the present invention, 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.
[0080] 本発明の重合性組成物にお!、ては、組成物の高!、硬化性、硬化膜の所望の物性 を得るために、一般式 (X)で表される化合物とともに、ォキセタン環の 2位が置換され て 、な 、ォキセタンィ匕合物を併用することが好ま 、。 [0080] In the polymerizable composition of the present invention, in order to obtain the high composition, curability, and desired physical properties of the cured film, together with the compound represented by the general formula (X), oxetane It is preferable to use an oxetane compound in combination when the 2-position of the ring is substituted.
[0081] 2位が置換されていないォキセタン化合物の一例としては、特開 2004— 143135 号公報の段落番号 0091 (化 16)に記載されている一般式（101)で示される化合物 が挙げられる。 [0081] As an example of an oxetane compound which is not substituted at the 2-position, a compound represented by the general formula (101) described in paragraph No. 0091 (Chemical Formula 16) of JP-A-2004-143135 can be mentioned.
[0082] 本発明の重合性組成物において、組成物の粘度や保存性などに起因する組成物 の適当な取り扱いやすさを得るためには、ォキセタン環をひとつのみ含むォキセタン 化合物を併用することが好ましぐ例えば以下の株式会社東亞合成製ァロンォキセタ ン OXT— 101 (例示化合物 1)、ΟΧΤ— 212 (例示化合物 2)等が挙げられる。 [0082] In the polymerizable composition of the present invention, 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), ΟΧΤ-212 (Exemplary Compound 2) manufactured by Toagosei Co., Ltd., and the like.
[0083] [化 16] 例示化合物 1 例示化合物 2
Figure imgf000026_0001
[0083] [Chemical Formula 16] Exemplary Compound 1 Exemplary Compound 2
Figure imgf000026_0001
[0084] 更に、本発明で好ましく併用出来るォキセタン化合物として、 2個のォキセタン環を 有する化合物が、得られる組成物が粘着性に優れ、低粘度で作業性に優れるため、 特に好ましい。 2個のォキセタン環を有する化合物の一例としては、特開 2004— 14 3135号公報の段落番号 0094 (ィ匕 17)に記載されて 、る一般式（102)で示される化 合物等が挙げられる。 [0084] Further, as an oxetane compound that can be preferably used in the present invention, a compound having two oxetane rings is particularly preferable because the resulting composition has excellent adhesiveness, low viscosity, and excellent workability. As an example of a compound having two oxetane rings, a compound represented by the general formula (102) described in paragraph No. 0094 (ii) of JP-A-2004-143135 is exemplified. It is done.
[0085] 2個のォキセタン環を有する化合物の具体例としては、特開 2004— 143135号公 報の段落番号 0106 (化 22)に記載されている例示化合物 41、 42が挙げられる。  [0085] Specific examples of the compound having two oxetane rings include Exemplified Compounds 41 and 42 described in paragraph No. 0106 (Chemical Formula 22) of JP 2004-143135 A.
[0086] 2個のォキセタン環を有する化合物において、上記の化合物以外の好ましい例とし ては、特開 2004— 143135号公報の段落番号 0109 (化 23)に記載されている一般 式（107)で示される化合物がある。 [0086] Among the compounds having two oxetane rings, preferable examples other than the above-described compounds include those represented by general formula (107) described in paragraph No. 0109 (Chemical Formula 23) of JP-A-2004-143135. There are compounds shown.
[0087] また、 3〜4個のォキセタン環を有する化合物の一例としては、特開 2004— 14313[0087] Examples of the compound having 3 to 4 oxetane rings include JP-A-2004-14313.
5号公報の段落番号 0111 (化 24)に記載されて ヽる一般式（108)で示される化合 物が挙げられる。 Examples include compounds represented by general formula (108) described in paragraph No. 0111 (Chemical Formula 24) of No. 5 publication.
[0088] 3〜4個のォキセタン環を有する化合物の一例としては、特開 2004— 143135号 公報の段落番号 0116 (化 26)に記載されて 、る例示化合物 43が挙げられる。  [0088] As an example of a compound having 3 to 4 oxetane rings, Exemplified Compound 43 described in paragraph No. 0116 (Chemical Formula 26) of JP-A-2004-143135 can be mentioned.
[0089] さらに、上記説明した以外の 1〜4個のォキセタン環を有する化合物の例としては、 特開 2004— 143135号公報の段落番号 0118 (化 27)に記載されている一般式（10[0089] Further, 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.
9)で示される化合物が挙げられる。 The compound shown by 9) is mentioned.
[0090] 本発明で使用するォキセタンィ匕合物の好ましい具体例としては、特開 2004— 143[0090] Preferable specific examples of the oxetane compound used in the present invention include JP-A-2004-143.
135号公報の段落番号 0121 (化 28)に記載されている例示化合物 44〜46を挙げ ることがでさる。 [0091] 上述したォキセタン環を有する各化合物の製造方法は特に限定されず、従来知ら れた方法に従えばよぐ例えば、パティソン（D. B. Pattison, J. Am. Chem. Soc. , 3455, 79 (1957) )が開示している、ジオールからのォキセタン環合成法等がある 。また、これら以外にも、分子量 1000〜5000程度の高分子量を有する 1〜4個のォ キセタン環を有する化合物も挙げられる。これらの具体的化合物例としては、特開 20 04— 143135号公報の段落番号 0123 (化 29)に記載されている化合物を挙げるこ とがでさる。 Exemplified compounds 44 to 46 described in paragraph No. 0121 (Chemical 28) of No. 135 publication can be mentioned. [0091] The production method of each compound having an oxetane ring described above is not particularly limited. For example, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79 ( 1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also exemplified. Specific examples of these compounds include compounds described in paragraph No. 0123 (Chemical 29) of JP-A No. 2004-143135.
[0092] 本発明の重合性組成物においては、一般式 (X)で表される化合物とともに、下記 一般式 (A)で表される脂環式ェポキサイド (本明細書中では脂環式ェポキサイドとも 記載する）を併用することができ、硬化膜に柔軟性などの所望の物性を付与する必 要がある場合にはこれらを併用することが好まし 、。  [0092] In the polymerizable composition of the present invention, together with the compound represented by the general formula (X), 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.
[0093] [化 17] 一般式 (A) [0093] [Chemical Formula 17] General formula (A)
Figure imgf000027_0001
Figure imgf000027_0001
[0094] 式中、 R はカチオン重合性あるいはラジカル重合性の反応性の官能基を含まな [0094] In the formula, R does not contain a reactive functional group that is cationically polymerizable or radically polymerizable.
101  101
い置換基を表し、 mlOは 1、 2、 3または 4を表す。  MlO represents 1, 2, 3 or 4.
[0095] 一般式 (A)にお 、て、 R はカチオン重合性あるいはラジカル重合性の反応性の [0095] In the general formula (A), R represents a cationically polymerizable or radically polymerizable reactive group.
101  101
官能基を含まない置換基を表す、置換基の例としては、ハロゲン原子 (例えば、塩素 原子、臭素原子、フッ素原子等）、炭素数 1〜20個のアルキル基 (例えば、メチル基 、ェチル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 3〜6個のシクロアル キル基（例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシ ル基等）、炭素数 1〜20個のアルコキシ基 (例えば、メトキシ基、エトキシ基、 n—プロ ポキシ基、 iso—プロポキシ基、 n—ブトキシ基、 tert—ブトキシ基等）、炭素数 2〜20 のァシル基 (例えば、ァセチル基、プロピオニル基、トリフルォロアセチル基等）、炭素 数 2〜20のァシルォキシ基（例えば、ァセトキシ基、プロピオ-ルォキシ基、トリフル ォロアセトキシ基等）、炭素数 2〜20のァシルチオ基 (例えば、ァセチルチオ基、プロ ピオ-ルチオ基、トリフルォロアセチルチオ基等）、炭素数 2〜20のアルコキシカルボ -ル基（例えば、メトキシカルボ-ル基、エトキシカルボ-ル基、 tert ブトキシカルボ -ル基等）、炭素数 2〜20のアルキルチオカルボ-ル基 (例えば、メチルチオカルボ -ル基、ェチルチオカルボ-ル基、 tert—ブチルチオカルボ-ル基等）等が挙げら れる。 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). , Propyl group, isopropyl group, butyl group, etc.), cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), 1 to 20 carbon atoms 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, propio-thio group, trifluoroacetylthio group, etc.), C2-C20 alkoxycarbo group (for example, methoxycarbo group). -Alkyl group, ethoxycarbol group, tert-butoxycarbol group, etc.), alkylthiocarbol group having 2 to 20 carbon atoms (for example, methylthiocarbol group, ethylthiocarbol group, tert-butylthiocarbole group) Group, etc.).
[0096] これらの基は更に置換基を有して 、てもよ 、。置換基としては、ハロゲン原子 (例え ば、塩素原子、臭素原子、フッ素原子等）、炭素数 1〜20個のアルコキシ基 (例えば 、メトキシ基、エトキシ基、 n プロポキシ基、 iso プロポキシ基、 n ブトキシ基、 tert ブトキシ基等）、炭素数 2〜20のァシル基 (例えば、ァセチル基、プロピオニル基、 トリフルォロアセチル基等）、炭素数 2〜20のァシルォキシ基 (例えば、ァセトキシ基、 プロピオ-ルォキシ基、トリフルォロアセトキシ基等）、炭素数 2〜20のアルコキシ力 ルポ-ル基（例えば、メトキシカルボ-ル基、エトキシカルボ-ル基、 tert ブトキシカ ルポニル基等）、炭素数 2〜20のアルキルチオカルボ-ル基 (例えば、メチルチオ力 ルボニル基、ェチルチオカルボ-ル基、 tert—ブチルチオカルボ-ル基等）、ァリー ルォキシカルボ-ル基、アルキルスルホ-ル基、ァリールスルホ-ル基、シァノ基、二 トロ基等が挙がられる。置換基として好ましいのは、ハロゲン原子、アルコキシ基、ァ シルォキシ基、アルコキシカルボ-ル基である。  [0096] These groups may further have a substituent. Examples of the substituent 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). Group, tert-butoxy group, etc.), 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 alkoxycarbo group.
[0097] 高硬度の硬化膜を生成し、更に硬化膜の基材密着性を良くすると言う点でより好ま LV、脂環式ェポキサイドは、下記一般式 (A— I)で表される化合物である。  [0097] 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.
[0098] [化 18] 一般式 (A I) [0098] [Chemical Formula 18] General formula (A I)
Figure imgf000028_0001
Figure imgf000028_0001
[0099] 式中、 R は置換基を表し、 mi lは 0、 1、 2または 3を表す。 R 、R 、R はそれ [0099] In the formula, R represents a substituent, and mi 1 represents 0, 1, 2, or 3. R, R, R are
111 112 113 114 ぞれ独立に水素原子、置換または無置換のアルキル基を表す。 Y 及び Y はそれ ぞれ独立に Oまたは Sを表し、 pl lは 0、 1または 2を、 ql lは 0または 1を、 rl lは 0ま たは 1を、 si 1は 0または 1を表す。 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.
[0100] 一般式 (A— I)において、 R が表す置換基の例としては、ハロゲン原子 (例えば、 [0100] In the general formula (AI), examples of the substituent represented by R include a halogen atom (for example,
111  111
塩素原子、臭素原子、フッ素原子等）、炭素数 1〜20個のアルキル基 (例えば、メチ ル基、ェチル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 1〜20個のアル コキシ基（例えば、メトキシ基、エトキシ基、 n—プロポキシ基、 iso プロポキシ基、 n ブトキシ基、 tert ブトキシ基等）、ァシル基 (例えば、ァセチル基、プロピオ-ル基 、トリフルォロアセチル基等）、炭素数 1〜20個のァシルォキシ基 (例えば、ァセトキシ 基、プロピオ-ルォキシ基、トリフルォロアセトキシ基等）、炭素数 1〜20個のアルコキ シカルボ-ル基（例えば、メトキシカルボ-ル基、エトキシカルボ-ル基、 tert—ブトキ シカルボニル基等）、炭素数 2〜20のアルキルチオカルボ-ル基 (例えば、メチルチ ォカルボ-ル基、ェチルチオカルボ-ル基、 tert—ブチルチオカルボ-ル基等）、ァ リールォキシカルボ-ル基、アルキルスルホ-ル基、ァリールスルホ-ル基、シァノ基 、ニトロ基等が挙げられる。置換基として好ましいのは、アルキル基、アルコキシ基、 アルコキシカルボ-ル基である。  Chlorine atom, bromine atom, fluorine atom, etc.), alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), alkoxy having 1 to 20 carbon atoms. 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), § reel O propoxycarbonyl - group, alkylsulfonyl - group, Arirusuruho - group, Shiano group, and a nitro group. Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxycarbo group.
[0101] R 、R 、R は水素原子、置換または無置換のアルキル基を表す。アルキル基  [0101] R 1, R 2 and R 3 represent a hydrogen atom or a substituted or unsubstituted alkyl group. Alkyl group
112 113 114  112 113 114
の例としては、上述した R のアルキル基の例と同義の基を挙げることができる。置換  Examples of these include groups having the same meanings as the examples of the alkyl group of R described above. Replace
111  111
基を有するアルキル基の置換基の例としては、ハロゲン原子 (例えば、塩素原子、臭 素原子、フッ素原子等）、炭素数 1〜20個のアルコキシ基 (例えば、メトキシ基、ェトキ シ基、 n—プロポキシ基、 iso プロポキシ基、 n—ブトキシ基、 tert ブトキシ基等）、 ァシル基 (例えば、ァセチル基、プロピオニル基、トリフルォロアセチル基等）、炭素 数 1〜20個のァシルォキシ基 (例えば、ァセトキシ基、プロピオ-ルォキシ基、トリフ ルォロアセトキシ基等）、炭素数 1〜20個のアルコキシカルボ-ル基 (例えば、メトキ シカルボ-ル基、エトキシカルボ-ル基、 tert ブトキシカルボ-ル基等）、炭素数 2 〜20のアルキルチオカルボ-ル基（例えば、メチルチオカルボ-ル基、ェチルチオ カルボ-ル基、 tert—ブチルチオカルボ-ル基等）、ァリールォキシカルボ-ル基、 アルキルスルホ-ル基、ァリールスルホ-ル基、シァノ基、ニトロ基等が挙げられ、置 換基として好ましいのは、アルコキシ基、アルコキシカルボ-ル基である。 [0102] Y 、 Y は Οまたは Sを表し、 Oが好ましい。 11111は0〜3を表し、 1または 2が好まし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 (for example, methylthiocarbol group, ethylthiocarbol group, tert-butylthiocarbol group, etc.), aryloxy - group, alkylsulfonyl - group, Arirusuruho - group, Shiano group, a nitro group and the like, the preferred location substituent is an alkoxy group, an alkoxycarbonyl - is Le group. [0102] Y and Y represent は or S, and O is preferred. 11111 represents 0-3, 1 or 2 is preferred
11 12 11 12
い。 pl lは 0、 1または 2を表し、 ql l、 rl l、 sl lは 0または 1を表す。  Yes. pl l represents 0, 1 or 2; ql l, rl l, sl l represents 0 or 1;
[0103] 高硬度の硬化膜を生成し、更に硬化膜の基材密着性を良くすると言う点で特に好 ましい脂環式ェポキサイドは、下記一般式 (A— II)で表される化合物である。 [0103] 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.
[0104] [化 19] [0104] [Chemical 19]
—般式 (A— Π)
Figure imgf000030_0001
—General formula (A—Π)
Figure imgf000030_0001
[0105] 式中、 R は置換基を表し、 ml2は 0、 1または 2を表す。 R 、R 、R はそれぞ [0105] In the formula, R represents a substituent, and ml2 represents 0, 1 or 2. R, R, R are each
121 122 123 124 れ独立に水素原子、置換または無置換のアルキル基を表す。 Y  121 122 123 124 Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. Y
21および Y  21 and Y
22はそれぞ れ独立に 0、または Sを表し、 pl2は 0、 1または 2を表し、 ql2は 0または 1を表し、 rl 2は 0または 1を表し、 sl2は 0または 1を表す。  22 each independently represents 0 or S, pl2 represents 0, 1 or 2, ql2 represents 0 or 1, rl 2 represents 0 or 1, and sl2 represents 0 or 1.
