WO2007148558A1 - Composition durcissable par rayonnement actif, procédé destiné à durcir cette composition, composition d'encre durcissable par rayonnement actif, procédé de formation d'image et composé associé - Google Patents

Composition durcissable par rayonnement actif, procédé destiné à durcir cette composition, composition d'encre durcissable par rayonnement actif, procédé de formation d'image et composé associé Download PDF

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WO2007148558A1
WO2007148558A1 PCT/JP2007/061797 JP2007061797W WO2007148558A1 WO 2007148558 A1 WO2007148558 A1 WO 2007148558A1 JP 2007061797 W JP2007061797 W JP 2007061797W WO 2007148558 A1 WO2007148558 A1 WO 2007148558A1
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group
general formula
ray curable
compound
actinic ray
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PCT/JP2007/061797
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Japanese (ja)
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Takeshi Kurata
Kimihiko Ookubo
Toshiyuki Takabayashi
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Konica Minolta Medical & Graphic, Inc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/235—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters

Definitions

  • Actinic ray curable composition its curing method, actinic ray curable ink composition, image forming method, and compound
  • the present invention relates to a photosensitizing compound, an actinic ray curable composition containing the compound, an actinic ray curable ink composition, a curing method thereof, and an image forming method.
  • Patent Document 1 European Patent Application No. 1621593
  • Patent Document 2 JP 2000-344704 A
  • Patent Document 3 Japanese Patent No. 3437069
  • Patent Document 4 Japanese Patent Laid-Open No. 11-322952
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2005-139425
  • An object of the present invention is to provide an actinic ray curable composition having high sensitivity and good storage stability, an actinic ray curable ink composition having high image quality, excellent cured film properties, and good storage stability, and a curing method thereof , An image forming method, and a novel 9,10-dietherified anthracene compound.
  • An actinic ray comprising at least one compound represented by the general formula (1), at least one cationically polymerizable compound, and at least one compound capable of generating an acid upon irradiation with actinic rays.
  • a curable composition comprising at least one compound represented by the general formula (1), at least one cationically polymerizable compound, and at least one compound capable of generating an acid upon irradiation with actinic rays.
  • R to R each represent a hydrogen atom or a substituent, and at least R to R
  • R and R are it
  • 11 1 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, Y is either a halogen atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or a 2-naphthyl group, 1 Is an integer of 2 8. ],
  • the following partial structural formula (2) is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, Y is either a halogen atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or a 2-naphthyl group, 1 Is an integer of 2 8. ].
  • 11 12 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, z is
  • C1-C8 linear or branched alkyl group C1-C8 linear or branched saturated or unsaturated acyl group, aryl group, glycidyl group, phenyl group, benzyl group, cyclohexyl group A group, a 2-phenylethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a benzoyl group, a cyclohexylmethyl group, a 1-naphthyl group, or a 2-naphthyl group, and m and n is an integer of 1 to 4.
  • Aryl group glycidyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-tert-butylcyclohexyl group or It represents the deviation of 4-methyl 3-pentale group.
  • At least one of R, R, R, and R is an alkyl of C5 to C10.
  • actinic ray curable composition as described in 1 above, which is a ruthenium group or a cycloalkyl group.
  • any one of R, R, R, and R is an alkyl of C5 to C10.
  • any one of R, R, R, and R is a branched alkyl group.
  • R and R are alkyl groups.
  • actinic ray curable composition according to any one of the above.
  • R and R forces are each located at the ⁇ -position of the bonded oxygen atom.
  • actinic ray curable composition according to any one of 1 to 6 above, which is a group branched on a carbon atom.
  • a compound represented by the following general formula (I 1), (I 2) or (I 3) is included as the compound that generates an acid upon irradiation with at least one actinic ray:
  • the actinic ray curable composition according to any one of 1 to 7 above.
  • R 1, R 2 and R 3 represent substituents, and m, n and p each represents an integer of 0 to 2.
  • X — is the counter ion
  • R represents a substituent
  • q represents an integer of 0 to 2.
  • R represents a substituent, and r represents an integer of 0 to 3.
  • R is a hydrogen atom or substituted, none
  • R 1 and R 2 are each a substituted or unsubstituted alkyl group, substituted or unsubstituted.
  • X— represents a counter ion.
  • a curing method of an actinic ray curable composition wherein the actinic ray curable composition according to 1 above is cured by irradiating the actinic ray with an actinic ray.
  • An actinic ray curable ink composition comprising the actinic ray curable composition according to any one of 1 to 8 above.
  • the actinic ray curable ink composition described in 10 above is ejected or applied imagewise, An image forming method comprising curing by irradiation with actinic rays.
  • R to R each represents a hydrogen atom or a substituent, and at least R to R
  • R and R are it
  • 11 1 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, Y is a halogen atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or a 2-naphthyl group, 1 is an integer of 2-8. ]
  • the following partial structural formula (2) is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, Y is a halogen atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or a 2-naphthyl group, 1 is an integer of 2-8. ].
  • 11 12 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, z is
  • C1-C8 linear or branched alkyl group C1-C8 linear or branched saturated or unsaturated acyl group, aryl group, glycidyl group, phenyl group, benzyl group, cyclohexyl group Group, 2-phenylethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, benzoyl group, cyclohexylmethyl group, 1-naphthyl group Or any one of 2 naphthyl groups, and m and n are integers of 1 to 4.
  • Aryl group glycidyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-tert-butylcyclohexyl group or It represents the deviation of 4-methyl 3-pentale group.
  • At least one of R, R, R, and R is C5 to C10
  • any one of R, R, R, and R is C5 to C10.
