JP2007270078A - Ink set for ink-jet recording and ink-jet recording method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for ink-jet recording which has a stability to low-intensity light, exhibits excellent polymerizability in the formation of an image on a medium to be recorded, and has excellent curing properties, and to provide an ink-jet recording method using the same which hardly causes the delivery failure and which has excellent curing properties on the medium to be recorded. <P>SOLUTION: The ink-jet recording ink set and the ink-jet recording method include (I) a liquid comprising an oxetane compound and (II) a liquid comprising an oxirane compound, in which the ratio (mass ratio) p/q between the total amount of the oxetane compound (p1) and the total amount of the oxirane compound (q1) is ≥90/10 even when the liquid (I) comprises the oxirane compound or not, and in which the ratio (mass ratio) p2/q2 between the total amount of the oxetane compound (p2) and the total amount of the oxirane compound (q2) is ≥10/90 even when the liquid (II) comprises the oxetane compound or not. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ink set for ink jet recording and an image forming method, and more specifically, a multi-liquid type ink set for ink jet recording which is difficult to cause ejection failure and has excellent curability on a recording medium, and the ink set The present invention relates to the ink jet recording method used.

  An ink jet system that ejects ink from an ink ejection port such as a nozzle is small and inexpensive, and is used in many printers because it can form an image in a non-contact manner on a recording medium. Among these ink jet systems, the piezoelectric ink jet system that ejects ink using deformation of piezoelectric elements and the thermal ink jet system that ejects ink using the boiling phenomenon of ink due to thermal energy are excellent in high resolution and high speed printability. Has characteristics.

Currently, image storability and high image quality when printing on a non-permeable recording medium such as plastic by an ink jet printer are important issues. In particular, as a serious problem when printing on a non-permeable recording medium, it is known that ink has poor fixability on a recording medium and is inferior in abrasion resistance and water resistance. In addition, if it takes time to dry the droplets after printing, image bleeding tends to occur, and droplet ejection interference occurs due to mixing between adjacent ink droplets, which hinders sharp image formation.
The droplet ejection interference is a phenomenon in which droplets ejected adjacent to each other are united to reduce the surface energy (to reduce the surface area). Since the movement of the droplets occurs when adjacent droplets coalesce, they deviate from the landing position, especially when drawing thin lines with ink containing colorant, the line width is non-uniform and the surface is drawn If it does, it will appear uneven.

In order to improve the fixability and bleeding in the non-penetrable recording medium as described above, as one of the methods for promoting the curing of the ink and fixing it to the recording medium, the ink solvent is not volatilized, A polymerization curable ink for ink jet recording which is cured and fixed by radiation has been proposed (for example, see Patent Document 1).
However, the material used for the polymerization curable ink jet recording ink is a material having a relatively high viscosity, and it is difficult to obtain an ink that is curable and stable at a viscosity that can be discharged by a conventional printer. there were.

On the other hand, as an ink having a low viscosity, excellent photopolymerizability, and excellent curability on a recording medium, a cation polymerization type ink jet recording ink has been proposed.
That is, an active energy ray-curable ink jet recording ink comprising 10 to 50% by weight of a compound containing an oxirane group, 50 to 90% by weight of a compound containing an oxetane ring, and 0 to 40% by weight of a vinyl ether compound is disclosed. (For example, refer to Patent Documents 2 and 3).
However, when a cationic polymerization type ink jet recording ink is used, the polymerization reaction proceeds even when a small amount of acid is generated. Therefore, when the ink is used in a conventionally used ultraviolet curable ink jet printer, There is a problem in that ejection failure occurs due to polymerization of ink attached to the nozzle surface due to leakage light of an ultraviolet light source installed in the printer.

Further, as a cationic polymerization type multi-liquid type ink jet recording method, a recording method using a liquid composed of 30 to 90% oxetane compound, 5 to 70% oxetane compound and 0 to 40% vinyl ether compound is disclosed (for example, , See Patent Document 4). Even the means disclosed here are insufficient to provide light stability against low-intensity light.
Thus, an ink for ink jet recording and a recording method that satisfy both of curability and light stability with respect to low illumination light have not been established.
JP-A-10-323975 JP 2002-188025 A JP 2004-91552 A JP 2005-96254 A

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink set for ink jet recording which is excellent in stability against low illuminance light and has excellent polymerization reactivity and good curability when an image is formed on a recording medium.
Another object of the present invention is to provide an ink jet recording method using the ink set for ink jet recording.

In view of the above circumstances, the present inventors have conducted intensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> An ink set for ink jet recording having at least two kinds of liquids, liquid (I) containing at least a compound having an oxetane ring and liquid (II) containing at least a compound having an oxirane group, ) Does not contain a compound having an oxirane group, or the ratio (mass ratio) p1 / q1 of the total amount of compounds having an oxetane ring (p1) and the total amount of compounds having an oxirane group (q1) is 90/10. In addition, the liquid (II) does not contain a compound having an oxetane ring or the liquid (II) has a ratio of the total amount of compounds having an oxetane ring (p2) to the total amount of compounds having an oxirane group (q2) ( An ink set for ink-jet recording, wherein the mass ratio p2 / q2 is 10/90 or less.
<2> The ink set for inkjet recording according to <1>, wherein the liquid (I) or (II) contains a polymerization initiator.