[0106] 上記の式中、 R は前記 R と同義である。 Y 、Y は Οまたは Sを表し、 Οが好まし [0106] In the above formula, R is as defined above. Y and Y represent Ο or S, Ο is preferred
121 111 21 22  121 111 21 22
ml2iま 0〜2を表し、 0また ίま 1力好まし!/ヽ。 ρ12ίま 0、 1また ίま 2を表し、 ql2、 rl2 、 sl2は 0または 1を表す。 R 、R 、R は R 、R 、R と同義である。  ml2i represents 0-2, 0 or ί or 1 power! / ヽ. ρ12ί to 0, 1 or ί 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.
122 123 124 112 113 114  122 123 124 112 113 114
[0107] 硬化感度が高ぐ硬化膜の基材密着性を良くし、更に印字環境の変動によっても硬 ィ匕感度が影響されにくいという点で更に好ましい脂環式ェポキサイドは、下記一般式 (A— 111)、一般式 (A— IV)または一般式 (A—V)で表される化合物である。  [0107] 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).
[0108] [化 20] 一般式 (A— III)
Figure imgf000030_0002
[0108] [Chemical formula 20] General formula (A—III)
Figure imgf000030_0002
[0109] 式中、 R は置換基を表し、 ml3は 0、 1または 2を表す。 R 、R 、R はそれぞ れ独立に水素原子、置換または無置換のアルキル基を表す。 pl3は 0、 1または 2を 、 ql3〖ま 0また〖ま 1を表す。 [0109] In the formula, R represents a substituent, and 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
[0110] [化 21] 一般式 (A - IV)
Figure imgf000031_0001
[0110] [Chemical Formula 21] General formula (A-IV)
Figure imgf000031_0001
[0111] 式中、 R は置換基を表し、 ml4は 0、 1または 2を表す。 R 、R 、R はそれぞ In the formula, R represents a substituent, and ml4 represents 0, 1 or 2. R, R, R are each
141 142 143 144 れ独立に水素原子、置換または無置換のアルキル基を表す。 pl4は 0、 1または 2を 表す。  141 142 143 144 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. pl4 represents 0, 1 or 2.
[0112] [化 22] 一般式 (A— V)
Figure imgf000031_0002
[0112] [Chemical 22] General formula (A— V)
Figure imgf000031_0002
[0113] 式中、 R は置換基を表し、 ml5は 0、 1または 2を表す。 R は水素原子、置換ま [0113] In the formula, R represents a substituent, and ml5 represents 0, 1 or 2. R is a hydrogen atom or substituted
151 154  151 154
たは無置換のアルキル基を表す。 s 15は 0または 1を表す。  Or represents an unsubstituted alkyl group. s 15 represents 0 or 1.
[0114] 上記の式中、 R 、R 、R は前記 R と同義である。 ml3、 ml4、 ml5は 0〜2を  [0114] In the above formula, R 1, R 2 and R 3 have the same meanings as R. ml3, ml4, ml5 should be 0-2
131 141 151 111  131 141 151 111
表し、 0また ίま 1力好まし!/ヽ。 ρ13、 ρ14ίま 0、 1また ίま 2を表し、 ql3、 sl5iま 0また ίま 1 を表す。 R 、R 、R 、R 、R 、R 、R は R 、R 、R と同義である。  Represents 0 or ί or 1 power! / ヽ. ρ13, ρ14ί up to 0, 1 or ί up to 2, ql3, sl5i up to 0 or ί 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.
132 133 134 142 143 144 154 112 113 114  132 133 134 142 143 144 154 112 113 114
[0115] 硬化感度が高ぐ硬化膜の基材密着性を良くし、更に印字環境の変動によっても硬 ィ匕感度が影響されにくいという点で特に好ましい脂環式ェポキサイドは、下記一般式 [0115] 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.
(A— VI)で表される化合物である。 It is a compound represented by (A-VI).
[0116] [化 23] -般式 (A— VI) [0116] [Chemical 23] -General formula (A—VI)
Figure imgf000032_0001
Figure imgf000032_0001
[0117] 上記の式中、 R 、R は水素原子または炭素数 1〜6個のアルキル基 (例えば、 [0117] In the above formula, R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example,
1611 1612  1611 1612
メチル基、ェチル基、プロピル基、イソプロピル基、ブチル基、 sec—ブチル基、 tーブ チル基、ペンチル基、へキシル基等）を表し、アルキル基として好ましいのは、メチル 基、ェチル基、プロピル基である。 R 、R 、R は R 、R 、R と同義である。 ql  Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, etc.). 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
162 163 164 112 113 114  162 163 164 112 113 114
6は 0または 1を表す。  6 represents 0 or 1.
[0118] 以下、本発明に用いることのできる一般式 (A)で表される脂環式ェポキサイドの具 体例を示すが、本発明はこれらに限定されない。  [0118] Specific examples of the alicyclic epoxide represented by the general formula (A) that can be used in the present invention are shown below, but the present invention is not limited thereto.
[0119] [化 24] [0119] [Chemical 24]
Figure imgf000033_0001
5]
Figure imgf000033_0001
Five]
Figure imgf000034_0001
6]
Figure imgf000035_0001
Figure imgf000034_0001
6]
Figure imgf000035_0001
SEP— 36 SEP— 37
Figure imgf000035_0002
SEP— 36 SEP— 37
Figure imgf000035_0002
SEP— 38 SEP— 39
Figure imgf000035_0003
SEP— 38 SEP— 39
Figure imgf000035_0003
SEP -40 SEP— 41  SEP -40 SEP— 41
Figure imgf000035_0004
Figure imgf000035_0004
27]
Figure imgf000036_0001
27]
Figure imgf000036_0001
[0123] [化 28] [0123] [Chemical 28]
Figure imgf000037_0001
9]
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
Figure imgf000037_0001
9]
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
SEP— 84
Figure imgf000038_0004
30] SEP— 89 SEP -90 SEP— 84
Figure imgf000038_0004
30] SEP— 89 SEP -90
Figure imgf000039_0001
1]
Figure imgf000039_0001
1]
Figure imgf000040_0001
Figure imgf000040_0001
SEP -108 SEP— 109  SEP -108 SEP— 109
Figure imgf000040_0002
32] SEP— 114 SEP- 115
Figure imgf000041_0001
Figure imgf000040_0002
32] SEP— 114 SEP- 115
Figure imgf000041_0001
SEP— 116 SEP— 117
Figure imgf000041_0002
SEP— 116 SEP— 117
Figure imgf000041_0002
SEP— 118 SEP— 119  SEP—118 SEP—119
Figure imgf000041_0003
Figure imgf000041_0003
SEP— 122 SEP— 123  SEP—122 SEP—123
Figure imgf000041_0004
Figure imgf000041_0004
SEP -126 SEP— 127
Figure imgf000041_0005
33] SEP— 128 SEP-129 SEP -126 SEP— 127
Figure imgf000041_0005
33] SEP— 128 SEP-129
Figure imgf000042_0001
34]
Figure imgf000042_0001
34]
SEP-134 SEP— 135 SEP— 136 SEP-134 SEP— 135 SEP— 136
Figure imgf000043_0001
Figure imgf000043_0001
SEP— 146 SEP -147 SEP -148 SEP— 146 SEP -147 SEP -148
Figure imgf000043_0002
Figure imgf000043_0002
SEP- 152 SEP— 153
Figure imgf000043_0003
35] SEP - 154 SEP— 155 SEP - 156
Figure imgf000044_0001
SEP- 152 SEP— 153
Figure imgf000043_0003
35] SEP-154 SEP— 155 SEP-156
Figure imgf000044_0001
SEP— 157 SEP - 158 SEP— 159
Figure imgf000044_0002
SEP— 157 SEP-158 SEP— 159
Figure imgf000044_0002
SEP— 160 SEP— 161 SEP -162
Figure imgf000044_0003
SEP— 160 SEP— 161 SEP -162
Figure imgf000044_0003
SEP— 163 SEP -164 SEP— 165
Figure imgf000044_0004
SEP— 163 SEP -164 SEP— 165
Figure imgf000044_0004
SEP -166 SEP -167 SEP - 168  SEP -166 SEP -167 SEP -168
Figure imgf000044_0005
Figure imgf000044_0005
[0131] 本発明の重合性組成物において、一般式 (X)で表される化合物の含有量に特に制 限はないが、 0. 1質量％力 60質量％の範囲であることが好ましい。 [0131] In the polymerizable composition of the present invention, 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%.
[0132] 本発明の重合性組成物においては、一般式 (X)で表される化合物、ォキセタン化 合物と一般式 (A)で表される単官能ェポキサイドと共に、多官能の脂環式ェポキサイ ドを併用することができる。それによつて更なる感度向上効果あるいは硬化膜物性の 改良効果を得ることができる。 [0133] 2官能の脂環式ェポキサイドとして好ましいのは、以下の一般式 (B)で表される多 官能のェポキサイドである。 [0132] In the polymerizable composition of the present invention, a polyfunctional alicyclic epoxide together with a compound represented by the general formula (X), an oxetane compound and a monofunctional epoxide represented by the general formula (A). Can be used in combination. As a result, it is possible to obtain a further effect of improving the sensitivity or improving the properties of the cured film. [0133] The difunctional alicyclic epoxide is preferably a polyfunctional epoxide represented by the following general formula (B).
[0134] [化 36] 一般式 (B)  [0134] [Chemical 36] General formula (B)
Figure imgf000045_0001
Figure imgf000045_0001
[0135] 式中、 R 、R は置換基を表し、 m20、 n20は 0、 1または 2を表し、 0または 1が好 [0135] In the formula, R 1 and R 2 represent substituents, m20 and n20 represent 0, 1 or 2, and 0 or 1 is preferred.
201 202  201 202
ましい。 rOは 1〜3を表す。 Lは主鎖に酸素原子または硫黄原子を含んでもよい炭素  Good. rO represents 1-3. L is carbon which may contain an oxygen atom or a sulfur atom in the main chain
0  0
数 1〜 15の rO + 1価の連結基または単結合を表す。  It represents an rO + monovalent linking group or a single bond of the number 1 to 15.
[0136] 上記の式中、 R 、R が表す置換基の例としては、ハロゲン原子 (例えば、塩素原 In the above formula, examples of the substituent represented by R 1 and R 2 include a halogen atom (for example, chlorine atom
201 202  201 202
子、臭素原子、フッ素原子等）、炭素数 1〜6個のアルキル基 (例えば、メチル基、ェ チル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 ι〜6個のアルコキシ基（ 例えば、メトキシ基、エトキシ基、 n プロポキシ基、 iso プロポキシ基、 n ブトキシ 基、 tert—ブトキシ基等）、ァシル基 (例えば、ァセチル基、プロピオ-ル基、トリフル ォロアセチル基等）、ァシルォキシ基 (例えば、ァセトキシ基、プロピオニルォキシ基、 トリフルォロアセトキシ基等）、アルコキシカルボニル基 (例えば、メトキシカルボ-ル 基、エトキシカルボニル基、 tert ブトキシカルボニル基等)等が挙げられる。置換基 として好ましいのは、アルキル基、アルコキシ基、アルコキシカルボ-ル基である。  , A bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.), an alkoxy group having a carbon number of ι to 6 ( 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, propiool group, trifluoroacetyl group, etc.), isyloxy group (for example, Acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, tertbutoxycarbonyl group, etc.) and the like. Preferable substituents are an alkyl group, an alkoxy group, and an alkoxycarbo group.
[0137] Lが表す主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜15の 2価の連 [0137] A divalent chain having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain represented by L
0  0
結基の例としては、以下の基及びこれらの基と O 基、 S 基、 CO 基、 C S 基を複数組み合わせてできる基を挙げることができる。  Examples of the linking group 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.
[0138] メチレン基 [― CH -] [0138] Methylene group [― CH-]
2  2
ェチリデン基 [ >CHCH ]
Figure imgf000045_0002
Ethylidene group [> CHCH]
Figure imgf000045_0002
2—エチレン基 [ CH CH -] 1.2—プロピレン基 [— CH(CH )CH -] 2-Ethylene group [CH CH-] 1.2—Propylene group [— CH (CH) CH-]
3 2  3 2
1.3—プロパンジィノレ基 [— CH CH CH— ]  1.3—propandinole group [— CH CH CH—]
2 2 2  2 2 2
2, 2—ジメチル— 1， 3—プロパンジィル基 [― CHC(CH) CH -]  2, 2-Dimethyl-1, 3-propanediol group [-CHC (CH) CH-]
2 3 2 2  2 3 2 2
2, 2—ジメトキシ— 1, 3—プロパンジィル基 [― CHC(OCH) CH -]  2, 2-dimethoxy-1, 3-propanediyl [-CHC (OCH) CH-]
2 3 2 2  2 3 2 2
2， 2—ジメトキシメチル— 1， 3—プロパンジィル基 [― CH C(CH OCH ) CH -]  2,2-Dimethoxymethyl-1,3-propanediyl group [-CH C (CH OCH) CH-]
2 2 3 2 2 2 2 3 2 2
1—メチル― 1， 3—プロパンジィル基 [― CH(CH )CH CH -] 1-Methyl-1,3-propanediyl group [-CH (CH) CH CH-]
3 2 2  3 2 2
1.4—ブタンジィル基 [— CH CH CH CH― ]  1.4—Butanyl group [— CH CH CH CH—]
2 2 2 2  2 2 2 2
1.5—ペンタンジィル基 [— CH CH CH CH CH― ]  1.5—Pentandyl group [— CH CH CH CH CH—]
2 2 2 2 2  2 2 2 2 2
ォキシジエチレン基 [一 CH CH OCH CH一]  Oxydiethylene group [One CH CH OCH CH One]
2 2 2 2  2 2 2 2
チオジェチレン基 [一 CH CH SCH CH一]  Thiogetylene group [One CH CH SCH CH]
2 2 2 2  2 2 2 2
3—ォキソチオジェチレン基 [— CH CH SOCH CH -]  3-Oxothiojetylene group [— CH CH SOCH CH-]
2 2 2 2  2 2 2 2
3, 3—ジォキソチオジェチレン基 [— CH CH SO CH CH― ]  3, 3-Dioxothiojetylene group [— CH CH SO CH CH—]
2 2 2 2 2  2 2 2 2 2
1.4—ジメチル― 3—ォキサ—1, 5—ペンタンジィル基 [― CH (CH ) CH OCH (  1.4—Dimethyl-3-oxa-1,5-pentanediyl group [— CH (CH) CH OCH (
3 2 3 2
CH )CH一] CH) CH 1]
3 2  3 2
3—ォキソペンタンジィル基 [— CH CH COCH CH -]  3-Oxopentanediol [— CH CH COCH CH-]
2 2 2 2  2 2 2 2
1.5—ジォキソ一 3—ォキサペンタンジィル基 [— COCH OCH CO— ]  1.5-Dioxo 1-Oxapentanediol [— COCH OCH CO—]
2 2  twenty two
4—ォキサ― 1, 7—ヘプタンジィル基 [— CH CH CH OCH CH CH -]  4-Oxa-1, 7-heptaneyl group [— CH CH CH OCH CH CH-]
2 2 2 2 2 2  2 2 2 2 2 2
3, 6—ジォキサ一 1， 8—オクタンジィル基 [— CH CH OCH CH OCH CH一]  3, 6-dioxa 1,8-octane diyl group [—CH CH OCH CH OCH CH]
2 2 2 2 2 2 2 2 2 2 2 2
1, 4, 7—トリメチノレー 3, 6—ジォキサ一 1, 8—オクタンジィル基 [― CH(CH)CH 1, 4, 7-trimethinole 3, 6-dioxa 1,8-octanediyl [-CH (CH) CH
3 Three
OCH(CH )CH OCH(CH )CH一] OCH (CH) CH OCH (CH) CH
2 3 2 3 2  2 3 2 3 2
5, 5—ジメチル— 3, 7—ジォキサ— 1, 9—ノナンジィル基 [― CH CH OCH C(C  5, 5-Dimethyl- 3, 7-Dioxa-1, 9-nonandyl group [-CH CH OCH C (C
2 2 2 2 2 2
H ) CH OCH CH一] H) CH OCH CH
3 2 2 2 2  3 2 2 2 2
5， 5—ジメトキシ一 3, 7—ジォキサ一 1, 9—ノナンジィル基 [— CH CH OCH C(  5,5-dimethoxy-1,3,7-dioxa-1,9-nonanediyl [— CH CH OCH C (
2 2 2 2 2 2
OCH ) CH OCH CH -] OCH) CH OCH CH-]
3 2 2 2 2  3 2 2 2 2
5, 5—ジメトキシメチル一 3, 7—ジォキサ一 1, 9ーノナンジィル基 [― CH CH OC  5,5-Dimethoxymethyl-1,3,7-Dioxa-1,9-nonandyl [-CH CH OC
2 2 twenty two
H C(CH OCH ) CH OCH CH -] H C (CH OCH) CH OCH CH-]
2 2 3 2 2 2 2  2 2 3 2 2 2 2
4, 7—ジォキソ— 3, 8—ジォキサ— 1, 10—デカンジィル基 [― CH CH O— CO  4, 7-Dioxo-3,8-Dioxa-1, 10-decandyl group [-CH CH O- CO
2 2  twenty two
CH CH CO -OCH CH -]  CH CH CO -OCH CH-]
2 2 2 2 3, 8 ジォキソ— 4, 7 ジォキサ— 1, 10 デカンジィル基 [― CH CH CO 2 2 2 2 3, 8 Dioxo- 4, 7 Dioxa 1, 10 Decandyl group [-CH CH CO
2 2 twenty two
CH CH O-COCH CH -] CH CH O-COCH CH-]
1, 3 シクロペンタンジィル基 [ 1, 3 - -C H - ]  1, 3 cyclopentandyl group [1, 3--C H-]
5 8  5 8
1, 2—シクロへキサンジィル基 [ 1, 2 -C H - - ]  1,2-cyclohexanediyl group [1, 2 -C H--]
6 10  6 10
1, 3 シクロへキサンジィル基 [ 1, 3 -C H - - ]  1, 3 cyclohexanyl group [1, 3 -C H--]
6 10  6 10
1, 4ーシクロへキサンジィル基 [ 1, 4 -C H - - ]  1,4-cyclohexanediyl group [1, 4 -C H--]
6 10  6 10
2, 5—テトラヒドロフランジィル基 [2, 5- -C Η Ο - ]  2,5-tetrahydrofuranyl group [2, 5- -C Η Ο-]
4 6  4 6
ρ フエ二レン基 [ ρ— C H一]  ρ Phenylene group [ρ—CH 1]
6 4  6 4
m フエ二レン基 [ πι· -C H一]  m Phenylene group [πι · -C H 1]
ひ， ひ ο キシリレン基 [ ο— CH— C H— CH—」  ，, ο xylylene group [ο— CH— C H— CH—]
2 6 4 2  2 6 4 2
α , α m キシリレン基 [ m— CH—C H—CH—]  α, α m Xylylene group [m— CH—C H—CH—]
2 6 4 2  2 6 4 2
α , α ρ キシリレン基 [ p— CH—C H—CH—]  α, α ρ Xylylene group [p— CH—C H—CH—]
2 6 4 2  2 6 4 2
フラン一 2， 5 ジィル一ビスメチレン基 [2， 5-CH -C H O-CH -]  Furan 2,5 diyl bismethylene [2, 5-CH 2 -CH 2 O-CH 2-]
2 4 2 2  2 4 2 2
チォフェン一 2， 5 ジィル一ビスメチレン基 [2， 5-CH -C H S-CH -]  Thiophene-1,5-diyl-bismethylene group [2,5-CH -C H S-CH-]
2 4 2 2 イソプロピリデンビスー p フエ二レン基 [一 p— C H 一 C (CH ) 一 p— C H 一]  2 4 2 2 Isopropylidenebis- p phenylene group [one p— C H one C (CH) one p— C H one]
6 4 3 2 6 4 6 4 3 2 6 4
3価以上の連結基としては、以上に挙げた 2価の連結基から任意の部位の水素原 子を必要なだけ除いてできる基、及びそれらと O 基、 S 基、 CO 基、 C S 基を複数組み合わせてできる基を挙げることができる。 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は置換基を有していてもよい。置換基の例としては、ハロゲン原子 (例えば、塩素 L may have a substituent. Examples of substituents include halogen atoms (e.g. chlorine
0 0
原子、臭素原子、フッ素原子等）、炭素数 1〜6個のアルキル基 (例えば、メチル基、 ェチル基、プロピル基、イソプロピル基、ブチル基等）、炭素数 1〜6個のアルコキシ 基（例えば、メトキシ基、エトキシ基、 n—プロポキシ基、 iso プロポキシ基、 n—ブトキ シ基、 tert ブトキシ基等）、ァシル基 (例えば、ァセチル基、プロピオ-ル基、トリフ ルォロアセチル基等）、ァシルォキシ基 (例えば、ァセトキシ基、プロピオニルォキシ 基、トリフルォロアセトキシ基、等）、アルコキシカルボ-ル基 (例えば、メトキシカルボ -ル基、エトキシカルボ-ル基、 tert ブトキシカルボ-ル基等）等が挙げられる。置 換基として好ましいのは、アルキル基、アルコキシ基、アルコキシカルボ-ル基である [0140] Lとしては主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜8の 2価の連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. Preferred as a substituent is an alkyl group, an alkoxy group, or an alkoxycarbo group. [0140] 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.