  • a kill group or a cycloalkyl group the other three are hydrogen atoms, R, R, R,
  • any one of R, R, R, and R is branched alkyl.
  • R and R are alkyl groups.
  • R and R forces are each located at the ⁇ -position of the oxygen atom to which they are bonded.
  • an actinic ray curable composition having high sensitivity and good storage stability, a method for curing the composition, and a novel 9, 10 diether anthracene compound useful as a sensitizer can be provided. .
  • Fig. 1 is a 1- NMR measurement chart of-27.
  • R to R are a hydrogen atom or a substituent, and the substituent represented by R to R
  • alkyl groups e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert butyl group, iso butyl group, sec butyl group, pentyl group, tert pentyl group, hexyl group
  • Heptyl group octyl group, nonyl group, 2-ethylhexyl group, decyl group, dodecyl group, etc.
  • cycloalkyl group eg cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group
  • alkenyl group for example, bur group, 1 probe group, 2-probe group, 2-butyl group, aryl group, etc.
  • cycloalkenyl group cyclopentenyl group, cyclo Pentagenyl group, cyclohexyl group
  • Triazyl group imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1 isoxylyl group), non-aromatic A heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholino group, oxazolidyl group, 2-tetrahydrofuryl group, 2-tetrahydrophenyl group, 2-tetrahydrobiral group, 3-tetrahydrobiranyl group, etc.), A halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyan group and the like can be mentioned.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • These groups which may be further substituted include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkyl group, an alkyl group, an aryl group, a heterocyclic group, and a cyan group.
  • R 1 to R are preferably a hydrogen atom or an aliphatic group (an alkyl group, a cycloalkyl group,
  • alkyl group a cycloalkenyl group, an alkyl group, a cycloalkyl group, and the like, more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group.
  • Preferred alkyl groups include, for example, ethyl group, n propyl group, n butyl group, n pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nor group, n-decyl group.
  • cycloalkyl group examples include a cycloheptyl group, a cyclohexyl group, and a cyclopentyl group.
  • At least one of R 1 to R 5 is a C5-C10 alkyl group or a silyl group.
  • a chloroalkyl group for example, C5-C10 among the above alkyl groups or cycloalkyl groups, and a branched alkyl group or a cycloalkyl group is preferred tert-pentyl group, 2,2-dimethylpropyl Group, cyclohexyl group, and 1-methyl-1-cyclohexyl group are more preferable, and tert pentyl group is most preferable!
  • the C5-C10 alkyl group or cycloalkyl group is R 1, R 2,
  • R and R be preferred. More preferred.
  • alkyl group which may be substituted from C1 to C30 of R and R include, for example:
  • substituents that can be substituted for these include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, strong rubamoyloxy group, alkoxycarboxyloxy group, aryloxycarboxyloxy group, amino group, arlino group , Acylamino group, aminocarbo-lamino group, alkoxycarbo-lamino group, aryloxycarbo-lamino group, sulfamoylamino group, alkyl and arylsulfo-lamino group, mercapto group, alkylthio group, arylthio group, hetero
  • Silyl group hydrazino group, ureido group, boronic acid group, phosphato group, sulfato group and other known substituents.
  • R 1 and R 2 in the partial structural formula (1) are a hydrogen atom, a halogen atom or an alkyl.
  • a hydrogen atom or an alkyl group preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group.
  • 1 in the formula is multiple, multiple R and
  • R and R in the partial structural formula (2) are the same as R and R in the partial structural formula (1).
  • R and R are plural, the plural R and R may be the same or different.
  • multiple n may be the same or different.
  • partial structural formula (1) include, for example, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2 1 (1 naphthyl) ethyl group, 3 fluoropropyl group, 3 chloropropyl group, 3 bromopropyl group, 3 propylpropyl group, 3 cyclohexylpropyl group, 3— (1-naphthyl) propyl group, 4 fluorbutyl group, 4 Chlorobutyl group, 4-bromobutyl group, 4-phenylbutyl group, 4-cyclohexylbutyl group, 4-1- (1-naphthyl) butyl group, 5-fluoropentyl group, 5-chloropentyl group, 5-bromopentyl group, 5-phenol -Rupentyl group, 5 cycl
  • 2-methoxy-1-methylethyl group 2-ethoxy-1-methylethyl group, 2-acetyl-1-methylethyl group, 1-methyl-2-phenoxychetyl group, 2-cyclohexyl-1-methylethyl group, 2- (2-methoxy-1-methylethoxy) 1-methylethyl Group, 2- (2-ethoxy 1-methylethoxy) 1 methylethyl group, 2- (2-acetyloxy 1-methylethoxy) 1 methylethyl group, 2- (1-methyl-2-phenoxyethoxy) 1 methylethyl group, 2- (2 —Cyclohexyloxy 1-methylethoxy) 1 methylethyl group, 2— (2- (2-methoxy1 methylethoxy) 1 methylethoxy) 1 methylethyl group, 2— (2- (2-ethoxy1-methylethoxy) 1 methylethoxy) 1 methylethyl group, 2- (2- (2-acetoxy
  • R and R are optionally substituted alkyl groups having 1 to 30 carbon atoms
  • new alkyl groups include n-butyl, n-pentyl, n-xyl, n-butyl, n-octyl, n-nor, n-decyl, n-undecyl and n-dodecyl.
  • R and R may be the same or different, but are preferably the same.
  • R and R are branched on the carbon atom located at the ⁇ -position of the oxygen atom in the general formula (1).
  • the group is not.
  • the group that is not branched on the carbon atom located in the ⁇ -position of the oxygen atom in the general formula (1) will be described in detail.