<3> The ink set for ink jet recording according to <2>, wherein the liquid not containing the polymerization initiator contains a sensitizer.

<4> Any one of <1> to <3>, wherein either one of the liquid (I) and the liquid (II) is a recording liquid containing a colorant, and the other is a treatment liquid. 2. An ink set for ink jet recording according to item 1.

<5> The ink set for ink jet recording according to any one of <4>, wherein the treatment liquid contains a surfactant.
<6> A step of forming an image by ejecting at least two kinds of liquids contained in the ink set for ink jet recording according to any one of <1> to <5> onto a recording medium. A method of applying energy to the cured image and curing the image.

<7> The inkjet recording method according to <6>, wherein the energy is applied by light irradiation or heating.
<8> In the step of forming the image, the ratio (mass ratio) p / q of the total amount (p) of the compound having an oxetane ring contained in two or more liquids and the total amount (q) of the compound having an oxirane group is The inkjet recording method according to <6> or <7>, wherein the method is a step of forming an image by applying the two or more kinds of liquids to the recording medium at 10/90 or more and 90/10 or less.

  INDUSTRIAL APPLICABILITY According to the present invention, an ink set for ink jet recording that is excellent in stability against low illuminance light and has excellent polymerization reactivity and good curability when an image is formed on a recording medium, and the ink for ink jet recording An ink jet recording method using the set can be provided.

The ink set for inkjet recording of the present invention comprises a liquid (I) containing at least a compound having an oxetane ring (hereinafter also referred to as “oxetane ring-containing compound”) and a compound having an oxirane group (hereinafter referred to as “oxirane group-containing compound”). Ink jet recording ink set having at least two types of liquids (II) containing at least a liquid (II), and the liquid (I) does not contain or contain a compound having an oxirane group. However, the ratio (mass ratio) p1 / q1 of the total amount (p1) of the compound having an oxetane ring and the total amount (q1) of the compound having an oxirane group is 90/10 or more, and the liquid (II) contains oxetane. The total amount of compounds having an oxetane ring (p2) and the total amount of compounds having an oxirane group (with or without a compound having a ring) The ratio (mass ratio) p2 / q2 of q2) is 10/90 or less.
The ink set for ink-jet recording of the present invention has the above-described configuration, so that a polymerization reaction or gelation is not promoted even when a very small amount of light such as light leaked from an ultraviolet light source is irradiated. When an image is formed on a recording medium, the ink set for ink jet recording can be provided with excellent polymerization reactivity and good curability.
Next, liquid physical properties, liquids (I) and (II), main components constituting these, and the like of the ink set for inkjet recording of the present invention will be described in detail below.

-Liquid (I)-
The liquid (I) containing at least the compound having an oxetane ring may be liquid at room temperature, but from the viewpoint of ink droplet ejection suitability, the viscosity at 25 ° C. is 100 mPa · s or less, or the viscosity at 60 ° C. is 30 mPa · s. The viscosity at 25 ° C. is preferably 50 mPa · s or lower, or the viscosity at 60 ° C. is more preferably 20 mPa · s or lower. The viscosity at 25 ° C. is 30 mPa · s or lower, or the viscosity at 60 ° C. is 15 mPa · s or lower. It is particularly preferred that it is s or less.
Further, from the viewpoint of fixing the ink to a recording medium and preventing ink bleeding, the liquid (I) preferably contains 50% by mass to 98% by mass of the compound containing the oxetane ring, and 70% by mass to 98%. % By mass is more preferable, and 80% by mass to 98% by mass is particularly preferable.
Further, the liquid (I) is preferably non-aqueous because it takes time to fix when it contains water or an aqueous solvent.

  In addition, the liquid (I) does not contain a compound having an oxirane group, or the liquid (I) contains a compound having an oxirane group and a weight concentration p1 of the compound having an oxetane ring contained in the liquid (I). The relationship of the weight concentration q1 is (p1 / q1) ≧ 90/10. The relationship between p1 and q1 is preferably (p1 / q1) ≧ 99/1, and more preferably the liquid (I) does not contain a compound having an oxirane group.

-Liquid (II)-
The liquid (II) containing at least the compound having an oxirane group may be a liquid at room temperature, but the viscosity at 25 ° C. is 100 mPa · s or less or the viscosity at 60 ° C. is 30 mPa · s or less from the viewpoint of ink droplet ejection suitability. More preferably, the viscosity at 25 ° C. is 50 mPa · s or less, or the viscosity at 60 ° C. is more preferably 20 mPa · s or less, and the viscosity at 25 ° C. is 30 mPa · s or less or the viscosity at 60 ° C. is 15 mPa · s. It is particularly preferred that
Further, from the viewpoint of fixing the ink to a recording medium and preventing ink bleeding, the liquid (II) preferably contains 50% by mass to 98% by mass of the oxirane group-containing compound, and 70% by mass to 98%. % By mass is more preferable, and 80% by mass to 98% by mass is particularly preferable.
The liquid (II) is preferably non-aqueous because it takes time to fix when it contains water or an aqueous solvent.
Further, the liquid (II) does not contain a compound having an oxetane ring, or the liquid (II) contains a compound having an oxirane group and a weight concentration p2 of the compound having the oxetane ring contained in the liquid (II). The relationship of the weight concentration q2 is (p2 / q2) ≦ 10/90. The relationship between p1 and p2 is preferably (p2 / q2) ≦ 1/99, and more preferably the liquid (II) does not contain a compound having an oxetane ring.