0 0
結基が好ましぐ主鎖が炭素のみ力 なる炭素数 1〜5の 2価の連結基がより好ましい  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.
[0141] 高硬度の硬化膜を生成し、更に硬化膜の基材密着性を良くすると言う点で特に好 ま 、脂環式ェポキサイドは、以下の一般式 (B— I)または (B— II)で表される化合物 である。 [0141] 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. ).
[0142] [化 37]  [0142] [Chemical 37]
Figure imgf000048_0001
Figure imgf000048_0001
[0143] 式中、 R 、R は置換基を表し、 m21、n21は 0、 1または 2を表し、 0または 1が好 [0143] In the formula, R 1 and R 2 represent a substituent, m21 and n21 represent 0, 1 or 2, and 0 or 1 is preferred.
211 212  211 212
ましい。 pl、 qlはそれぞれ 0または 1を表す。 rlは 1〜3を表す。 Lは主鎖に酸素原  Good. pl and ql represent 0 or 1, respectively. rl represents 1-3. L is oxygen source in the main chain
1  1
子または硫黄原子を含んでもよい炭素数 1〜15の rl + 1価の連結基または単結合を 表す。  It represents an rl + 1 monovalent linking group or a single bond having 1 to 15 carbon atoms which may contain a child or a sulfur atom.
[0144] [化 38] 一般式 (B— Π)
Figure imgf000048_0002
[0144] [Chemical 38] General formula (B— Π)
Figure imgf000048_0002
[0145] 式中、 R 、R は置換基を表し、 m22、 n22は 0、 1または 2を表し、 0または 1が好 [0145] In the formula, R 1 and R 2 represent a substituent, m22 and n22 represent 0, 1 or 2, and 0 or 1 is preferred.
221 222  221 222
ましい。 p2、 q2はそれぞれ 0または 1を表す。 r2は 1〜3を表す。 Lは主鎖に酸素原  Good. p2 and q2 each represents 0 or 1. r2 represents 1-3. L is oxygen source in the main chain
2  2
子または硫黄原子を含んでもよ!、炭素数 1〜 15の r2 + 1価の連結基または単結合を 表す。  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.
[0146] 上記の式中、 R 、R 、R 、R は前記一般式 (A— 1)における R と同義である [0147] L、 Lが表す主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜15の 2価[0146] In the above formula, R 1, R 2, R 3 and R 4 have the same meaning as R in the general formula (A-1). [0147] 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
1 2 1 2
の連結基の例としては、 Lの説明で示したものを同じものが挙げられる。 L、 Lとして  Examples of the linking group are the same as those described in the description of L. L, as L
0 1 2 は主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜8の 2価の連結基が好 ましぐ主鎖が炭素のみ力 なる炭素数 1〜5の 2価の連結基がより好ましい。  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.
[0148] 硬化感度が高ぐ更に印字環境の変動によっても硬化感度が影響されにくいという 点で特に好ましい脂環式ェポキサイドは、以下の一般式 (B— III)または (B— IV)で 表される化合物である。 [0148] 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.
[0149] [化 39] [0149] [Chemical 39]
Figure imgf000049_0001
式中、 R 、R は置換基を表し、 m23、 n23は 0または 1を表す。 p3、 q3はそれぞ
Figure imgf000049_0001
In the formula, R 1 and R 2 represent a substituent, and m23 and n23 each represents 0 or 1. p3 and q3 are
231 232 231 232
れ 0または 1を表す。 r3は 1〜3を表す。 Lは主鎖に酸素原子または硫黄原子を含ん でもよい炭素数] ' 15の r3 + 1価の連結基または単結合を表す。  This 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.
[0151] [化 40] 一般式 (B— IV)
Figure imgf000049_0002
[0151] [Chemical 40] General formula (B—IV)
Figure imgf000049_0002
[0152] 式中、 R 、R は置換基を表し、 m24、 n24は 0または 1を表す。 p4、 q4はそれぞ [0152] In the formula, R 1 and R 2 represent a substituent, and m24 and n24 represent 0 or 1. p4 and q4 are
241 242  241 242
れ 0または 1を表す。 r4は 1〜3を表す。 Lは主鎖に酸素原子または硫黄原子を含ん  This represents 0 or 1. r4 represents 1-3. L contains oxygen or sulfur atoms in the main chain
4  Four
でもよ 、炭素数 1〜 15の r4 + 1価の連結基または単結合を表す。  However, it represents an r4 + 1 monovalent linking group or a single bond having 1 to 15 carbon atoms.
[0153] 上記の式中、 R 、R 、R 、R は前記一般式 (A— 1)における R と同義である 。 L、 Lが表す主鎖に酸素原子または硫黄原子を含んでもよい炭素数 1〜15の 2価[0153] In the above formula, 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
3 4 3 4
の連結基の例としては、 Lの説明で示したものを同じものが挙げられる。  Examples of the linking group are the same as those described in the description of L.
0  0
[0154] 以下に好ましい脂環式ェポキサイドの具体例を示す力 本発明はこれらに限定され ない。  [0154] The following are specific examples of preferable alicyclic epoxides. The present invention is not limited to these.
[0155] [化 41]
Figure imgf000050_0001
[0155] [Chemical 41]
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0003
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Figure imgf000050_0003
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EP-8 EP-8
Figure imgf000050_0006
[0156] [化 42]
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0003
Figure imgf000051_0004
Figure imgf000051_0005
Figure imgf000050_0006
[0156] [Chemical 42]
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0003
Figure imgf000051_0004
Figure imgf000051_0005
[0157] [化 43] [0157] [Chemical 43]
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Figure imgf000052_0001
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Figure imgf000053_0001
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Figure imgf000053_0001
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Figure imgf000058_0002
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Figure imgf000058_0003
Figure imgf000058_0003
Figure imgf000058_0004
Figure imgf000058_0005
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Figure imgf000058_0005
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Figure imgf000059_0001
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52]
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52]
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53]
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53]
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54] / Ϊ92ϊε900/:ί1£ 3909ί/-ε/ Oϊ900ίAV
Figure imgf000062_0001
54] / Ϊ92ϊε900 /: ί1 £ 3909ί / -ε / Oϊ900ίAV
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Figure imgf000064_0001
Figure imgf000064_0002
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56] 奮〔〕〔」0171 56] [] [] 0171
Figure imgf000065_0001
Figure imgf000065_0001
一oc CHCHCOCHl—---I 一 o O oen
Figure imgf000066_0001
One oc CHCHCOCHl —--- I One o O oen
Figure imgf000066_0001
Figure imgf000066_0002
Figure imgf000066_0002
Figure imgf000066_0003
Figure imgf000066_0003
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60]
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Figure imgf000068_0001
60]
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000069_0002
[0175] これらのェポキサイドの添加量としては、硬化環境 (温度、湿度）により硬化性の安 定度向上、且つ、硬化後の膜物性を適性に保つ観点から、添加量としては 10質量 %〜40質量％含有することが好ましぐ更に好ましくは、 20質量％〜40質量％の範 囲である。 [0175] 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.
[0176] 本発明では、多官能ェポキサイドの 1種を単独で使用してもよいが、 2種以上を適 宜組み合わせて使用してもよい。  [0176] In the present invention, one type of polyfunctional epoxide may be used alone, or two or more types may be used in appropriate combination.
[0177] これらの脂環式ェポキサイドは、その製法は問わないが、例えば、丸善 KK出版、 第四版実験化学講座 20有機合成 II、 213〜、平成 4年、 Ed. by Alfred Hasfner , The chemistry of heterocyclic compounds― Small Ring Heterocycl es part 3 Oxiranes, John & Wiley and Sons, An Interscience Public ation, New York, 1985、吉村、接着、 29卷 12号、 32、 1985、吉村、接着、 30 卷 5号、 42、 1986、吉村、接着、 30卷 7号、 42、 1986、特開平 11— 100378号公 報、同 4— 36263号公報、同 4— 69360号公報の各公報等の文献を参考にして合 成できる。 [0177] The production method of these alicyclic epoxides is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycl es part 3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, 29-12, 32, 1985, Yoshimura, Adhesion, 30-5, 42, 1986, Yoshimura, Adhesion, 30-7, 42, 1986, Japanese Patent Laid-Open No. 11-100378 In addition, it can be synthesized with reference to documents such as the publications No. 4-36263 and No. 4-69360.
[0178] 本発明の重合性組成物は従来公知の重合開始剤を用いることができ、重合開始剤 は酸発生剤であることが好ましぐインク組成物として用いる場合には光酸発生剤で あることが好ましい。重合開始剤を用いることにより、本発明の重合性組成物は活性 光線または熱、あるいはその両方をカ卩えることによって重合させることができる力 本 発明の重合性組成物をインク組成物 (インク組成物については、後に詳細に説明す る。）として用いる場合には、活性光線を照射することによって重合させることが好まし ぐ紫外線を照射することによって重合させることがより好ましい。  [0178] In the polymerizable composition of the present invention, a conventionally known polymerization initiator can be used. When the polymerization initiator is used as an ink composition that is preferably an acid generator, a photoacid generator is used. Preferably there is. By using a polymerization initiator, 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.) When it is used, it is preferable to polymerize by irradiating with actinic rays, and it is more preferable to polymerize by irradiating with ultraviolet rays.
[0179] 本発明の重合性組成物を用いたカチオン重合型インクで用いる光酸発生剤として は、例えば、化学増幅型フォトレジストや光力チオン重合に利用される化合物が用い られる（有機エレクトロニクス材料研究会編、「イメージング用有機材料」、ぶんしん出 版（1993年）、 187〜192ページ参照)。本発明に好適な化合物の例を以下に挙げ る。  [0179] As 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.
[0180] 第 1に、ジァゾ二ゥム、アンモニゥム、ョードニゥム、スノレホニゥム、ホスホニゥムなど の芳香族ォ -ゥム化合物の B (C F )―、 PF―、 AsF―、 SbF―、 p— CH C H SO—塩、  [0180] Firstly, B (CF)-, PF-, AsF-, SbF-, p-CH CH SO-- salt,
6 5 4 6 6 6 3 6 4 3 6 5 4 6 6 6 3 6 4 3
CF SO—塩などのスルホン酸塩を挙げることができる。対ァ-オンとしてボレートイ匕合Mention may be made of sulfonates such as CF 2 SO—salts. Borate as a match
3 3 3 3
物をもつもの及び PF—塩が酸発生能力が高く好ましい。ォニゥム化合物の具体的例  Those having substances and PF-salts are preferred because of their high acid generation ability. Specific examples of onium compounds
6  6
として例えば、特開 2004— 143135号公報、段落番号 0149 (化 31)に記載されて As described in, for example, JP-A-2004-143135, paragraph number 0149 (Chemical Formula 31)
V、る化合物を挙げることができる。 V, and the like.
[0181] 第 2に、スルホン酸を発生するスルホンィ匕物を挙げることができ、具体的例として例 えば、特開 2004— 143135号公報、段落番号 0151 (化 32)に記載されている化合 物を挙げることができる。 [0181] Secondly, 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.
[0182] 第 3に、ハロゲンィ匕水素を発生するハロゲン化物も用いることができ、具体的例とし て例えば、特開 2004— 143135号公報、段落番号 0152 (化 33)に記載されている 化合物を挙げることができる。 [0182] Thirdly, a halide that generates halogenated hydrogen can also be used. As specific examples, for example, compounds described in JP-A-2004-143135, paragraph No. 0152 (Chemical Formula 33) are used. Can be mentioned.
[0183] 第 4に、鉄アレン錯体を挙げることができ、具体的例として例えば、特開 2004— 14[0183] Fourthly, an iron allene complex can be mentioned, and specific examples thereof include, for example, JP-A-2004-14.