  • the group is branched on the carbon atom located at the ⁇ -position of the oxygen atom in the general formula (1) !, and the group ( ⁇ ) is in the ex-position of the oxygen atom in the general formula (1). It is a branched group on the carbon atom located.
  • the compound of the present invention may be synthesized by any method. For example, 9, 10-anthraquinones, which are conventionally known compounds, are reduced using an appropriate reducing agent, and are appropriately obtained in the presence of an appropriate base. Can be easily synthesized by reacting with various alkylating agents
  • Shape, integral ratio 0.5-0. 7, t, 3H; 1. 2- 1. 6, m, 12H; 1. 7- 1. 9, m, 2H; 4.0 0-4. 2 , m, 4H; 7. 3— 7. 7, m, 3H; 8. 4— 8. 6, m, 4H.
  • FIG. 1 shows a 1 H-NMR measurement chart of AE-27.
  • AE-4 10.5 g (22. lmmol, 44%) was obtained in the same manner as the synthesis of AE-28 except that n-heptyl tosylate was used instead of isopentyl tosylate.
  • AE-1 10.5 g (22. lmmol, 44%) was obtained in the same manner as in the synthesis of AE-28 except that n-butyl tosylate was used instead of isopentyl tosylate.
  • 2-tert-pentyl-9, 10-anthraquinone 8. 35 g (30 mmol), 5% palladium on carbon catalyst (wet, manufactured by Kawaken Fine Chemicals) 2. 09 g, sodium hydroxide hydrated in a mortar 2.52 g (63 mmol) Then, 30.76 g (120 mmol) of 2-methylpentyl tosylate was mixed, 200 ml of DMF was added, and the mixture was vigorously stirred for 9 hours in a hydrogen atmosphere.
  • Shape, integral ratio 0.6-1. 1, m, 9H; 1. 2.1.8, m, 24H; 2. 1-2. 3, m, 4H ; 3.8-4.1, m, 4H; 7.3- 7.7, m, 3H; 8.5- 8.7, m, 4H.
  • AE-50, 2.7 g (3.18 mmol, 11% yield) was obtained in the same manner as the synthesis of AE-31 except that 2-octyldodecyl tosylate was used instead of 2-methylpentyl tosylate. It was.
  • AE-42 3.8 g (7.5 mmol, 25% yield) was obtained in the same manner as the synthesis of AE-31, except that 2-ethylhexyl tosylate was used instead of 2-methylpentyl tosylate. It was.
  • AE-2, AE-3, AE-12, AE-17, AE-18, AE-45-47, AE-51-54, AE-57, AE-67, AE-68, AE-70 , AE-85, AE-94, AE-97, AE-102, AE-105, AE-107, AE-109, AE-110 were synthesized and their structures were confirmed by NMR.
  • Examples of the compound that generates acid upon irradiation with actinic rays used in the actinic ray curable composition of the present invention include, for example, a chemically amplified photoresist and light.
  • the compounds used for force thione polymerization are used (see Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Examples of compounds suitable for the present invention are listed below.
  • sulfonates such as CF 2 SO—salts.
  • CF 2 SO—salts Mention may be made of sulfonates such as CF 2 SO—salts.
  • borate compounds as anti-ons and PF-salts are preferred because of their high acid generation ability.
  • halide that generates halogen hydrogen can also be used.
  • Specific compounds are exemplified below.
  • arylsulfurum salt derivatives for example, Union 'Carbide's Cyracure UVI-6990, Cyracure UVI-6974, Asahi Denka Kogyo Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172), Allylhodonium salt derivatives (for example, RP-2074 from Rhodia), allene-ion complex derivatives (eg Irgacure 261 from Ciba-Gaigi), diazodium salt derivatives, triazine initiators And other acid generators such as halides.
  • arylsulfurum salt derivatives for example, Union 'Carbide's Cyracure UVI-6990, Cyracure UVI-6974, Asahi Denka Kogyo Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172
  • the photoacid generator is preferably contained at a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. If the content of the polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, there is no further effect of improving curability.
  • One or more of these photopower thione polymerization initiators can be selected and used.
  • Preferred photoacid generators used in the present invention are onium salts such as sulfonium salts, odonium salts, ammonium salts, phospho- um salts, and the like, and among them, sulfo-um chlorides. Compounds are preferred.
  • a more preferred structure of the sulfoyuium salt compound is a sulfonium salt represented by the general formula (1-1), (I 2) or (I 3).
  • R 1, R 2 and R 3 represent a substituent.
  • substituents include
  • Halogen atom for example, chlorine atom, bromine atom, fluorine atom, etc.
  • C1-C6 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
  • carbon number 3 ⁇ 6 cycloalkyl groups for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl groups having 1 to 6 carbon atoms for example, beryl group, 1 A probe group, a 2-probe group, a 2-buture group, etc., an alkynyl group having 1 to 6 carbon atoms (for example, an acetyl group, a 1-propyl group, a 2-propyl group, 2-butylyl group, etc.)
  • alkoxy group having 1 to 6 carbon atoms for example, methoxy group, ethoxy group, n propoxy group, iso
  • n, n and p each represents an integer of 0 to 2, and each is preferably 1 or more.
  • X— represents a counter-on.
  • Examples include complex ions such as F- and sulfonate ions such as p-CH C H SO- and CF SO-.
  • borate ion and PF- are preferred because of their high acid generation capacity.
  • R represents a substituent.
  • substituents include halogen
  • Atom for example, chlorine atom, bromine atom, fluorine atom, etc.
  • C1-C6 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
  • C3-6 Cycloalkyl group for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group having 1 to 6 carbon atoms for example, vinyl group, 1 probe group) , 2 probe groups, 2 butyr groups, etc.