3135号公報、段落番号 0155 (化 34)に記載されている化合物を挙げることができる [0184] 本発明で用いられる光力チオン重合開始剤としては、ァリールスルホ-ゥム塩誘導 体（例えば、ユニオン 'カーバイド社製のサイラキュア UVI— 6990、サイラキュア UVI 6974、旭電化工業社製のアデカオプトマー SP— 150、アデカオプトマー SP— 15 2、アデカオプトマー SP— 170、アデカオプトマー SP— 172)、ァリルョードニゥム塩 誘導体 (例えば、ローディア社製の RP— 2074)、アレン—イオン錯体誘導体 (例え ば、チバガイギ一社製のィルガキュア 261)、ジァゾ -ゥム塩誘導体、トリアジン系開 始剤及びその他のハロゲンィ匕物等の酸発生剤が挙げられる。カチオン重合開始剤 は、カチオン重合性を有する化合物 100質量部に対して、硬化性向上の観点から、 0. 2質量部〜 20質量部の比率で含有させることが好ま 、。 Examples include compounds described in Japanese Patent No. 3135, paragraph 0155 (Chemical Formula 34). [0184] 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 of the compound having cationic polymerizability from the viewpoint of improving curability.
[0185] 本発明で用いられる光酸発生剤として好ましいのは、スルホニゥム塩、ョードニゥム 塩、アンモ-ゥム塩、ホスホ-ゥム塩、等のォ-ゥム塩であり、中でもスルホ -ゥム塩化 合物が好ましい。より好ましいスルホユウム塩ィ匕合物の構造として、特開 2004— 143 135号の請求項 8に記載されている一般式 (1—1)、 (1- 2) (I 3)で表されるスルホ 二ゥム塩を挙げることができる。  [0185] 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. As a more preferred structure of the sulfoyuium salt compound, 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.
[0186] さらに、一般式 (1—1)、（1—2)、（I 3)で表されるスルホ-ゥム塩についてのより 詳しい説明は、特開 2004— 143135号公報の段落番号 0159〜0171に記載され ている。  [0186] Further, a more detailed description of the sulfo salt represented by the general formulas (1-1), (1-2), and (I 3) is described in paragraph No. 0159 of JP-A-2004-143135. ~ 0171.
[0187] 一般式 (I 1)、（I 2) (I— 3)で表されるスルホニゥム塩の具体例は特開 2004— 143135号公報の段落番号 0174〜0178 (ィ匕 35〜39)に記載されている PI— 1〜P 1— 37を挙げることができる。  Specific examples of the sulfonium salt represented by the general formulas (I 1), (I 2) (I-3) are described in paragraph Nos. 0174 to 0178 (I 匕 35 to 39) of JP-A-2004-143135. The described PI-1 to P1-37 can be mentioned.
[0188] 本発明の重合性組成物には、上記説明した構成要素のほかに各種の添加剤を用 いることがでさる。  [0188] In addition to the constituent elements described above, various additives can be used in the polymerizable composition of the present invention.
[0189] 本発明の重合性組成物に使用できる添加剤として、例えば光重合促進剤などが挙 げられる。  [0189] Examples of additives that can be used in the polymerizable composition of the present invention include a photopolymerization accelerator.
[0190] 光重合促進剤としては、アントラセン、アントラセン誘導体 (例えば、旭電化工業社 製のアデカオプトマー SP— 100)、フエノチアジン（10H—フエノチアジン）、フエノチ ァジン誘導体が（例えば、 10—メチルフエノチアジン、 10—ェチルフエノチアジン、 1 0—デシルフエノチアジン、 10—ァセチルフエノチアジン、 10—デシルフエノチアジン —5—ォキシド、 10—デシルフエノチアジン一 5, 5—ジォキシド、 10—ァセチルフエ ノチアジン 5, 5—ジォキシド等)挙げられる。これらの光重合促進剤は 1種または 複数を組み合わせて使用することができる。 [0190] 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). Thiazine, 10-ethylphenothiazine, 1 0-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylethylnothiazine 5, 5 —Dioxide, etc.). These photopolymerization accelerators can be used alone or in combination.
[0191] 本発明の重合性組成物を硬化膜形成の為の硬化性組成物として使用する場合、 粘度が 0. ImPa's〜： LOOOmPa'sであることが好ましぐ 0. lmPa's〜500mPa's であることがより好ましぐ 0. lmPa's〜300mPa'sであることがさらに好ましぐ 0.1 mPa · s〜 150mPa · sであることが最も好まし!/ヽ。  [0191] When the polymerizable composition of the present invention is used as a curable composition for forming a cured film, 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! / ヽ.
[0192] 《インク組成物》  [0192] <Ink composition>
本発明のインク組成物（単にインクとも 、う）につ 、て説明する。  The ink composition of the present invention (simply ink) will be described.
本発明のインク組成物とは本発明の重合性組成物と色材を含む組成物を ヽ、その 他各種添加物を含んで ヽても良 、。  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.
[0193] 本発明の重合性組成物を用いたインク組成物で用いる色材としては、重合性化合 物の主成分に溶解または分散できる色材であれば制限無く使用でき、油溶性染料も しくは顔料が好ましく、耐候性 ·耐光性の点から顔料が好ま U、。  [0193] 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.
[0194] 本発明で好ましく用いることのできる顔料を、以下に列挙する。  [0194] Pigments that can be preferably used in the present invention are listed below.
C. I. Pigment Yellow— 1、 3、 12、 13、 14、 17、 81、 83、 87、 95、 109、 42 C. I. Pigment Yellow—1, 3, 12, 13, 14, 17, 81, 83, 87, 95, 109, 42
C. I. Pigment Orange— 16、 36、 38 C. I. Pigment Orange— 16, 36, 38
C. I. Pigment Red— 5、 22、 38、 48:1、 48:2、 48:4、 49:1、 53:1、 57:1、 6 C. I. Pigment Red—5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 6
3:1 、 144、 146、 185、 101 3: 1, 144, 146, 185, 101
C. I. Pigment Violet— 19、 23  C. I. Pigment Violet— 19, 23
C. I. Pigment Blue— 15:1、 15:3、 15:4、 18、 60、 27、 29  C. I. Pigment Blue—15: 1, 15: 3, 15: 4, 18, 60, 27, 29
C. I. Pigment Green— 7、 36  C. I. Pigment Green— 7, 36
C. I. Pigment White— 6、 18、 21  C. I. Pigment White— 6, 18, 21
C. I. Pigment Black -7  C. I. Pigment Black -7
上記顔料の分散には、例えば、ボールミル、サンドミル、アトライター、ロー -ルミル、 アジテータ、ヘンシェルミキサ、コロイドミル、超音波ホモジナイザー、パールミル、湿 式ジェットミル、ペイントシェーカー等を用いることができる。また、顔料の分散を行う 際に分散剤を添加することも可能である。分散剤としては、高分子分散剤を用いるこ と力 子ましく、高分子分散剤としては Avecia社の Solsperseシリーズが挙げられる。 また分散助剤として、各種顔料に応じたシナージストを用いることも可能である。これ らの分散剤及び分散助剤は、顔料 100質量部に対し、 1質量部〜 50質量部添加す ることが好ましい。分散媒体は、溶剤または重合性ィ匕合物を用いて行うが、本発明に 用いるインク組成物では、インク着弾直後に反応 '硬化させるため、無溶剤であること が好ましい。溶剤が硬化画像に残ってしまうと、耐溶剤性の劣化、残留する溶剤の V OCの問題が生じる。よって、分散媒体は溶剤ではなく重合性化合物、その中でも最 も粘度の低 、モノマーを選択することが分散適性上好ま 、。 For the dispersion of the pigment, for example, 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. Also disperse the pigment It is also possible to add a dispersing agent. As the dispersing agent, it is encouraging to use a polymer dispersing agent, and as the polymer dispersing agent, there is Avecia's Solsperse series. Also, a synergist according to various pigments can be used as a dispersion aid. These 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.
[0196] 顔料の分散は顔料粒子の平均粒径を 0. 08 μ m〜0. 5 μ mとすることが好ましぐ 最大粒径は 0. 3 111〜10 111、好ましくは0. 3 /ζ πι〜3 /ζ πιとなるよう、顔料、分散 剤、分散媒体の選定、分散条件、ろ過条件を適宜設定する。この粒径管理によって 、ヘッドノズルの詰まりを抑制し、インクの保存安定性、インク透明性及び硬化の感度 を維持することができる。  [0196] For the dispersion of the pigment, it is preferable that the average particle size of the pigment particles is 0.08 μm to 0.5 μm. 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 ζπι-3 / ζπι. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.
[0197] 本発明のインク組成物においては、色材濃度として、インク全体の 1質量％〜10質 量％であることが好まし!/、。  [0197] In the ink composition of the present invention, the colorant concentration is preferably 1% by mass to 10% by mass of the whole ink! /.
[0198] 本発明においては、吐出安定性、保存性を向上させる目的で、熱塩基発生剤も用 いることがでさる。  [0198] In the present invention, a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.
[0199] 熱塩基発生剤としては、例えば、加熱により脱炭酸して分解する有機酸と塩基の塩 、分子内求核置換反応、ロッセン転位、ベックマン転位等の反応により分解してァミン 類を放出する化合物や、加熱により何らかの反応を起こして塩基を放出するものが好 ましく用いられる。具体的には、英国特許第 998, 949号明細書記載のトリクロ口酢酸 の塩、米国特許第 4, 060, 420号明細書に記載のアルファースルホ -ル酢酸の塩、 特開昭 59— 157637号公報に記載のプロピール酸類の塩、 2—カルボキシカルボキ サミド誘導体、特開昭 59— 168440号公報に記載の塩基成分に有機塩基の他にァ ルカリ金属、アルカリ土類金属を用いた熱分解性酸との塩、特開昭 59— 180537号 公報に記載のロッセン転位を利用したヒドロキサム力ルバメート類、加熱により-トリル を生成する特開昭 59— 195237号公報に記載のアルドキシム力ルバメート類等が挙 げられる。その他、英国特許第 998, 945号明細書、米国特許第 3, 220, 846号明 細書、英国特許第 279, 480号明細書の各明細書、特開昭 50— 22625号公報、同 61— 32844号公報、同 61— 51139号公報、同 61— 52638号公報、同 61— 5114 0号公報、同 61— 53634号公報〜同 61— 53640号公報、同 61— 55644号公報、 同 61— 55645号公報の各公報等に記載の熱塩基発生剤が有用である。 [0199] As 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. Specifically, 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. In addition, British Patent No. 998,945, U.S. Pat.No. 3,220,846, British Patent No.279,480, JP-A-50-22625, 61- 32844, 61-51139, 61-52638, 61-5114, 61-53634 to 61-53640, 61-55644, 61- The thermal base generator described in each publication of 55645 is useful.
[0200] 更に、具体的に例を挙げると、トリクロ口酢酸グァ-ジン、トリクロ口酢酸メチルダァ- ジン、トリクロ口酢酸カリウム、フエ-ルスルホ-ル酢酸グァ-ジン、 p クロ口フエ-ル スルホ-ル酢酸グァ-ジン、 p—メタンスルホ -ルフヱ-ルスルホ-ル酢酸グァ-ジン 、フエ-ルプロピオール酸カリウム、フエ-ルプロピオール酸グァ-ジン、フエ-ルプロ ピオール酸セシウム、 p クロ口フエ-ルプロピオール酸グァ-ジン、 p フエ-レン— ビス フエ-ルプロピオール酸グァ-ジン、フエ-ルスルホ-ル酢酸テトラメチルアン モ-ゥム、フエ-ルプロピオ一ル酸テトラメチルアンモ-ゥムがある。上記の熱塩基発 生剤は広い範囲で用いることができる。  [0200] Further, specific examples include chlorodiacetate guanidine, trichlorodiethyl acetate darzine, trichlorodiethyl acetate potassium, phenolsulfol acetate guanidine, p-cyclodiethylsulfol-sulfone. Guarazine acetate, p-methanesulfurylsulfol acetate guanidine acetate, potassium phenolpropiolate, guanidine phenolpropiolate, cesium phenolpropiolate, p-cyclopropanolate guanate Gin, p-phenol-bis-phenolpropiolic acid guanidine, phenolsulfonylacetate tetramethylammonium, and tetramethylammonium phenolpropiolate. The thermal base generator can be used in a wide range.
[0201] 本発明のインク組成物は、特開平 8— 248561号公報、同 9— 34106号公報の各 公報を始めとし、既に公知となっている活性光線の照射で発生した酸により新たに酸 を発生する酸増殖剤を含有することも可能である。  [0201] 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.
[0202] 本発明のインク組成物は、重合性組成物、顔料分散剤と共に、顔料をサンドミル等 の通常の分散機を用いてよく分散することにより製造される。予め、顔料高濃度の濃 縮液を調製しておき、重合性組成物で希釈することが好ましい。通常の分散機による 分散でも充分な分散が可能であり、このため、過剰な分散エネルギーが力からず、多 大な分散時間を必要としないため、インク成分の分散時の変質を招きにくぐ安定性 に優れたインクが調製される。インクは孔径 3 μ m以下、更には 1 μ m以下のフィルタ 一にて濾過することが好ましい。  [0202] 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 μm or less, more preferably 1 μm or less.
[0203] 本発明のインク組成物は、高周波数のヘッドにおいて、吐出の追随性の低下を防 止し、吐出の安定性を向上させるという観点から、 25°Cでの粘度が 5mPa ' sを超え、 40mPa ' s以下になるように調整することが好ましい。さらに、 25°Cでの粘度が 7mPa • s〜80mPa · sに調整することが好ましく、 7mPa · s〜40mPa · sに調整することがより 好ましい。 25°〇での粘度が7111?& ' 5〜40111?& ' 5のィンクは、特に通常の 4kHz〜： LO kHzの周波数を有するヘッドから、 10〜50KHzの高周波数のヘッドにお!、ても安定 した吐出特性を示す。 [0203] 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.
[0204] また、本発明のインク組成物は、ピエゾヘッドにおいては 10 μ SZcm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とすることが好ましい。また、コンテ ィ-ユ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. 5mSZcm以上の電導度に調整する必要がある。  [0204] In addition, the ink composition of the present invention preferably has an electric conductivity of 10 μSZcm or less in a piezo head and does not cause electrical corrosion inside the head. 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.
[0205] 本発明においては、インクの粘度や含水率を制御しながらインクの出射（吐出ともい う）、光照射や加熱等が行われ、また、様々な支持体に対して均一なドット径を得るこ とが求められる力 前記のような場合においても、安定した出射（吐出ともいう）が行わ れ、且つ、所望のドット径を得るという観点からは、インクの 25°Cにおける表面張力が 25mNZn！〜 40mNZmの範囲にあることが好まし!/、。  [0205] In the present invention, ink ejection (also referred to as ejection), light irradiation, heating, and the like are performed while controlling the viscosity and water content of the ink, and uniform dot diameters are provided for various supports. Force required to be obtained In the above case, 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!
[0206] 表面張力を調整するために、必要に応じて界面活性剤を含有させてもょ 、。本発 明のインク組成物に好ましく使用される界面活性剤としては、例えば、ジアルキルス ルホコハク酸塩類、アルキルナフタレンスルホン酸塩類、脂肪酸塩類等のァ-オン性 界面活性剤、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキル ァリルエーテル類、アセチレングリコール類、ポリオキシエチレン 'ポリオキシプロピレ ンブロックコポリマー類等のノ-オン性界面活性剤、アルキルアミン塩類、第 4級アン モ -ゥム塩類等のカチオン性界面活性剤、重合性基を有する界面活性ィ匕合物など が挙げられる。これらの中で、特にシリコーン変性アタリレート、フッ素変性アタリレート 、シリコーン変性エポキシ、フッ素変性エポキシ、シリコーン変性ォキセタン、フッ素変 性ォキセタンなど、不飽和結合やォキシラン、ォキセタン環など重合性基を有する界 面活性ィ匕合物が好ましい。  [0206] In order to adjust the surface tension, a surfactant may be added as necessary. Examples of 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. Among these, silicone-modified acrylate, fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, fluorine-modified oxetane, etc. Active compounds are preferred.