  • alkynyl groups having 1 to 6 carbon atoms for example, acetyl group, 1 propyl group, 2-propyl group, 2-propyl group
  • alkoxy group 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.
  • aryloxy group for example, phenoxy group, naphthoxy group, etc.
  • arylthio group having 6 to 10 carbon atoms for example, phenylthio group, naphthylthio group, etc.
  • acyl group for example, acetyl group, propio group, etc.) -L group, trifluoroacetyl group, benzoyl group, etc.
  • acyloxy A group for example, acetooxy group, propio-loxy group, trifluoroacetoxy group, benzoyloxy group, etc.
  • alkoxy carbo yl group methoxy carbo yl group, ethoxy carbo yl group, tert butoxy carbonyl group, etc.
  • hetero atom-containing aromatic ring group having 4 to 8 carbon atoms
  • furyl group for example, furyl group, chenyl group, etc.
  • nitro group cyan group and the like.
  • a halogen for example,
  • q represents an integer of 0 to 2, and is preferably 1 or more, more preferably 2.
  • R 1 and R 2 are substituted, unsubstituted alkyl groups, substituted, unsubstituted alkenyl groups, substituted,
  • Examples of the substituent include a halogen atom (for example, a chlorine atom, 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.), a cycloalkyl group having 3 to 6 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkyl group having 1 to 6 carbon atoms.
  • a halogen atom for example, a chlorine atom, 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 iso
  • alkynyl group having 1 to 6 carbon atoms for example, acetyl group, 1 propyl group) Group, 2 propyl group, 2 butur group, etc.
  • alkoxy group 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.
  • an alkylthio group having 1 to 6 carbon atoms for example, methyl) Ruthio group, ethylthio group, n propylthio group, iso propylthio group, n-butylthio group, tert-butylthio group, etc.
  • aryl group having 6 to 14 carbon atoms eg, phenyl group, naphthyl group, anthracene group
  • 6-carbon L0 aryloxy group
  • R 1 and R 2 are preferably a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group.
  • a substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group or a hydroxyl group.
  • X— represents counter-on.
  • the counter-on includes BF-, B (C F)-, PF-, AsF-, Sb
  • Examples include complex ions such as F- and sulfonate ions such as p-CH C H SO- and CF SO-.
  • borate ion and PF- are preferred because of their high acid generation capacity.
  • R represents a substituent.
  • substituents include halogen
  • Atom for example, chlorine atom, bromine atom, fluorine atom, etc.
  • C1-C6 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
  • C3-6 Cycloalkyl group for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group having 1 to 6 carbon atoms for example, vinyl group, 1 probe group) , 2 probe groups, 2 butyr groups, etc.
  • alkynyl groups having 1 to 6 carbon atoms for example, acetyl group, 1 propyl group, 2-propyl group, 2-propyl group
  • alkoxy group 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.
  • r represents an integer of 0 to 3, and is preferably 1 or more, more preferably 2.
  • R represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R and R are substituted or unsubstituted.
  • Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group). , A butyl group, etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkyl group having 1 to 6 carbon atoms.
  • a halogen atom eg, chlorine atom, bromine atom, fluorine atom, etc.
  • an alkyl group having 1 to 6 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group.
  • a butyl group, etc. a cycloalky
  • alkynyl group having 1 to 6 carbon atoms for example, acetyl group, 1 propyl group
  • alkoxy group 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. an aryl group having 6 to 14 carbon atoms
  • acyl group for example, acetyl group, propiol group, trifluoroacetyl group, benzoyl group, etc.
  • acyloxy group for example, acetoxy group, propio-loxy group, trifluoro group
  • R is preferably a hydrogen atom or an unsubstituted lower alkyl group (methyl group, ethyl
  • R 1 and R 2 are preferably substituted or unsubstituted alkyl groups, and
  • Is a substituted or unsubstituted aryl group preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an acyl group.
  • X— represents counter-on.
  • the counter-on includes BF-, B (C F)-, PF-, AsF-, Sb
  • Examples include complex ions such as F- and sulfonate ions such as p-CH C H SO- and CF SO-.
  • borate ion and PF- are preferred because of their high acid generation capacity.
  • the cationically polymerizable compound used in the actinic ray curable composition of the present invention is a type in which a polymer is formed by force thione polymerization, and (1) a compound having an oxysilane ring (epoxy group). (2) styrene derivatives, (3) vinyl naphthalene derivatives, (4) vinyl ethers, (5) N-vinyl compounds, and (6) compounds having an oxetane ring.
  • the type (1) having an oxysilane ring is not particularly limited, and examples thereof include compounds having an oxysilane ring in one molecule.
  • examples of such epoxy compounds include alicyclic epoxides (also referred to as alicyclic epoxies and alicyclic epoxy compounds), glycidyl esters of polybasic acids, glycidyl ethers of polyhydric alcohols, and polyoxyalkylenes.
  • examples thereof include glycidyl ethers of glycols, glycidyl ethers of aromatic polyols, hydrogenated compounds of glycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxy polybutadienes. These compounds can be used alone or in a combination of two or more.
  • An epoxy compound that can be suitably used in the present invention is an alicyclic epoxy compound.
  • a further sensitivity improvement effect or a cured film property improvement effect can be obtained by using a polyfunctional alicyclic epoxy compound in combination.
  • polyfunctional alicyclic epoxides preferred as the bifunctional alicyclic epoxides are polyfunctional epoxy compounds represented by the following general formula (B).
  • R 1 and R 2 represent a substituent
  • m20 and n20 each represents 0, 1 or 2.
  • rO represents 1-3
  • the L may contain oxygen or sulfur atoms in the main chain rO + 1 valence with 1 to 15 carbon atoms
  • R 1 and R 2 represent a substituent.
  • substituents include a halogen atom (eg
  • a chlorine atom, 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.), a C 1-6 carbon atom Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n butoxy group, tert butoxy group, etc.), acyl groups (for example, acetyl group, propiool group, trifluoroacetyl group, etc.) ), An acyloxy group (for example, an acetoxy group, a propio-loxy group, a trifluoroacetoxy group, etc.), an alkoxy carbo group (a methoxy carbo ol group, an ethoxy carbo ol group, a tert butoxy
  • m20 and n20 each represents 0 to 2, preferably 0 or 1.
  • L may contain an oxygen atom or a sulfur atom in the main chain.
  • Examples of the divalent linking group having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain include the following groups and these groups and the O group, S group, CO group and CS group: The group which can be combined together can be mentioned.
  • the divalent linking basic forces listed above can be formed by removing as many hydrogen atoms as necessary, and those with —O— groups, —S— groups, —CO— groups, —CS — List groups that can be formed by combining multiple groups.
  • L may have a substituent.
  • substituents include halogen atoms (e.g. chlorine
  • 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 having 1 to 6 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.
  • An acyloxy group for example, an acetooxy group, a propionyloxy group, a trifluoroacetoxy group, etc.
  • an alkoxy carbo group a methoxy carbo ol group, an ethoxy carbonyl group, a tert-butoxy carbo ol group, etc.
  • Etc Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxycarbo group.
  • 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.
  • a divalent linking group having 1 to 5 carbon atoms in which the main chain preferred by the group is only carbon is more preferred.
  • Preferred alicyclic epoxides are compounds represented by the following general formula (B—I) or (B—II):
  • R 1 and R 2 represent substituents, and m21, n21i, 0, 1 and ⁇ 2 are represented. p21, q21i
  • rl represents 1-3.
  • L is oxygen or sulfur atom in the main chain
  • R 1 and R 2 represent a substituent
  • m22 and n22 each represent 0, 1 or 2.
  • p22 and q22 are
  • r2 represents 1-3.
  • L is oxygen or sulfur atom in the main chain
  • the cycloaliphatic epoxides are represented by the following general formulas (B-III) or (B-IV). It is a compound.
  • R 1 and R 2 represent a substituent
  • m23 and n23 each represents 0 or 1.
  • p23, q23 is it
  • L contains oxygen or sulfur atoms in the main chain.
  • R R represents a substituent
  • m24 n24 represents 0 or hi.
  • p24 q24 is it
  • r4 represents 1 3 L contains oxygen or sulfur atoms in the main chain.
  • R R R R represents a substituent.
  • substituents include halogen
  • Atoms eg, chlorine, bromine, fluorine, etc.
  • C 16 alkyl groups eg, methyl, ethyl, propyl, isopropyl, butyl, etc.
  • C 16 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, propiool group, trifluoro group
  • Acetyl group, etc. acyloxy group (for example, acetooxy group, propio-loxy group, trifluoroacetoxy group, etc.)
  • alkoxy carb group methoxy carbo yl group, ethoxy carbo yl group, tert butoxy carbo ol) Group, etc.
  • Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxy carbo group
  • m23 n23 m24 ⁇ 24 ⁇ or 0 2 represents 0 or ⁇ or 1 power ⁇ Preferred! / ⁇ .
  • L may contain an oxygen atom or a sulfur atom in the main chain, and has r15 + 1 valence having 1 to 15 carbon atoms.
  • L may contain an oxygen or sulfur atom in the main chain
  • Examples of the divalent linking group having 115 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain, are the same as those described in the description of L.
  • L L is a divalent valence having 18 carbon atoms that may contain oxygen or sulfur atoms in the main chain.
  • Preferred is a divalent linking group with 15 carbon atoms whose main chain is only carbon. Good.
  • the addition amount of the epoxy compound is preferably 10 to 40% by mass in consideration of curability due to the curing environment (temperature, humidity) and film physical properties after curing.
  • one kind of polyfunctional epoxy compound may be used alone, or two or more kinds may be used in appropriate combination.
  • styrene ⁇ -methylol styrene, ⁇ -methoxy styrene, 13-methylol styrene, p-methylolene ⁇ -methyl styrene, ⁇ -methylol styrene, ⁇ -methoxy 13-methyl styrene, etc.
  • Vinyl naphthalene derivatives For example, 1-Burnaphthalene, ⁇ -Methyl 1-Burnaphthalene, j8-Methyl 1-Vinylnaphthalene, 4-Methyl 1-Vinylnaphthalene, 4-Methoxy-1-vinylnaphthalene, etc.
  • any known oxetane compound as disclosed in JP-A-2001-220526 and JP-A-2001-310937 can be used.
  • the compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.
  • R 1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or the like, an alkyl group having 16 carbon atoms, a fluoroalkyl group having 16 carbon atoms, an aryl group, an aryl A group, a furyl group or a chenyl group.
  • R 2 is an alkyl group having 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a 1 probe group, a 2 probe group, a 2-methyl-1 probe group, 2-Methyl-2-propellyl group, 1-Butul group, 2-Butul group, 3 Butul group, etc.
  • an aromatic ring such as a methoxybenzyl group or a phenoxychetyl group
  • a 26-carbon alkyl group such as an ethylcarbol group, a propylcarbol group or a butylcarbol group, an ethoxycarbol group, Number of carbon atoms such as propoxycarbol group, butoxycarbol group, etc.