[0207] 本発明のインク組成物には、上記説明した以外に様々な添加剤を用いることができ る。例えば、レべリング添加剤、マット剤、膜物性を調整するためのポリエステル系榭 脂、ポリウレタン系榭脂、ビニル系榭脂、アクリル系榭脂、ゴム系榭脂、ワックス類を添 加することができる。記録媒体との密着性を改善するため、極微量の有機溶剤を添 加することも有効である。この場合、耐溶剤性や VOCの問題が起こらない範囲での 添加が有効であり、その使用量は 0. 1質量％〜5質量％の範囲であり、好ましくは 0 . 1質量％〜3質量％である。また、ラジカル重合性モノマーと開始剤を組み合わせ、 ラジカル'カチオンのハイブリッド型硬化インクとすることも可能である。 [0207] Various additives other than those described above can be used in the ink composition of the present invention. For example, leveling additives, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes to adjust film properties should be added. Can do. In order to improve the adhesion with the recording medium, it is also effective to add a trace amount of organic solvent. In this case, 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. It is also possible to combine a radical polymerizable monomer and an initiator into a radical cation hybrid curable ink.
[0208] 《画像形成方法》  [0208] <Image Forming Method>
本発明の画像形成方法について説明する。  The image forming method of the present invention will be described.
[0209] 本発明の画像形成方法においては、本発明のインク組成物をインクジェット記録方 式により記録材料上に吐出、描画し、次いで、紫外線等などの活性光線を照射する 力 または、加熱によりインク組成物（単にインクともいう）を硬化させる。  [0209] In the image forming method of the present invention, 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.
[0210] 本発明の画像形成方法においては、インク出射（吐出ともいう）時にはインクをイン クジェットノズルごと加温し、インク液を低粘度させることが好ましい。加熱温度として は 35°C〜100°C、好ましくは 35°C〜60°Cである。  [0210] In the image forming method of the present invention, it is preferable to warm the ink together with 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.
[0211] 本発明において、インクが着弾し、活性光線を照射して硬化した後の総インク膜厚  [0211] In the present invention, the total ink film thickness after the ink has landed and cured by irradiation with actinic rays
2 μ m〜20 μ mであることが好ましい。スクリーン印刷分野のインク組成物ジェット 記録では、総インク膜厚が 20 /z mを越えているのが現状である力 記録材料が薄い プラスチック材料であることが多 、軟包装印刷分野では、前述した記録材料のカー ル 'しわの問題でだけでなぐ印刷物全体のこし'質感が変わってしまうという問題が 有るため使えない。また本発明では、各ノズルより吐出する液滴量が 2〜15plである ことが好ましい。  It is preferable that it is 2 micrometers-20 micrometers. In the ink composition jet recording in the screen printing field, 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. In the present invention, the amount of liquid droplets discharged from each nozzle is preferably 2 to 15 pl.
[0212] 本発明にお ヽては、高精細な画像を形成するためには、照射タイミングができるだ け早い方が好ましいが、本発明においては、インクの粘度または含水率が好ましい状 態となるタイミングで光照射を開始することが好ましい。  [0212] In the present invention, in order to form a high-definition image, it is preferable that the irradiation timing is as early as possible. However, in the present invention, the viscosity or water content of the ink is preferable. It is preferable to start the light irradiation at the following timing.
[0213] 詳しくは発生光線の照射条件として、インク着弾後 0. 001秒〜 1. 0秒の間に活性 光線照射を開始することが好ましぐより好ましくは 0. 001秒〜 0. 4秒である。また 0. 1秒〜 3秒後、好ましくは 0. 2秒〜 1秒以内に、インクの流動性が失われる程度まで 光照射を行なった後、終了させることが好ましい。上記条件とすることにより、ドット径 の拡大やドット間の滲みを防止することができる。  [0213] Specifically, it is preferable to start irradiation with actinic rays between 0.001 seconds and 1.0 seconds after ink landing, more preferably 0.001 seconds to 0.4 seconds. It is. Further, it is preferable that the irradiation is terminated after 0.1 seconds to 3 seconds, preferably within 0.2 seconds to 1 second, until the ink fluidity is lost. By setting it as the above condition, it is possible to prevent the dot diameter from being enlarged and bleeding between dots.
[0214] 活性光線の照射方法として、その基本的な方法が特開昭 60— 132767号公報に 開示されている。これ〖こよると、記録ヘッドユニットの両側に光源を設け、シャトル方式 で記録ヘッドと光源を走査する。照射はインク着弾後、一定時間を置いて行われるこ とになる。更に駆動を伴わない別光源によって硬化を完了させる。米国特許第 6, 14 5, 979号明細書では、照射方法として、光ファイバ一を用いた方法や、コリメートされ た光源を記録ヘッドユニット側面に設けた鏡面に当て、記録部へ UV光を照射する方 法が開示されている。本発明の画像形成方法においては、これらのいずれの照射方 法も用 、ることができる。 [0214] 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. In US Pat. No. 6, 14 5, 979, as an irradiation method, 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.
[0215] また活性光線を照射を 2段階に分け、まずインク着弾後 0. 001秒〜 1. 0秒の間に 前述の方法で活性光線を照射し、且つ全印字終了後、更に活性光線を照射する方 法も好ましい態様の 1つである。活性光線の照射を 2段階に分けることで、よりインク 硬化の際に起こる記録材料の収縮を抑えることが可能となる。  [0215] In addition, irradiation with actinic rays is divided into two stages. First, 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.
[0216] 活性光線照射で用いる光源の例としては、水銀アークランプ、キセノンアークランプ 、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高圧水銀ランプ 、メタルハライドランプ、無電極 UVランプ、低圧水銀ランプ、 UVレーザー、キセノン フラッシュランプ、捕虫灯、ブラックライト、殺菌灯、冷陰極管、 LEDをなどがあるが、 これらに限定されないが、この中でも蛍光管が低エネルギー ·低コストであり、好まし い。光源波長としては 250nm〜370nm、好ましくには 270ηπ！〜 320nmに発光波 長のピークがある光源力 感度の点で好ましい。照度は lmWZcm2〜3000mWZc 好ましくは lmWZcm2〜200mWZcm2である。また電子線により硬化させる場 合には、通常 300eVの以下のエネルギーの電子線で硬化させる力 l〜5Mradの 照射量で瞬時に硬化させることも可能である。 [0216] 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 270ηπ! 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 . In addition, when curing with an electron beam, it is possible to cure instantaneously with an irradiation dose of 1 to 5 Mrad, which is usually cured with an electron beam with an energy of 300 eV or less.
[0217] 本発明のインク組成物を用いて、被記録媒体 (基材とも ヽぅ）への画像印字を行うが 、被記録媒体としては従来各種の用途で使用されて 、る広汎な合成樹脂を全て用い ることができ、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、アクリル榭脂、ポリカーボネート、ポリスチレン、アタリロニトリ ルーブタジエン 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 、。  [0217] The ink composition of the present invention is used to perform image printing on a recording medium (both of the base materials). As 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.
[0218] 本発明で用いることのできる基材としては、通常の非コート紙、コート紙などの他に 、非吸収性支持体を用いることができるが、その中でも基材として非吸収性支持体を 用いることが好ましい。 [0219] 本発明においては、非吸収性支持体としては各種非吸収性のプラスチック及びそ のフィルムを用いることができ、各種プラスチックフィルムとしては、例えば、 PETフィ ルム、 OPSフィルム、 OPPフィルム、 ONyフィルム、 PVCフィルム、 PEフィルム、 TA cフィルムを挙げることができる。その他のプラスチックとしては、ポリカーボネート、ァ クリル樹脂、 ABS、ポリアセタール、 PVA、ゴム類などが使用できる。また、金属類や ガラス類にも適用可能である。これらの記録材料の中でも、特に熱でシュリンク可能 な、 PETフィルム、 OPSフィルム、 OPPフィルム、 ONyフィルム、 PVCフィルムへ画像 を形成する場合に本発明の構成は有効となる。これらの基材はインクの硬化収縮、 硬化反応時の発熱などにより、フィルムのカール、変形が生じやすいば力りでなぐィ ンク膜が基材の収縮に追従し難 、。 [0218] As a base material that can be used in the present invention, 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. [0219] In the present invention, 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. Among these recording materials, 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.
[0220] これら、各種プラスチックフィルムの表面エネルギーは大きく異なり、記録材料によ つてインク着弾後のドット径が変わってしまうことが、従来力も問題となっていた。本発 明の構成では、表面エネルギーの低い OPPフィルム、 OPSフィルムや表面エネルギ 一の比較的大き 、PETまでを含む力 基材として濡れ指数力 S40mN/m〜60mN Zmであることが好まし!/、。  [0220] The surface energy of these various plastic films varies greatly, and the dot diameter after ink landing varies depending on the recording material. In the configuration of the present invention, it is preferable that 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! / ,.
[0221] 本発明において、包装の費用や生産コスト等の記録材料のコスト、プリントの作製 効率、各種のサイズのプリントに対応できる等の点で、長尺（ウェブ)な記録材料を使 用する方が有利である。  [0221] In the present invention, 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.
[0222] 《インクジェット記録装置》  [0222] <Inkjet recording apparatus>
次 ヽで、本発明のインクジェット記録装置にっ 、て説明する。  Next, the ink jet recording apparatus of the present invention will be described.
[0223] 以下、本発明のインクジェット記録装置について、図面を適宜参照しながら説明す る。なお、図面の記録装置はあくまでも本発明のインクジェット記録装置の一態様で あり、本発明のインクジェット記録装置はこの図面に限定されない。  [0223] The ink jet recording apparatus of the present invention will be described below with reference to the drawings as appropriate. Note that the recording apparatus in the drawings is merely one aspect of the inkjet recording apparatus of the present invention, and the inkjet recording apparatus of the present invention is not limited to this drawing.
[0224] 図 1は、本発明のインクジェット記録装置の要部の構成を示す正面図である。記録 装置 1は、ヘッドキャリッジ 2、記録ヘッド 3、照射手段 4、プラテン部 5等を備えて構成 される。この記録装置 1は、記録材料 Pの下にプラテン部 5が設置されている。プラテ ン部 5は、紫外線を吸収する機能を有しており、記録材料 Pを通過してきた余分な紫 外線を吸収する。その結果、高精細な画像を非常に安定に再現できる。 [0225] 記録材料 Pは、ガイド部材 6に案内され、搬送手段（図示せず)の作動により、図 1に おける手前から奥の方向に移動する。ヘッド走査手段（図示せず）は、ヘッドキヤリツ ジ 2を図 1における Y方向に往復移動させることにより、ヘッドキャリッジ 2に保持され た記録ヘッド 3の走査を行なう。 [0224] 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. In this recording apparatus 1, 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. [0225] 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.
[0226] ヘッドキャリッジ 2は記録材料 Pの上側に設置され、記録材料 P上の画像印刷に用 いる色の数に応じて後述する記録ヘッド 3を複数個、吐出口を下側に配置して収納 する。ヘッドキャリッジ 2は、図 1における Y方向に往復自在な形態で記録装置 1本体 に対して設置されており、ヘッド走査手段の駆動により、図 1における Y方向に往復 移動する。  [0226] 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. Store. 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.
[0227] なお、図 1ではヘッドキャリッジ 2がホワイト（W)、イェロー（Y)、マゼンタ（M)、シァ ン（C)、ブラック (K)、ホワイト（W)の記録ヘッド 3を収納するものとして描図を行なつ ているが、実施の際にはヘッドキャリッジ 2に収納される記録ヘッド 3の色数は適宜決 められるちのである。  In FIG. 1, the head carriage 2 houses the recording head 3 of white (W), yellow (Y), magenta (M), sheen (C), black (K), and white (W). However, at the time of implementation, the number of colors of the recording head 3 housed in the head carriage 2 is appropriately determined.
[0228] 記録ヘッド 3は、インク供給手段（図示せず）により供給されたインク組成物（例えば 、紫外線硬化インク)を、内部に複数個備えられた吐出手段（図示せず)の作動により 、吐出ロカも記録材料 Pに向けて吐出する。記録ヘッド 3により吐出される紫外線硬 ィ匕インクは色材、重合性モノマー、開始剤等を含んで組成されており、紫外線の照射 を受けることで開始剤が触媒として作用することに伴なうモノマーの架橋、重合反応 によって硬化する性質を有する。  [0228] 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.
[0229] 記録ヘッド 3は記録材料 Pの一端からヘッド走査手段の駆動により、図 1における Y 方向に記録材料 Pの他端まで移動するという走査の間に、記録材料 Pにおける一定 の領域 (着弾可能領域）に対して紫外線硬化インクをインク滴として吐出し、該着弾 可能領域にインク滴を着弾させる。  [0229] 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.
[0230] 上記走査を適宜回数行ない、 1領域の着弾可能領域に向けて紫外線硬化インクの 吐出を行なった後、搬送手段で記録材料 Pを図 1における手前から奥方向に適宜移 動させ、再びヘッド走査手段による走査を行ないながら、記録ヘッド 3により上記着弾 可能領域に対し、図 1における奥方向に隣接した次の着弾可能領域に対して紫外線 硬化インクの吐出を行なう。 [0231] 上述の操作を繰り返し、ヘッド走査手段及び搬送手段と連動して記録ヘッド 3から 紫外線硬化インクを吐出することにより、記録材料 P上に紫外線硬化インク滴の集合 体からなる画像が形成される。 [0230] After the above-mentioned scanning is performed as many times as necessary to discharge ultraviolet curable ink toward one landable area, 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
[0232] 照射手段 4は特定の波長領域の紫外線を安定した露光エネルギーで発光する紫 外線ランプ及び特定の波長の紫外線を透過するフィルターを備えて構成される。ここ で、紫外線ランプとしては、水銀ランプ、メタルノヽライドランプ、エキシマーレーザ、紫 外線レーザ、冷陰極管、ブラックライト、 LED (light emitting diode)等が適用可 能であり、帯状のメタルハライドランプ管、冷陰極管、水銀ランプ管もしくはブラックラ イトが好ま 、。特に波長 365nmの紫外線を発光する冷陰極管及びブラックライトが 滲み防止、ドット径制御を効率よく行なえ、且つ硬化の際の皺も低減でき好ましい。 ブラックライトを照射手段 4の放射線源に用いることで、紫外線硬化インクを硬化する ための照射手段 4を安価に作製することができる。  [0232] 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. Here, mercury lamps, metal nitride lamps, excimer lasers, ultraviolet lasers, cold cathode tubes, black lights, LEDs (light emitting diodes), etc. can be applied as ultraviolet lamps. Cold cathode tube, mercury lamp tube or black light is preferred. In particular, 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. By using 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.
[0233] 照射手段 4は、記録ヘッド 3がヘッド走査手段の駆動による 1回の走査によって紫外 線硬化インクを吐出する着弾可能領域のうち、記録装置 (紫外線硬化型インクジ ッ トプリンタ） 1で設定できる最大のものとほぼ同じ形状か、着弾可能領域よりも大きな形 状を有する。  [0233] 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.
[0234] 照射手段 4はヘッドキャリッジ 2の両脇に、記録材料 Pに対してほぼ平行に、固定し て設置される。  [0234] 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.
[0235] 前述したようにインク吐出部の照度を調整する手段としては、記録ヘッド 3全体を遮 光することはもちろんであるが、加えて照射手段 4と記録材料 Pの距離 hiより、記録 ヘッド 3のインク吐出部 31と記録材料 Pとの距離 h2を大きくしたり（hl <h2)、記録へ ッド 3と照射手段 4との距離 dを離したり（dを大きく）することが有効である。又、記録へ ッド 3と照射手段 4の間を蛇腹構造 7にすると更に好ましい。  [0235] As described above, as a means for adjusting the illuminance of the ink discharge portion, not only the entire recording head 3 is shielded, but in addition, 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.
[0236] ここで、照射手段 4で照射される紫外線の波長は、照射手段 4に備えられた紫外線 ランプ又はフィルターを交換することで適宜変更することができる。  Here, 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.
[0237] 図 2は、インクジェット記録装置の要部の構成の他の一例を示す図である。  FIG. 2 is a diagram showing another example of the configuration of the main part of the ink jet recording apparatus.
[0238] 図 2で示したインクジェット記録装置は、ラインヘッド方式と呼ばれており、ヘッドキヤ リッジ 2に、各色のインクジェット記録ヘッド 3を、記録材料 Pの全幅をカバーするように して、複数個、固定配置されている。ヘッドキャリッジ 2は遮光されている。 [0238] 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.
[0239] 一方、ヘッドキャリッジ 2の下流側には、同じく記録材料 Pの全幅をカバーするように して、インク印字面全域をカバーするように配置されて 、る照射手段 4が設けられて いる。照明手段 4に用いられる紫外線ランプは、図 1に記載したのと同様のものを用 いることがでさる。 [0239] On the other hand, on the downstream side of the head carriage 2, there is provided 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.