  • 26 carbon atoms such as alkoxycarboro group having 6 carbon atoms, or ethylcarbamoyl group, propyl carbamoyl group, butylcarbamoyl group, pentylcarbamoyl group, etc.
  • N-alkyl power ruber moyl Group such as alkoxycarboro group having 6 carbon atoms, or ethylcarbamoyl group, propyl carbamoyl group, butylcarbamoyl group, pentylcarbamoyl group, etc.
  • oxetane compound used in the present invention it is particularly preferable to use a compound having two oxetane rings because the resulting composition has excellent adhesiveness, low viscosity and excellent workability. .
  • An example of a compound having two oxetane rings includes a compound represented by the following general formula (102).
  • R 1 is the same group as that in the general formula (101).
  • R 3 is, for example, a linear or branched alkyl group such as an ethylene group, a propylene group, or a butylene group.
  • Linear or branched poly (alkyleneoxy) group such as xylene group, poly (ethyleneoxy) group, poly (propyleneoxy) group, probelene group, methylpropylene group, butylene group, etc.
  • a linear or branched unsaturated hydrocarbon group an alkylene group containing a carbol group or a carbonyl group, an alkylene group containing a carboxyl group, an alkylene group containing a strong rubamoyl group, and the like.
  • R 3 there can be mentioned a polyvalent group in which the basic forces represented by the following general formulas (103), (104) and (105) are also selected.
  • R 4 represents a hydrogen atom, an alkyl group having 14 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a propyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. It is an alkoxy group having 14 carbon atoms such as a Si group, a halogen atom such as a chlorine atom or a bromine atom, a nitrogen group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a strong rubamoyl group.
  • R 5 represents an oxygen atom, a sulfur atom, a methylene group, NH 2 SO 2 SO
  • R 6 is an alkyl group having 14 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group.
  • n is an integer of 0 2000.
  • R I s a methyl group, an ethyl group, a propyl group, a butyl group having 14 carbon atoms, or an aryl group.
  • R 7 there can be further mentioned groups in which the basic force represented by the following general formula (106) is also selected.
  • R 8 is an alkyl group having 14 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group.
  • m is an integer of 0 100.
  • Specific examples of the compound having two oxetane rings include the following compounds.
  • Exemplary compound 11 is a compound in which, in the general formula (102), R 1 is an ethyl group and R 3 is a carboxyl group.
  • Exemplified Compound 12 is a compound in which, in the general formula (102), R 1 is an ethyl group, R 3 is the general formula (105) in the R 6 and R 7 cate groups, and n is 1.
  • R 1 has the same meaning as R 1 in the general formula (101).
  • an example of a compound having 34 oxetane rings includes a compound represented by the following general formula (108).
  • R 1 has the same meaning as R 1 in the general formula (101).
  • R 9 for example, a branched alkylene group having 112 carbon atoms such as a group represented by the following AC, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polyoxy groups such as the above-mentioned groups.
  • j is 3 or 4.
  • R w is a lower alkyl group such as a methyl group, Echiru or propyl.
  • p is an integer of 1 10.
  • R 8 has the same meaning as R 8 in the general formula (106).
  • R 11 is a C 14 alkyl group or a trialkylsilyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and r is 14;
  • oxetane compound used in the present invention include the following compounds.
  • the method for producing each compound having an oxetane ring described above is not particularly limited, and may be performed according to a conventionally known method.
  • Pattyson DB Pattison, J. Am. Chem. Soc., 3455, 79 (1957) discloses a method for synthesizing an oxetane ring from a diol.
  • 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 the following compounds.
  • a coloring material when the ink composition of the present invention is used as an inkjet ink, a coloring material that can be dissolved or dispersed in the main component of the polymerizable compound can be used. preferable.
  • Pigments that can be preferably used in the present invention are listed below.
  • a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used.
  • a dispersant can be added when dispersing the pigment.
  • the 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 dispersants and dispersion aids 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 of the present invention is used as an ink-jet ink, it is preferably solvent-free in order to react and cure 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 terms of dispersibility.
  • the average particle size of the pigment particles is 0.08-0. 5 ⁇ m.
  • the maximum particle size is 0.3 to: LO / zm, preferably 0.3 to 3 Select the pigment, dispersant, and dispersion medium, and set the dispersion conditions and filtration conditions appropriately so that / zm is obtained.
  • the colorant concentration is preferably 1% by mass to 10% by mass with respect to the entire 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, and the like are decomposed to release amines A compound that releases a base by causing some kind of reaction by heating is preferably used.
  • More specific examples include trichlorodiethyl acetate guanidine, trichlorodimethylacetate acetate, potassium trichlorodiacetate, phenylsulfuracetate guanidine, p-diethylphenol sulfone.
  • the thermal base generator can be used in a wide range.
  • the ink composition of the present invention includes an acid-enhancement that newly generates an acid by an acid generated by irradiation with actinic rays that has been already known, such as those disclosed in JP-A-8-248561 and JP-A-9-34106. It is also possible to contain a breeding agent.
  • the ink composition of the present invention is produced by well dispersing the pigment together with an actinic ray curable composition and a pigment dispersant using a normal dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution with a high pigment concentration in advance and dilute with an active energy ray-curable compound. Sufficient dispersion is possible even with dispersion by ordinary dispersers.Therefore, no excessive dispersion energy is required, and a large amount of dispersion time is not required, so it is difficult to cause deterioration during dispersion of ink components. An ink having excellent properties is prepared. The ink is preferably filtered through a filter having a pore diameter of 3 m or less, more preferably 1 ⁇ m or less.
  • the actinic ray curable composition of the present invention may be used by adjusting the viscosity or the like so as to impart desired physical properties depending on the application.
  • the viscosity at 25 ° C. is preferably adjusted to be as high as 7 to 40 mPa ′s.
  • Inks with a viscosity of 7 to 40 mPa's at 25 ° C show stable ejection characteristics, especially from a head having a normal frequency of 4 to 10 KHz, even with a high frequency head of 10 to 50 KHz.
  • the piezo head has an electric conductivity of 10 SZcm or less and does not cause electrical corrosion inside the head.
  • the conductivity In the continuous type, it is necessary to adjust the conductivity with the electrolyte. In this case, it is necessary to adjust the conductivity to 0.5 mSZcm or more.
  • the surface tension at 25 ° C is preferably in the range of 25 to 40 mN / m! /. If the surface tension of the ink at 25 ° C is less than 25 mNZm, stable emission is difficult to obtain, and if it exceeds 40 mNZm, the desired dot diameter cannot be obtained. Outside the range of 25 to 40 mNZm, it is difficult to obtain uniform dot diameters on various supports even if light is emitted and irradiated while controlling the viscosity and water content of the ink as in the present invention.
  • a surfactant may be contained as necessary.
  • Examples of the surfactant preferably used in the ink-jet ink according to the present invention include, for example, cation surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, and polyoxyethylene alkyl ethers.
  • Nonionic surfactants such as polyoxyethylene alkylaryl ethers, acetylene glycols, polyoxyethylene 'polyoxypropylene block copolymers, alkylamine salts, quaternary ammonium salts, etc. Examples thereof include a cationic surfactant and a surface active compound having a polymerizable group.
  • silicone-modified acrylate, fluorine-modified Preferred are surface active compounds having a polymerizable group such as unsaturated bond, oxsilane, oxetane ring, etc., such as functional acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, and fluorine-modified oxetane.
  • additives other than those described above can be used in the inkjet ink according to the present invention.
  • leveling additives, matting agents, polyester resin to adjust film properties, polyurethane resin, vinyl resin, acrylic resin, rubber resin, and rubbers are added. be able to.
  • the ink composition is ejected and drawn on a recording material by an ink jet recording method, and then the ink is cured by irradiation with an actinic ray such as ultraviolet rays.
  • the ink is heated together with the ink jet nozzles when the ink is ejected so that the ink liquid has a low viscosity.
  • the heating temperature is 30-80 ° C, preferably 35-60. C.
  • the total ink film thickness after the ink has landed and cured by irradiation with actinic rays is preferably 20 to 20 m.
  • the current strength is that the total ink film thickness exceeds 20 / zm.
  • the recording material is thin!
  • the amount of liquid droplets discharged from each nozzle is preferably 2 to 15 pl.
  • the irradiation timing is as early as possible.
  • the ink viscosity or moisture content is in a preferable state. It is preferable to start the light irradiation.
  • it is preferable to start the irradiation of active light within 0.001 to 2.0 seconds after ink landing as the irradiation condition of the generated light, more preferably 0.001 to 0.4 seconds. is there.
  • the light irradiation be performed to the extent that the fluidity of the ink is lost after 0.1 to 3 seconds, and preferably within 0.2 to 1 second, and then terminated.
  • 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 is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven.
  • a method using an optical fiber is used as an irradiation method, or a collimated light source is applied to a mirror surface provided on the side of a recording head unit to irradiate a recording unit with UV light The method 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 by the above-described method within 0.001 to 2.0 seconds after ink landing, and after all printing is completed, actinic rays are further emitted.
  • the irradiation method is also a preferred embodiment.
  • 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, a UV laser, a xenon flash lamp, a trap lamp, a black light, a germicidal lamp, a cold cathode tube, and an LED. Among them, a fluorescent tube is preferable because of its low energy and low cost.
  • the light source wavelength is 250 to 370 nm, preferably a light source having a light emission wavelength peak at 270 to 320 nm in terms of sensitivity.
  • the illuminance is 1 to 3000 mWZcm 2 , preferably 1 to 200 mWZcm 2 .
  • it is usually cured with an electron beam of 300 eV or less, but it can also be cured instantaneously with a dose of 1-5 Mrad.
  • an image mark is printed on a recording medium (both the substrate and the substrate).
  • a recording medium any of a wide range of synthetic resins conventionally used for various purposes can be used. Specifically, for example, polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, Examples thereof include acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutaterene terephthalate, etc.
  • the thickness and shape of these synthetic resin substrates are not limited at all.
  • a non-absorbent support can be used in addition to ordinary non-coated paper, coated paper, and the like. Is preferably used.
  • various non-absorbable plastics and films thereof can be used as the non-absorbent support.
  • the various plastic films include PET film, OPS film, OPP film, ONy Examples include films, PVC films, PE films, and TAC films.
  • Other plastics include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubber. It can also be applied to metals and glasses.
  • the configuration of the present invention is particularly effective 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 surface energy of these various plastic films varies greatly, and the dot diameter after ink landing varies depending on the recording material.
  • the wetting index is 40 to 60 mN / m as a force base material including an OPP film having a low surface energy, an OPS film, a relatively large surface energy, and up to PET.
  • a long (web) recording material is used from the viewpoints of the cost of recording materials such as packaging costs and production costs, the efficiency of creating prints, and the ability to handle prints of various sizes. Is more advantageous.
  • Example [0241] The actinic ray curable composition was prepared by mixing the compound of the present invention, the comparative compound, the cationic polymerizable compound, and the photoacid generator as shown in Table 1.
  • OX-1 OXT-101: Toagosei Co., Ltd.