[0240] このラインヘッド方式では、ヘッドキャリッジ 2及び照射手段 4は固定され、記録材料 Pのみが、搬送されて、インク出射及び硬化を行って画像形成を行う。  [0240] In this line head system, 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.
実施例  Example
[0241] 以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されな い。  [0241] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[0242] 実施例 1  [0242] Example 1
《重合性組成物の作製》  << Preparation of polymerizable composition >>
重合性化合物、重合開始剤を表 1、表 2に示すように添加、塩化メチレン 50質量部 に溶解させて重合性組成物を調製した。  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.
[0243] 《重合性組成物の重合》 [0243] <Polymerization of polymerizable composition>
調製した重合性組成物に表 2に示すように活性光線または熱をカ卩えることによって 組成物を重合させた。  The prepared polymerizable composition was polymerized by applying actinic rays or heat as shown in Table 2.
[0244] 《活性光線の照射による重合》 [0244] << Polymerization by irradiation with actinic rays >>
重合性組成物を入れた容器上に設置した高圧水銀灯カゝら活性光線を 20分間照射 した。  Actinic rays were irradiated for 20 minutes from a high-pressure mercury lamp placed on a container containing the polymerizable composition.
[0245] 《加熱による重合》  [0245] << Polymerization by heating >>
重合性組成物を還流器を備えた容器に入れ、 20分間加熱還流した。  The polymerizable composition was placed in a container equipped with a refluxer and heated to reflux for 20 minutes.
[0246] 《重合性組成物の評価》 [0246] << Evaluation of Polymerizable Composition >>
《重合性の評価》  <Evaluation of polymerizability>
反応液力 ポリマーを濾取し、乾燥させた後に、得られたポリマーの質量を測定し て収率を算出し、それをもって重合性組成物の重合性を評価した。  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.
[0247] 《高湿条件での重合性の評価》 [0247] << Evaluation of Polymerizability under High Humidity Conditions >>
上記重合性組成物を湿度 80%の雰囲気下で重合させ、残留物を溶媒で洗 、流し 、乾燥させた後に、得られたポリマーの質量を測定して収率を算出し、それをもって 重合性組成物の高湿条件下での重合性を評価した。 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.
[0248] 《重合性の評価基準》  [0248] << Evaluation criteria for polymerizability >>
収率力 ¾0%を超えるものを A、 60%を超えて 80%以下のものを B、 40%を超えて 60%以下のものを C、 20%を超えて 40%以下のものを D、 20%以下のものを Eとし た。収率が高いほど重合性が高い。  Yield power ¾0% over A, over 60% over 80% B, over 40% over 60% C, over 20% over 40% D, E below 20%. The higher the yield, the higher the polymerizability.
[0249] 《重合性組成物の保存性の評価》 [0249] << Evaluation of Preservability of Polymerizable Composition >>
重合性組成物を 70°Cで 3日保存した後に、組成物を必要があれば振盪し目視によ つて組成物の着色及び増粘を下記のようにランク評価した。  After the polymerizable composition was stored at 70 ° C. for 3 days, the composition was shaken if necessary, and the coloration and thickening of the composition were visually evaluated as follows.
[0250] ◎:着色および増粘のないもの、 [0250] A: No coloring or thickening,
〇：着色および増粘が若干見られたもの、  ○: Some coloring and thickening were observed,
△：かなりの着色または増粘が見られたもの、  Δ: A considerable coloring or thickening was observed,
X：着色または増粘の程度が著しかったもの、  X: The degree of coloring or thickening was remarkable,
但し、重合性開始剤としてトリフルォロメタンスルホン酸を用いた試料 No. 101及び 比較試料 No. 101につ ヽては保存'性の評価は行わなかった。  However, the evaluation of storage ability was not performed for Sample No. 101 and Comparative Sample No. 101 using trifluoromethanesulfonic acid as a polymerizable initiator.
[0251] 重合性組成物の評価結果を表 1、表 2に示した。 [0251] Tables 1 and 2 show the evaluation results of the polymerizable compositions.
[0252] [表 1] [0252] [Table 1]
¾23025 ¾23025
Figure imgf000083_0001
Figure imgf000083_0001
重合開始剤 Polymerization initiator
高湿での  In high humidity
添加量 重合方法重合性 保存性 備考 種類 重合性  Amount added Polymerization method Polymerizability Storage stability Remarks Type Polymerizability
(質量部)  (Mass)
試料 No.101 ※丄 5.0 熱 D D 評価せず本発明 試料 o.102 WPI-113 5.0 C D Δ 本発明 試料 No .103 WPI-113 5.0 活性光線 C C Δ 本発明 試料 No.104 UV 1-6992 5.0 活性光線 C C 〇 本発明 試料 No.105 UV 1-6992 5.0 活性光線 B C 〇 本発明 試料 No.106 UV 1-6992 5.0 活性光線 B C ® 本発明 試料 No.107 UV 1-6992 5.0 活性光線 C C 〇 本発明 試料 No.108 UV 1-6992 5.0 活性光線 B C 〇 本発明 試料 No.109 UV 1—6992 5.0 活性光線 B B ◎ 本発明 試料 o.110 UV 1-6992 5.0 活性光線 B B ◎ 本発明 試料 No. Ill UV 1-6992 5.0 活性光線 B B ◎ 本発明 試料 No.112 UV 1-6992 5.0 活性光線 A B ◎ 本発明 試料 No.113 UV 1-6992 5.0 活性光線 A A 本発明 試料 No.114 UV 1-6992 5.0 活性光線 A A © 本発明 試料 No.115 UV 1-6992 5.0 活性光線 A A ◎ 本発明 試料 No.116 UV 1-6992 5.0 活性光線 A A ◎ 本発明 試料 No.117 UV 1-6992 5.0 活性光線 A A ◎ 本発明 試料 No.118 UV 1-6992 5.0 活性光線 A A ◎ 本発明 試料 No.119 UV 1-6992 5.0 活性光線 A A ® 本発明 試料 No.120 UV 1-6992 5.0 活性光線 A A ◎ 本発明 試料 No.121 UV 1-6992 5.0 活性光線 A A ◎ 本発明 比較試料 No.101 ※ 1 5.0 E E 評価せず比較例 比較試料 No.102 WPI— 113 5.0 熱 D E X 比較例 比較試料 No.103 UV 1-6992 5.0 活性光線 D D Δ 比較例 比較試料 No.104 WPI-113 5.0 熱 E E X 比較例 比較試料 No.105 UV 1-6992 5.0 活性光線 D D Δ 比較例 比較試料 No.106 UV 1-6992 5.0 活性光線 D D Δ 比較例 Sample No. 101 * 丄 5.0 Thermal DD Not evaluated Sample of the present invention o.102 WPI-113 5.0 CD Δ Present sample No. 103 WPI-113 5.0 Actinic ray CC Δ Present invention Sample No. 104 UV 1-6992 5.0 Activity Light CC ○ This invention Sample No.105 UV 1-6992 5.0 Actinic Ray BC ○ This invention Sample No.106 UV 1-6992 5.0 Actinic Ray BC ® This invention Sample No.107 UV 1-6992 5.0 Actinic Ray CC ○ This invention Sample No. 108 UV 1-6992 5.0 Actinic ray BC ○ The present invention Sample No. 109 UV 1-6992 5.0 Actinic ray BB ◎ Present invention sample o.110 UV 1-6992 5.0 Actinic ray BB ◎ Present invention Sample No. Ill UV 1-6992 5.0 Actinic ray BB ◎ Invention sample No.112 UV 1-6992 5.0 Actinic ray AB ◎ Invention sample No.113 UV 1-6992 5.0 Actinic ray AA Invention sample No.114 UV 1-6992 5.0 Actinic ray AA © Invention sample No. 115 UV 1-6992 5.0 Actinic ray AA ◎ Invention sample No. 116 UV 1-6992 5.0 Actinic ray AA ◎ Invention sample No. 117 UV 1-6992 5.0 Actinic ray AA ◎ Invention sample No.118 UV 1-6992 5.0 Actinic ray AA ◎ Invention sample No.119 UV 1-6992 5.0 Actinic ray AA ® Invention sample No.120 UV 1-6992 5.0 Actinic ray AA ◎ Invention sample No.121 UV 1-6992 5.0 Actinic ray AA ◎ Comparative sample No. 101 * 1 5.0 EE Not evaluated Comparative example Comparative sample No. 102 WPI— 113 5.0 Thermal DEX comparative example Comparative sample No. 103 UV 1-6992 5.0 Actinic ray DD Δ Comparative example Comparative sample No. 104 WPI-113 5.0 Thermal EEX Comparative Example Comparative Sample No. 105 UV 1-6992 5.0 Actinic Ray DD Δ Comparative Example Comparative Sample No. 106 UV 1-6992 5.0 Actinic Ray DD Δ Comparative Example
※丄 ： トリフルォロメタンスルホン酸 * 丄: Trifluoromethanesulfonic acid
[0254] 使用した化合物を以下に示す。 [0254] The compounds used are shown below.
[0255] 〈エポキシ化合物〉 [0255] <Epoxy compound>
ミアセンジオキサイド：セロキサイド 3000：ダイセル化学工業社製ターピノレンジォ キサイド： ATOFINA社製  Miasendioxide: Celoxide 3000: Daicel Chemical Industries' Tarpinorenioxide: ATOFINA
〈ォキセタン化合物〉  <Oxetane compound>
ΟΧΤ— 221：東亞合成社製 ΟΧΤ— 212：東亞合成社製 〈重合開始剤〉 ΟΧΤ—221: Toagosei Co., Ltd. ΟΧΤ—212: Toagosei Co., Ltd. <Polymerization initiator>
UVI 6992：ダウ'ケミカル社製 プロピオンカーボネート溶液  UVI 6992: Dow Chemical Propion carbonate solution
WPI-113 ：和光純薬社製 プロピオンカーボネート溶液  WPI-113: Propion carbonate solution manufactured by Wako Pure Chemical Industries
使用した、本発明に係る一般式 (X)で表される化合物の分子量は以下の通り、 X- 1:252.35、X— 3:338.48、X— 5:282.42  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
X— 21:226.31、 X— 28:240.30、 X— 38:324.50  X—21: 226.31, X—28: 240.30, X—38: 324.50
X— 55:480.63、 X— 63:410.59、 X— 64:266.38  X—55: 480.63, X—63: 410.59, X—64: 266.38
X— 65:268.39、 X— 72:394.59、 X— 74:380.52  X—65: 268.39, X—72: 394.59, X—74: 380.52
X— 75:622.37。  X—75: 622.37.
[0256] 実施例 2 [0256] Example 2
《重合性組成物の調製》  << Preparation of polymerizable composition >>
重合性化合物、酸発生剤、塩基性化合物を表 3、表 4に示すように溶解し重合性組 成物を調製した。  A polymerizable compound, an acid generator and a basic compound were dissolved as shown in Tables 3 and 4 to prepare a polymerizable composition.
[0257] [表 3] [0257] [Table 3]
Figure imgf000086_0001
Figure imgf000086_0001
Figure imgf000086_0002
Figure imgf000086_0002
酸発生剤 塩基性化合物 Acid generator Basic compound
添加量 添加量 種類 種類  Addition amount Addition amount Type Type
(質量部） (質量部） 試料 No.201 UVI-6992 5 塩基性化合物 A 0.5 試料 No.202 PI— 1 5 塩基性化合物 A 0.5 試料 No.203 PI— 1 5 塩基性化合物 A 0.5 試料 No.204 PI— 1 5 塩基性化合物 B 0.5 試料 No.205 PI— 1 5 塩基性化合物 A 0.5 試料 NQ.206 PI—oo t t 1 5 塩基性化合物 A 0.5 試料 No.207 PI— 1 cn 5 塩基性化合物 A 0.5 試料 No.208 PI— 1 5 塩基性化合物 A 0.5 試料 No.209 PJ-1 5 塩基性化合物 A 0.5 試料 o.210 PI— 1 5 塩基性化合物 A 0.5 試料 No. 11 PI— 1 5 塩基性化合物 A 0.5 試料 No.212 PI— 1 5 塩基性化合物 A 0.5 試料 No.213 PI— 1 5 塩基性化合物 A 0.5 試料 No.214 PI-1 5 塩基性化合物 A 0.5 試料 No.215 PI— 1 5 塩基性化合物 A 0.5 試料 No.216 PI-1 5 塩基性化合物 A 0.5 比較試料 No.201 5 塩基性化合物 A 0.5 比較試料 No.202 UVI-6992 5 塩基性化合物 A 0.5 比較試料 No.203 5 塩基性化合物 A 0.5 比較試料 No.204 UVI-6992 5 塩基性化合物 A 0.5 比較試料 No.205 UVI-6992 5 塩基性化合物 A 0.5 比較試料 No.206 UVI-6992 5 塩基性化合物 A 0.5 比較試料 No.207 UVI-6992 5 塩基性化合物 A 0.5  (Parts by mass) (parts by mass) Sample No.201 UVI-6992 5 Basic compound A 0.5 Sample No.202 PI—1 5 Basic compound A 0.5 Sample No.203 PI—1 5 Basic compound A 0.5 Sample No. 204 PI— 1 5 Basic compound B 0.5 Sample No. 205 PI— 1 5 Basic compound A 0.5 Sample NQ.206 PI—oo tt 1 5 Basic compound A 0.5 Sample No. 207 PI— 1 cn 5 Basic compound A 0.5 Sample No.208 PI—1 5 Basic Compound A 0.5 Sample No.209 PJ-1 5 Basic Compound A 0.5 Sample o.210 PI—1 5 Basic Compound A 0.5 Sample No. 11 PI—1 5 Base Basic Compound A 0.5 Sample No.212 PI—1 5 Basic Compound A 0.5 Sample No.213 PI—1 5 Basic Compound A 0.5 Sample No.214 PI-1 5 Basic Compound A 0.5 Sample No.215 PI— 1 5 Basic Compound A 0.5 Sample No.216 PI-1 5 Basic Compound A 0.5 Comparative Sample No.201 5 Basic Compound A0.5 Comparative Sample No.202 UVI-6992 5 Basic Compound A0.5 Comparative Sample No.203 5 Basic compound A 0.5 Comparative sample No.204 UVI-6992 5 bases Compound A 0.5 Comparative Sample No.205 UVI-6992 5 basic compound A 0.5 Comparative Sample No.206 UVI-6992 5 basic compound A 0.5 Comparative Sample No.207 UVI-6992 5 basic compound A 0.5
[0259] 使用した化合物を以下に示す。 [0259] The compounds used are shown below.
[0260] 〔塩基性化合物〕  [Basic compounds]
塩基性化合物 A： N—ェチルジェタノールァミン  Basic Compound A: N-Ethyljetanolamine
塩基性ィ匕合物 B:トリイソプロパノールァミン  Basic compound B: Triisopropanolamine
[0261] [化 61] PI-1 [0261] [Chemical 61] PI-1
Figure imgf000088_0001
ェポリ一ド GT403(ダイセル化学工業社製）
Figure imgf000088_0002
Figure imgf000088_0001
Epolyide GT403 (manufactured by Daicel Chemical Industries)
Figure imgf000088_0002
R: t—ブチル又は tーァミル  R: t-butyl or tamyl
n: 12〜18  n: 12-18
分子量 1050以上 (混合物）  Molecular weight 1050 or more (mixture)
[0262] 《硬化膜の作製》 [0262] << Production of cured film >>
重合性組成物を合成紙 (ュポコーポレーション社製合成紙 ュポ FGS)に膜厚が 3 μ mになるように塗布した後、 800miZcm2の紫外線をメタルノヽライドランプにより一 秒以内で照射し、硬化膜を得た。 After applying the polymerizable composition to synthetic paper (Synthetic paper YUPO FGS manufactured by YUPO Corporation) to a film thickness of 3 μm, UV irradiation of 800miZcm 2 was irradiated within 1 second with a metal nitride lamp. A cured film was obtained.
[0263] 《硬化膜の評価》 [0263] << Evaluation of cured film >>
得られた硬化膜の物理的特性を下記に示す試験で評価した。 （1)鉛筆引つ力ゝき試 験  The physical properties of the obtained cured film were evaluated by the following tests. (1) Pencil pulling test
JIS K 5400に従って、各硬化膜の硬度を測定した。  The hardness of each cured film was measured according to JIS K 5400.
[0264] 硬度のランクは（軟） 6B〜B、 HB、 F、 H〜9H (硬）の順に 6Bが最も柔らかぐ 9H が最も硬い。 （2)基盤目テープ剥離残留付着率試験 [0264] The hardness rank is (soft) 6B to B, HB, F, H to 9H (hard), 6B is the softest, and 9H is the hardest. (2) Base tape peeling residual adhesion rate test
JIS K 5400の碁盤目試験で得た硬化組成物試料に粘着テ―プ (スコッチ # 250 、住友スリーェム製)を張り合わせて 2kgのローラーで 1往復圧着した後、一気に剥が し、残留している碁盤目状の試料の数を調査した。（3)柔軟性の評価  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. (3) Flexibility evaluation
得られた硬化膜を JIS K 5600に規定されている耐屈曲性評価の方法にのっとり 評価した。  The obtained cured film was evaluated according to the method for evaluating bending resistance defined in JIS K 5600.
[0265] 《重合性組成物の粘度の評価》 調製した各重合性組成物の粘度を、レオメータ MCR300 (Physica製)を用い、温 度 25°C、 Shear Rate = 1000 (lZs)の条件下で測定し、下記のようにランク評価 を行った。 [0265] <Evaluation of viscosity of polymerizable composition> The viscosity of each prepared polymerizable composition was measured using a rheometer MCR300 (manufactured by Physica) under conditions of a temperature of 25 ° C. and a Shear Rate = 1000 (lZs), and rank evaluation was performed as follows.
[0266] ® : 25°Cにおける粘度が 150mPa · s以下の組成物、  [0266] ®: a composition having a viscosity at 25 ° C of 150 mPa · s or less,
〇：150mPa' s〜300mPa ' sの組成物、  A: 150 mPa's to 300 mPa's composition,
△： 300mPa， s〜500mPa · sの組成物、  Δ: 300 mPa, s to 500 mPa · s composition,
X : 500mPa' s以上の組成物、  X: a composition of 500 mPa's or more,
《硬化膜保存性の評価》  << Evaluation of cured film storage stability >>
得られた硬化組成物を、 85°C90%RHの高温高湿環境下で 1ヶ月保存した後の、 硬化組成物の鉛筆引つ力き試験および柔軟性の評価を上述したのと同様の試験し、 下記のようにランク評価した。  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.
[0267] ◎:試験結果に大きな変化の無いもの、 [0267] ◎: There is no significant change in test results,
〇：多少の劣化が見られるが実用上問題のないもの、  ○: Some deterioration is observed but there is no problem in practical use.
△:劣化が見られるもの  Δ: Deteriorated
X：大きく劣化が見られたものを X、  X: X, which shows significant deterioration
尚、◎および〇が実用上問題の無いレベルである。  Note that ◎ and 〇 are practically no problem levels.
[0268] 《硬化膜の温度変化への耐久性の評価》 [0268] << Evaluation of Durability to Temperature Change of Cured Film >>
《耐久性試験 (密着性)》  《Durability test (adhesion)》
得られた硬化膜を 85°Cで 30分保存し 40°Cで 30分保存した後に、硬化膜表面を 擦過し硬化膜が剥がれおちるかどうかを試験して温度変化への耐久性 (密着性)を 下記のようにランク評価した。  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.
[0269] 硬化膜が剥がれ落ちる力、ある!/、は剥がれ落ちな!/、まま 10サイクルに到達するま で繰り返した時に、 [0269] The force to peel off the cured film, there is! /, Does not peel off! /, And when repeated until reaching 10 cycles,
X：剥がれ落ちた時のサイクルの回数が 3以下のもの、  X: The number of cycles when peeling off is 3 or less,
△ :4以上 6以下のもの、  △: 4 or more and 6 or less,
〇： 7以上 10以下のもの、  ○: 7 to 10
剥がれ落ちないもの、  Things that won't come off
尚、実用上問題無いのは◎及び〇である。 [0270] 《耐久性試験 (耐屈曲性)》 Note that ◎ and ◯ have no practical problem. [0270] 《Durability test (flexibility)》
得られた硬化膜を 85°Cで 30分保存し、— 40°Cで 30分保存した後に、硬化膜を屈 曲させ硬化膜にヒビが入るかどうかを試験して温度変化への耐久性 (耐屈曲性)の評 価とした。硬化膜にヒビが入る力、あるいはヒビが入らないまま 10サイクルに到達する まで繰り返し、下記のようにランク評価した。  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.
[0271] X：ヒビが入った時のサイクルの回数が 3以下のもの、 [0271] X: No more than 3 cycles when cracked
△ :4以上 6以下のもの、  △: 4 or more and 6 or less,
〇： 7以上 10以下のもの、  ○: 7 to 10
◎：ヒビが入らな 、ものを◎、  ◎: Don't crack, ◎,
尚、実用上問題無いのは◎及び〇である。  Note that ◎ and ◯ have no practical problem.
[0272] 得られた結果は表 5に示す。 [0272] The results obtained are shown in Table 5.
[0273] [表 5] [0273] [Table 5]
Figure imgf000091_0001
表 5より、本発明の試料は、密着性及び硬度が十分であり、硬化膜 i ：長期間保存 後においても硬さと柔軟性を保持し、劣化が殆ど無ぐまた温度変化 、の耐久性にも 優れていることが判る。 [0275] 実施例 3
Figure imgf000091_0001
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
《インク組成物》  <Ink composition>
分散剤 (PB822 味の素ファインテクノネ土製)を 5質量部と、表 6、表 7に記載の各光 重合性ィ匕合物をステンレスビーカーに入れ、 65°Cのホットプレート上で加熱しながら 1時間かけて撹拌、混合して溶解させた。次いで、この溶液に各種顔料を 3質量部添 加した後、直径 lmmのジルコ-ァビーズ 200gと共にポリ瓶に入れ密栓し、ペイント シェーカーにて 2時間分散処理を行った。次いで、ジルコユアビーズを取り除き、各 光重合開始剤、塩基性化合物、界面活性剤等の各種添加剤を表 6、表 7に記載の組 み合わせで添カ卩し、これをプリンター目詰まり防止のため 0. 8 μ mメンブランフィルタ 一で濾過して、インク組成物セットを調製した。  Place 5 parts by weight of a dispersant (PB822 Ajinomoto Fine Technone Earth) and each photopolymerizable compound listed in Table 6 and Table 7 in a stainless steel beaker and heat them on a 65 ° C hot plate 1 Stir over time and mix to dissolve. Next, after adding 3 parts by mass of various pigments to this solution, it was sealed in a plastic bottle together with 200 g of zirconia beads having a diameter of 1 mm, and dispersed for 2 hours in a paint shaker. Next, remove the zircoyour beads and add various additives such as photopolymerization initiators, basic compounds, and surfactants in the combinations shown in Tables 6 and 7 to prevent printer clogging. Therefore, an ink composition set was prepared by filtration through a 0.8 μm membrane filter.
[0276] 使用した顔料は下記の通り [0276] The following pigments were used:
K:CI pigment Black 7  K: CI pigment Black 7
C:CI pigment Blue 15:3  C: CI pigment Blue 15: 3
M:CI pigment Red 57:1  M: CI pigment Red 57: 1
Y:CI pigment Yellow 13  Y: CI pigment Yellow 13
W:酸化チタン（アナターゼ型:粒径 0. 2μηι)  W: Titanium oxide (anatase type: particle size 0.2μηι)
Lk:CI pigment Black 7  Lk: CI pigment Black 7
Lc:CI pigment Blue 15:3  Lc: CI pigment Blue 15: 3
Lm:CI pigment Red 57: 1  Lm: CI pigment Red 57: 1
Ly :CI pigment Yellow 13  Ly: CI pigment Yellow 13
使用した化合物は以下の通り。  The compounds used are as follows.
[0277] F178k:メガファックス F178k [0277] F178k: Megafax F178k
パーフルォロアルキル基含有アクリルオリゴマー（大日本インキ化学工業社製） Perfluoroalkyl group-containing acrylic oligomer (Dainippon Ink and Chemicals)
F1405：メガファックス F1405 F1405: Megafax F1405
パーフルォロアルキル基含有エチレンオキサイド付加物（大日本インキ化学工業社 製）  Perfluoroalkyl group-containing ethylene oxide adduct (manufactured by Dainippon Ink & Chemicals, Inc.)
R100:ハリタック R100 (ロジン変性マレイン酸榭脂 播磨化学社製）  R100: Halitac R100 (Rosin-modified maleic acid rosin Harima Chemical Co., Ltd.)
145P:ハリタック 145P (ロジン変性マレイン酸榭脂 播磨化学社製） ¾027 145P: Halitak 145P (Rosin-modified maleic acid resin, Harima Chemical Co., Ltd.) ¾027
Figure imgf000093_0001
Figure imgf000093_0001
1：セロキサイ ド 3000 ミアセンジォキサイ ド  1: Seroxide 3000 Miasenzoxide
sffi0278 塩基性化合物 界面活性剤 相溶化剤 酸発生剤 添加量 添加量 添加量 sffi0278 Basic compound Surfactant Compatibilizer Acid generator Amount added Amount added Amount added
0.5質量部 0.5質量部 0.5質量部 添加量  0.5 parts by mass 0.5 parts by mass 0.5 parts by mass
種類 種類 種類 種類  Type Type Type Type
(質量部）  (Parts by mass)
試料 No.401 UV 1-6992 5 塩基性化合物 A F1405 145P 試料 No.402 P1-1 5 塩基性化合物 A F1405 145P 試料 No.403 PI-1 5 塩基性化合物 A F1405 145P 試料 No.404 PI-1 5 塩基性化合物 B F1405 145P 試料 No.405 PI-1 5 塩基性化合物 A F1405 145P 試料 No.406 PI-1 5 塩基性化合物 B F1405 145P 試料 No.407 PI-1 5 塩基性化合物 A F1405 145P 試料 No.408 PI-1 5 塩基性化合物 A F178k R100 試料 No.409 PI-1 5 塩基性化合物 A F178k 100 試料 No.410 PI-1 5 塩基性化合物 A F178k R100 試料 o.411 PI-1 5 塩基性化合物 A F178k R100 試料 o.412 PI-1 5 塩基性化合物 A F178k R100 試料 No.413 PI-1 5 塩基性化合物 A F178k 100 試料 No.414 PI-1 5 塩基性化合物 A F178k R100 試料 No.415 PI-1 5 塩基性化合物 A F178k 100 試料 No.416 PI-1 5 塩基性化合物 A F178k R100 比較試料 NQ.401 UV 1-6992 5 塩基性化合物 A F178k R100 比較試料 No.402 UV 1-6992 5 塩基性化合物 A F178k 8100 比較試料 NQ.403 UV 1-6992 5 塩基性化合物 A F178k R100 比較試料 No.404 UV 1-6992 5 塩基性化合物 A F178k R100 比較試料 No.405 UV 1-6992 5 塩基性化合物 A F178k 100 比較試料 No.406 U J-6992 5 塩基性化合物 A F178k 100 比較試料 NQ.407 UV 1—6992 5 塩基性化合物 A F178k 100  Sample No.401 UV 1-6992 5 Basic compound A F1405 145P Sample No.402 P1-1 5 Basic compound A F1405 145P Sample No.403 PI-1 5 Basic compound A F1405 145P Sample No.404 PI-1 5 Basic Compound B F1405 145P Sample No.405 PI-1 5 Basic Compound A F1405 145P Sample No.406 PI-1 5 Basic Compound B F1405 145P Sample No.407 PI-1 5 Basic Compound A F1405 145P Sample No.408 PI-1 5 Basic Compound A F178k R100 Sample No.409 PI-1 5 Basic Compound A F178k 100 Sample No.410 PI-1 5 Basic Compound A F178k R100 Sample o.411 PI-1 5 Base Compound A F178k R100 Sample o.412 PI-1 5 Basic Compound A F178k R100 Sample No.413 PI-1 5 Basic Compound A F178k 100 Sample No.414 PI-1 5 Basic Compound A F178k R100 Sample No. 415 PI-1 5 Basic compound A F178k 100 Sample No.416 PI-1 5 Basic compound A F178k R100 Comparative sample NQ.401 UV 1-6992 5 Basic compound A F178k R100 Comparative sample No.402 UV 1-6992 5 Basic compound A F178k 8100 Comparative sample NQ.403 UV 1 -6992 5 Basic compound A F178k R100 Comparative sample No. 404 UV 1-6992 5 Basic compound A F178k R100 Comparative sample No. 405 UV 1-6992 5 Basic compound A F178k 100 Comparative sample No. 406 U J-6992 5 Basic compound A F178k 100 Comparative sample NQ.407 UV 1—6992 5 Basic compound A F178k 100
《インクジェット画像形成方法》 << Inkjet image forming method >>
ピエゾ型インクジェットノズルを備えた図； Lに記載の構成力もなるインクジェット記録 装置に、上記調製した各インク組成物を装填し、巾 600mm、長さ 20mの長尺の各 記録材料へ、下記の画像記録を連続して行った。インク供給系は、インクタンク、供 給パイプ、ヘッド直前の前室インクタンク、フィルター付き配管、ピエゾヘッド力 なり、 前室タンク力もヘッド部分まで断熱して 50°Cの加温を行った。なお、各硬化糸且成物ィ ンクの粘度にあわせてヘッド部をカ卩温し、 2pl〜 15plの液滴量のマルチサイズドットを 720 X 720dpi (dpiとは 1インチ、即ち 2.54cm当たりのドット数を表す）の解像度で 吐出できるよう駆動して、上記記載のインク組成物を連続吐出した。また、記録材料 は面ヒーターにより 50°Cに加温した。着弾した後、キャリッジ両脇の照射光源 A：高圧 水銀ランプ VZero085 (INTEGRATION TECHNOLOGY社製）または、照射光 源 B :メタルハライドランプ（日本電池社製 MAL400NL 電力 = 3kW'hr 120W /cm)により瞬時 (着弾後 0. 4秒未満）に硬化させた。画像記録後に、総インク膜厚 を測定したところ、 2. 3 m〜 13 mの範囲であった。なお、インクジェット画像の形 成は、上記方法に従って、 27°C、 85%RHと 25°C、 25%RHの環境下で印字を行つ た。 Figure with a piezo-type inkjet nozzle; the ink composition prepared above is loaded into the inkjet recording apparatus having the constitutional power described in L, and the following images are applied to each recording material having a width of 600 mm and a length of 20 m. Recording was performed continuously. 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. After landing, 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). When the total ink film thickness was measured after image recording, it was in the range of 2.3 m to 13 m. In addition, according to the above method, the ink-jet image was printed in an environment of 27 ° C, 85% RH, 25 ° C, and 25% RH.
[0281] なお、各照射光源の照度は、岩崎電機社製の UVPF— A1を用いて、 254nmの積 算照度を測定した。  [0281] For the illuminance of each irradiation light source, the integrated illuminance at 254 nm was measured using UVPF-A1 manufactured by Iwasaki Electric Co., Ltd.
[0282] また、記載した各記録材料の略称の詳細は、以下の通りである。 [0282] Details of the abbreviations of the respective recording materials described are as follows.
[0283] 合成紙：ュポコーポレーション社製合成紙 ュポ FGS [0283] Synthetic paper: Synthetic paper made by YUPO Corporation YUPO FGS
PVC： polyvinyl chloride  PVC: polyvinyl chloride
《インク粘度の評価》  <Evaluation of ink viscosity>
調製した各インクの粘度を、レオメータ MCR300 (Physica製）を用い、温度 25°C、 Shear Rate = 1000 (lZs)の条件下で測定し、下記のようにランク評価した。  The viscosity of each prepared ink was measured using a rheometer MCR300 (manufactured by Physica) under the conditions of a temperature of 25 ° C. and a Shear Rate = 1000 (lZs), and rank evaluation was performed as follows.
[0284] ® : 25°Cにおける粘度が 7mPa · s〜40mPa · sの範囲内のインク、 [0284] ®: Ink having a viscosity in the range of 7 mPa · s to 40 mPa · s at 25 ° C,
〇：40mPa' sを超え、 80mPa' s未満のインク  ○: Ink of over 40mPa's and less than 80mPa's
X : 80mPa' s以上のインク、  X: ink of 80mPa's or more,
《インク射出性の評価》  <Evaluation of ink ejection properties>
連続でインクを 30分間吐出させた後、インク欠の状況を目視にて下記のようなラン ク評価を行った。  After discharging the ink continuously for 30 minutes, the following ink evaluation was performed to visually check the situation of ink shortage.