  • OX-2 OXT-121: Toagosei Co., Ltd.
  • OX-3 OXT-221: Toagosei Co., Ltd.
  • OXT—212 manufactured by Toagosei (Photopolymerization initiator)
  • SP- 1 SP— 152: Adekaoptomer SP— 152 Asahi Denka Co., Ltd.
  • UV-1 UVI6992: Dow Chemical Propion Carbonate 50% solution
  • ES-1 ESACURE1187: Lamberti Propion Carbonate 50% solution
  • Table 1 UV-1: UVI6992: Dow Chemical Propion Carbonate 50% solution
  • ⁇ indicates that it is sufficiently cured at 10 cm
  • ⁇ indicates that it is not sufficiently cured at 10 cm
  • ⁇ indicates that it is not sufficiently cured at 5 cm
  • X indicates that it is not sufficiently cured even at 5 cm.
  • the actinic ray curable composition shown in Table 1 was sealed in a sealed glass container, stored at ⁇ 20 ° C. for 1 month, and the inside of the container was visually observed.
  • the actinic ray curable composition shown in Table 1 was sealed in a sealed polypropylene bottle and stored at 50 ° C. for 1 week. Compared with the composition in the initial state, ⁇ indicates that no discoloration is observed, ⁇ indicates that discoloration is hardly observed, and X indicates that discoloration is clearly observed.
  • Titanium oxide (anatase type: particle size 0.2 m)
  • F1405 Megafax F1405 Perfluoroalkyl group-containing ethylene oxide additive (Dainippon Ink Chemical Co., Ltd.) 0.5 parts by mass
  • Halitak 145P (Rosin-modified maleic acid resin, manufactured by Harima Chemical Co., Ltd.) 0.5 parts by mass ⁇ Inkjet image forming method >>
  • Each ink composition set 101-126 prepared above is loaded into an ink jet recording apparatus equipped with a piezo type ink jet nozzle, and a long recording material of 600 mm and a length of 20 m (manufactured by YUPO Corporation, synthetic paper YUPO FGS) The following image recording was continuously performed.
  • the ink supply system was 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 heated according to the viscosity of each curable composition ink, and multi-size dots with a droplet volume of 2 to 15 pl are set to 720 x 720 dpi (1 dpi, that is, 2.5 dots per dot).
  • the cured composition ink described above was continuously ejected by being driven so that it could be ejected at a resolution of 2).
  • the recording material was heated to 50 ° C with a surface heater. After landing, it was cured instantaneously (less than 0.5 seconds after landing) with an irradiation light source (metal halide lamp) on both sides of the carriage (MAL400NL power: 3kW.hr 120WZcm, manufactured by Nihon Battery Co., Ltd.). When the total ink film thickness was measured after image recording, it was in the range of 2.3 to 13 m. Inkjet images were formed by printing in the environment of 30 ° C 80% RH and 25 ° C20% RH according to the above method.
  • the integrated illuminance at 254 nm was measured using UVPF-A1 manufactured by Iwasaki Electric Co., Ltd.
  • An image was formed in the same manner as Image Forming Method A, except that one lmm-thick Pyrex (registered trademark) glass was used as a filter (wavelengths below 300 nm were almost cut) during exposure.
  • Pyrex registered trademark
  • 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.
  • ⁇ Visible but can be distinguished as characters and can be used at the last minute
  • X A level that can not be used because the characters are harsh.
  • Y, M, C, K, and W colors are printed so that one dot is adjacent to each other, and each adjacent color dot is magnified with a loupe, visually observing the state of bleeding and wrinkles, and mixed according to the following criteria Was evaluated.
  • Adjacent dots are slightly blurred and the dot shape is slightly deformed.
  • Adjacent dots are blurred and mixed, and wrinkles are generated in the overlapping area, which is unusable.
  • the prepared ink composition was placed in a sealed container for each color and stored at room temperature for 2 months in the dark. Then, image formation and tests similar to those described above were performed to determine the storage stability.
  • O is storage stability with no practical problem.
  • Ink cured film A 3 cm x 1 cm square of cellotape (registered trademark) is applied and pressure-bonded firmly, and then quickly peeled off perpendicularly to the surface of the ink cured film.
  • ⁇ is a practical problem! /, Level.
  • the sample of the present invention has high image quality and excellent storage stability, and the hard film has excellent substrate adhesion.

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Abstract

L'invention concerne une composition durcissable par rayonnement actif présentant une haute sensibilité et une bonne stabilité de stockage. L'invention concerne également un procédé visant à faire durcir une telle composition durcissable par rayonnement actif, et un nouveau composé d'anthracène 9,10-diéthérifié. La composition durcissable par rayonnement actif de l'invention est caractérisée en ce qu'elle contient au moins un composé de formule [formule chimique 1] (1), au moins un composé cationiquement polymérisable, et au moins un composé qui génère un acide lorsqu'il est irradié par un rayonnement actif. Dans la formule (1), R1 à R8 désignent indépendamment un atome d'hydrogène ou un substituant, et au moins un élément compris entre R1 et R8 désigne un groupe alkyle C5-C10 ou un groupe cycloalkyle; et R9 et R10 désignent indépendamment un groupe alkyle présentant 1 à 30 atomes de carbone ou analogues.
PCT/JP2007/061797 2006-06-20 2007-06-12 Composition durcissable par rayonnement actif, procédé destiné à durcir cette composition, composition d'encre durcissable par rayonnement actif, procédé de formation d'image et composé associé WO2007148558A1 (fr)

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JP2020075905A (ja) * 2018-09-15 2020-05-21 川崎化成工業株式会社 高分子光重合増感剤
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