[0285] ◎:欠がなぐ良好なレベル、 [0285] ◎: Good level without lack,
〇：欠がわずかにあるが、問題の無いレベル、  〇: There is a shortage, but there is no problem,
△:欠があり、画質に影響を与えるレベル、  △: There is a lack, level that affects the image quality,
X：欠が多発し、許容できないレベル、  X: Unacceptable level due to frequent absences
尚、◎および〇が、実用上問題の無いレベルである、  In addition, ◎ and ○ are levels that have no practical problem.
《インクジェット記録画像の評価》  <Evaluation of inkjet recording image>
上記画像形成方法で記録した各画像につ!ヽて、下記の各評価を行った。 目標濃度で 6ポイント MS明朝体文字を印字し、文字のガサツキをルーペで拡大評 価し、下記の基準に則り文字品質の評価を行った。 Each image recorded by the above image forming method was subjected to the following evaluations. A 6-point MS Mincho font was printed at the target density, and the character roughness was magnified with a loupe, and the character quality was evaluated according to the following criteria.
[0286] ◎:ガサツキなし [0286] ◎: No roughness
〇：僅かにガサツキが見える  ◯: Slightly rough
△:ガサツキが見えるが、文字として判別でき、ギリギリ使えるレベル  △: Visible but can be distinguished as characters and can be used at the last minute
X：ガサツキがひどぐ文字がかすれていて使えないレベル  X: Level that can not be used due to severely blurred characters
◎および〇が、実用上問題の無いレベルである。  ◎ and ◯ are levels that have no practical problem.
[0287] 《色混じり (滲み、皺)》 [0287] 《Color mixing (bleeding, wrinkle)》
720dpiで、 Y、 M、 C、 K各色 1ドットが隣り合うように印字し、隣り合う各色ドットをル 一べで拡大し、滲み及び皺の具合を目視観察し、下記の基準に則り色混じりの評価 を行った。  At 720dpi, 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.
[0288] ◎:隣り合うドット形状が真円を保ち、滲みがない  [0288] ◎: Adjacent dot shape keeps perfect circle and no blur
〇：隣り合うドット形状はほぼ真円を保ち、ほとんど滲みがない  ◯: Adjacent dot shape keeps almost perfect circle and almost no bleeding
△：隣り合うドットが少し滲んでいてドット形状が少しくずれている力 ギリギリ使えレ ベノレ  △: Adjacent dots are slightly blurred and the dot shape is slightly broken.
X：隣り合うドットが滲んで混じりあっており、また、重なり部に皺の発生があり、使え な 、レべノレ  X: Adjacent dots are blurred and mixed, and there are wrinkles in the overlapping area.
尚、◎および〇が、実用上問題の無いレベルである。  In addition, (double-circle) and (circle) are the levels which do not have a problem practically.
[0289] 《硬化膜硬度、硬化膜の耐屈曲性の評価》 [0289] << Evaluation of Cured Film Hardness and Flexibility of Cured Film >>
マゼンタ顔料を分散したマゼンタインクを用い上記のインクジェット画像形成方法に よって印刷して作製した硬化膜の物理的特性を下記に示す試験で評価した。（1)鉛 筆引つかき試験: JIS Κ 5400に従って、各硬化膜の硬度を測定した。硬度のランク は（軟） 6B〜B、 HB、 F、 H〜9H (硬）の順に 6Bが最も柔らかぐ 9Hが最も硬い。（2 )柔軟性の評価:インクを PVCに膜厚が 3 μ mになるように射出塗布した後、 800mi Zcm2の紫外線をメタルハライドランプにより 1秒以内で照射し、硬化膜を得た。得ら れた硬化膜を JIS K 5600 の耐屈曲性評価の方法にのっとり評価した。 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. (1) 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. (2) Evaluation of flexibility: After ink was applied by injection onto PVC so that the film thickness was 3 μm, 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.
[0290] 《インク保存性の評価》 [0290] <Evaluation of ink storage stability>
調製したインクを密栓容器に入れ、暗所にて室温 1ヶ月間保存した後、上記の画像 形成方法によりインクジェット画像を形成し、下記のように保存安定性をランク評価し た。 Put the prepared ink in a sealed container and store it in the dark at room temperature for 1 month. An inkjet image was formed by the forming method, and the storage stability was ranked as follows.
[0291] 〇： 1ヶ月保存後も試験結果に大きな変動が無 、もの、  [0291] 〇: No significant change in test results after 1 month storage
△： V、ずれかの試験にお!、て一つ以上の項目で大きな変動が見られたもの、 X：インク粘度が増加し，画像形成ができな力つたもの、  △: V, deviation test! Great change in one or more items. X: Increased ink viscosity and force of image formation.
尚、〇が実用上問題の無い保存安定性である。  In addition, (circle) is the storage stability without a problem practically.
[0292] ここで、『 、ずれかの試験』とは、インク粘度、インク射出性、インクジェット記録画像 の評価、色混じり、硬化膜硬度、硬化膜の耐屈曲性評価から選択されるいずれか一 つの試験を示す。 [0292] Here, the "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.
[0293] 《硬化膜保存性の評価》 [0293] << Evaluation of cured film storage stability >>
得られたインク硬化組成物を、 85°C90%RHの高温高湿環境下で 1ヶ月保存した 後の、硬化組成物の鉛筆引つ力き試験および柔軟性の評価を上述したのと同様の 試験にて評価した。  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.
[0294] ◎:試験結果に大きな変化の無いもの、 [0294] ◎: There is no significant change in test results,
〇：多少の劣化が見られるが実用上問題のないもの、  ○: Some deterioration is observed but there is no problem in practical use.
△:劣化が見られるもの、  Δ: Deteriorated
X：大きく劣化が見られたもの  X: Deteriorated greatly
尚、◎および〇が実用上問題の無いレベルである。  Note that ◎ and 〇 are practically no problem levels.
[0295] 《硬化膜の温度変化への耐久性の評価》 [0295] <Evaluation of durability of cured film against temperature change>
《耐久性試験 (密着性)》  《Durability test (adhesion)》
得られたインク硬化膜を 85°Cで 30分保存し— 40°Cで 30分保存した後に、硬化膜 表面を擦過し硬化膜が剥がれおちるかどうかを試験して温度変化への耐久性 (密着 性)の評価とした。これを硬化膜が剥がれ落ちるか、あるいは剥がれ落ちないまま 10 サイクルに到達するまで繰り返し、下記のようにランク評価した。  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.
[0296] X：剥がれ落ちた時のサイクルの回数が 3以下のもの、 [0296] X: The number of cycles when peeling off is 3 or less,
△ :4以上 6以下のものを△、  △: △ from 4 to 6
〇： 7以上 10以下のものを〇、  ○: 7 to 10
◎：剥がれ落ちな 、ものを◎、 尚、実用上問題無いのは◎及び〇である。 ◎: Do not peel off ◎ Note that ◎ and ◯ have no practical problem.
[0297] 《耐久性試験 (耐屈曲性)》  [0297] Durability test (flexibility)
得られたインク硬化膜を 85°Cで 30分保存し— 40°Cで 30分保存した後に、硬化膜 を屈曲させ硬化膜にヒビが入るかどうかを試験して温度変化への耐久性 (耐屈曲性) の評価とした。これを硬化膜にヒビが入る力、あるいはヒビが入らないまま 10サイクル に到達するまで繰り返し、下記のようにランク評価した。  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.
[0298] X：ヒビが入った時のサイクルの回数が 3以下のもの、 [0298] X: The number of cycles when cracks are 3 or less,
△ :4以上 6以下のもの、  △: 4 or more and 6 or less,
〇： 7以上 10以下のもの、  ○: 7 to 10
◎：ヒビが入らないもの、  ◎: No cracks,
尚、実用上問題無いのは◎及び〇である。  Note that ◎ and ◯ have no practical problem.
[0299] 結果を表 8に示す。 The results are shown in Table 8.
[0300] [表 8] [0300] [Table 8]
1261 1261
- ¾¾※^ώ^※ Ί9 ε i Λ ^：：,'- Η
Figure imgf000099_0001
-¾¾ * ^ ώ ^ * Ί9 ε i Λ ^ ::, '-Η
Figure imgf000099_0001
表 8から、本発明の試料は、射出性も良ぐかつ、画質も向上している二とが判る。本 発明の試料は、環境の違いによらず、良好な硬化性を示すことが判る。本発明の試 料は、長期間保存後でも諸性能'諸物性を維持することが判る。 に 発明の試料 は温度変化に対する耐久性が優れていることが判る。 From Table 8, it can be seen that 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.

Claims

請求の範囲 下記一般式 (X)で表される分子量が 180〜 1000である化合物を含有することを特 徴とする重合性組成物。 A polymerizable composition comprising a compound having a molecular weight of 180 to 1000 represented by the following general formula (X):
[化 1]  [Chemical 1]
—般式 (X)—General formula (X)
Figure imgf000101_0001
Figure imgf000101_0001
( R4、 R5、 R6は、各々水素原子またはアルキル基を表し、 R3は一般式（ X)
Figure imgf000101_0002
結合している飽和炭化水素環の任意の位置で結合している置換基 であり、 nは 0から 7までの整数である。 nが複数の場合、 R3は互いに同じであっても異 なっていても良い。 Lは一般式 (X)
Figure imgf000101_0003
R2が結合している飽和炭化水素環と任 意の位置で結合している (p + 1)価の連結基または単なる結合手であり、 pは 1から 3 までの整数であり、 qは 1から 3までの整数である。 pが複数の場合、複数の R4、 R5、 R6 は各々互いに同じであっても異なっていても良ぐ qが複数の場合、複数の L、
Figure imgf000101_0004
R5 、 R6は各々互いに同じであっても異なっていても良い。 ) (R 4 , R 5 , and R 6 each represent a hydrogen atom or an alkyl group, and R 3 represents the general formula (X)
Figure imgf000101_0002
It is a substituent bonded at an arbitrary position of the bonded saturated hydrocarbon ring, and n is an integer from 0 to 7. When n is plural, R 3 may be the same as or different from each other. L is the general formula (X)
Figure imgf000101_0003
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, and q is It is an integer from 1 to 3. When p is plural, plural R 4 , R 5 , R 6 may be the same or different from each other. When q is plural, plural L,
Figure imgf000101_0004
R 5 and R 6 may be the same or different from each other. )
[2] R2の少なくとも一方がアルキル基であることを特徴とする請求の範囲第 1項に記 載の重合性組成物。 [2] The polymerizable composition of at least one of R 2 is placing serial to claim 1, characterized in that an alkyl group.
[3] R2の 、ずれか一方がアルキル基で、他方が水素原子であることを特徴とする請 求の範囲第 1項または第 2項に記載の重合性組成物。 [3] The polymerizable composition as set forth in claim 1 or 2, wherein one of R 2 is an alkyl group and the other is a hydrogen atom.
[4] R2の 、ずれか一方が炭素数 1から 3までのアルキル基で、他方が水素原子であ ることを特徴とする請求の範囲第 1項〜第 3項に記載の重合性組成物。 [4] The polymerizable composition according to any one of claims 1 to 3, wherein one of R 2 is an alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom. object.
[5] R5及び R6が、各々アルキル基であることを特徴とする請求の範囲第 1項〜第 4項の ヽ ずれ力 1項に記載の重合性組成物。 [5] R 5 and R 6 are each polymerizable composition according toヽdisplacement force 1 wherein the first to fourth terms of claims, characterized in that an alkyl group.
[6] 酸発生剤を含有することを特徴とする請求の範囲第 1項〜第 5項のいずれか 1項に 記載の重合性組成物。 [6] The polymerizable composition as set forth in any one of [1] to [5], further comprising an acid generator.
[7] 請求の範囲第 1項〜第 6項のいずれか 1項に記載の重合性組成物を含有することを 特徴とするインク組成物。 [7] An ink composition comprising the polymerizable composition according to any one of claims 1 to 6.
[8] 25°Cにおける粘度が 7mPa · s〜40mPa · sであることを特徴とする請求の範囲第 7項 に記載のインク組成物。 [8] The ink composition according to claim 7, wherein the viscosity at 25 ° C. is 7 mPa · s to 40 mPa · s.
[9] 顔料を含有することを特徴とする請求の範囲第 7項または 8項に記載のインク組成物  [9] The ink composition according to claim 7 or 8, comprising a pigment.
[10] インクジェット記録ヘッドより、請求の範囲第 7項〜第 9項のいずれか 1項に記載のィ ンク組成物を記録材料上に画像様に噴射し、該記録材料上に印刷を行う画像形成 方法であって、該インク組成物が着弾した後、加熱する工程、または、 0. 001秒〜 1 . 0秒間活性光線を照射する工程を経て、前記インク組成物を硬化させることを特徴 とする画像形成方法。 [10] An image in which the ink composition according to any one of claims 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. A method of forming, wherein the ink composition is cured through a step of heating after the ink composition has landed, or a step of irradiating actinic rays for 0.001 seconds to 1.0 seconds. Image forming method.
[11] 前記インクジェット記録ヘッドのノズルより吐出する最小インク液滴量力 2pl〜15pl であることを特徴とする請求の範囲第 10項に記載の画像形成方法。  11. The image forming method according to claim 10, wherein the minimum ink droplet volume force ejected from the nozzle of the ink jet recording head is 2 pl to 15 pl.
[12] 請求の範囲第 10項または第 11項に記載の画像形成方法に用いられるインクジェット 記録装置であって、記録ヘッドを 35°C〜100°Cに加熱した後、インク組成物を吐出 することを特徴とするインクジェット記録装置。 [12] An ink jet recording apparatus for use in the image forming method according to claim 10 or 11, wherein the recording head is heated to 35 ° C to 100 ° C, and then the ink composition is discharged. An ink jet recording apparatus.
[13] 請求の範囲第 10項または第 11項に記載の画像形成方法に用いられるインクジェット 記録装置であって、インク組成物を吐出する際、記録媒体を 35°C〜60°Cに加温す ることを特徴とするインクジェット記録装置。 [13] An ink jet recording apparatus for use in the image forming method according to claim 10 or 11, wherein the recording medium is heated to 35 ° C to 60 ° C when the ink composition is ejected. An ink jet recording apparatus characterized by comprising:
[14] 下記一般式 (X— A)で表される分子量が 180〜1000であることを特徴とする化合物 [14] A compound having a molecular weight of 180 to 1000 represented by the following general formula (X—A)
[化 2] [Chemical 2]
—般式 (X— A) Rii R 3)- —General formula (X— A) R ii R 3) -
(式中、 Ru、 R12、 R15、 R16は水素原子またはアルキル基を表し、 は一般式 (X— A) 中の飽和炭化水素環の任意の位置に結合して 、るアルキル基を表し、 mは 0〜7ま での整数を表し、 R14は水素原子またはアルキル基を表し、 L2は一般式 (X— A)中の 飽和炭化水素環の任意の位置に結合しているアルキレン基、酸素原子または、該ァ ルキレン基と該酸素原子の組み合わせにより形成される二価の連結基を表す。 ) 前記一般式 (X—A)が下記一般式 (X—B)で表されることを特徴とする請求の範囲 第 14項に記載の化合物。 (In the formula, R u , R 12 , R 15 and R 16 represent a hydrogen atom or an alkyl group, and represents a general formula (X—A) An alkyl group bonded to any position of the saturated hydrocarbon ring therein, m represents an integer from 0 to 7, R 14 represents a hydrogen atom or an alkyl group, and L 2 represents a general formula ( X— represents an alkylene group, an oxygen atom, or a divalent linking group formed by a combination of the alkylene group and the oxygen atom bonded to an arbitrary position of the saturated hydrocarbon ring in A—A). The compound according to claim 14, wherein the general formula (X-A) is represented by the following general formula (X-B).
[化 3] 一般式 (X— B)[Chemical formula 3] General formula (X— B)
Figure imgf000103_0001
Figure imgf000103_0001
(式中、 R b、 R ま、各々アルキル基を表し、 は、水素原子またはアルキル基を表 し、 L3は、アルキレン基、酸素原子または、該アルキレン基と該酸素原子の組み合わ せにより形成される二価の連結基を表す。 ) (Wherein R b and R each represents an alkyl group, represents a hydrogen atom or an alkyl group, and L 3 represents an alkylene group, an oxygen atom, or a combination of the alkylene group and the oxygen atom. Represents a divalent linking group.
PCT/JP2006/311261 2005-06-20 2006-06-06 Polymerizable composition, ink composition, image-forming method, inkjet recorder, and alicyclic epoxide WO2006137260A1 (en)

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