<Oxetane ring-containing compound>
The oxetane ring-containing compound can be appropriately selected from compounds containing at least one oxetane ring (oxetanyl group) in the molecule.
For example, as a compound having one oxetane ring in the molecule, a compound represented by the following general formula (1-a) is preferable, and as a compound having two or more oxetane rings in the molecule, the following general formula ( The compounds represented by 1-b) are preferred.

First, the oxetane ring-containing compound represented by the general formula (1-a) will be described.
In the general formula (1-a), Z represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable. R ^1a is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl Represents a group, a furyl group or a thienyl group, preferably an alkyl group having 1 to 6 carbon atoms (particularly a methyl group or an ethyl group).

R ^2a is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or a butyl group), an alkenyl group having 1 to 6 carbon atoms (for example, a 1-propenyl group, 2- Propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, etc.), aryl group (for example, phenyl group, benzyl group, fluoro A benzyl group, a methoxybenzyl group, a phenoxyethyl group, etc.), an alkylcarbonyl group having 1 to 6 carbon atoms (for example, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, etc.), an alkoxycarbonyl group having 1 to 6 carbon atoms ( For example, ethoxycarbonyl group, propoxycarbonyl group, butyroxycarbonyl group, etc.), C1-C6 alkoxycarbamoyl group (example) If, ethoxy carbamoyl group, propoxy carbamoyl group, butyl pentyl b alkoxy carbamoyl group), representing the like.

Of the oxetane ring-containing compounds represented by the general formula (1-a), R ^1a is a lower alkyl group (particularly an ethyl group), and R ^2a is a hydrogen atom, a butyl group, a phenyl group, or a benzyl group. An embodiment in which Z is an oxygen atom is particularly preferred. Here, the lower alkyl group refers to an alkyl group having 1 to 3 carbon atoms (the same applies hereinafter).
In addition, the oxetane ring-containing compound represented by the general formula (1-a) may be used alone or in combination of two or more.

Next, the oxetane ring-containing compound represented by the general formula (1-b) will be described.
In the general formula (1-b), m represents 2, 3 or 4, Z represents an oxygen atom or a sulfur atom, and Z is preferably an oxygen atom.

In the general formula (1-b), R ^1b is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group), a phenyl group, or a carbon number. 1 to 6 fluoroalkyl groups, allyl groups, aryl groups, or furyl groups are represented.

R ^2b represents a linear or branched alkylene group having 1 to 12 carbon atoms, a linear or branched poly (alkyleneoxy) group, or a divalent group selected from the group consisting of the following general formulas (3), (4) and (5). Represents a group of

The linear or branched alkylene group having 1 to 12 carbon atoms is preferably a group represented by the following general formula (2). R ³ in the following general formula (2) represents a lower alkylene group such as a methylene group, an ethylene group, or a propylene group.

In the general formula (3), n represents 0 or an integer of 1 to 2000, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, or the like) or a group selected from groups represented by the following general formula (6). R ⁵ represents an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, etc.), preferably a methyl group It is.

In the general formula (6), j represents 0 or an integer of 1 to 100, and R ⁶ represents an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, etc.), preferably a methyl group.

In the general formula (4), R ⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl groups, etc.), C1-C10 alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), halogen atoms (eg, fluorine, chlorine, bromine, iodine, etc.) ), A nitro group, a cyano group, a mercapto group, an alkoxycarbonyl group (for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, etc.), or a carboxyl group.

In the general formula (5), R ⁸ represents an oxygen atom, a sulfur atom, NH, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) ₂ .

Of the oxetane ring-containing compounds represented by the general formula (1-b), in the general formula (1-b), R ^1b represents a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.). And particularly preferably an ethyl group, and R ^2b is a group in which R ^{7 in the} general formula (4) is a hydrogen atom, a hexamethylene group, R ^{3 in the} general formula (2) is an ethylene group, or a general formula (3) R ⁵ is and R ⁴ are methyl group is a group R ⁶ in the general formula (6) is a methyl group, a Z is an oxygen atom, aspect m is 2 are preferred.

  Furthermore, examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following general formula (7) or (8).

In the general formula (7), r represents an integer of 25 to 200, and R ⁹ represents an alkyl group having 1 to 4 carbon atoms or a trialkylsilyl group. In addition, R ¹ in the general formulas (7) and (8) and R ⁶ in the general formula (7) are respectively R ^1b in the general formula (1-b) and R ^{6 in the} general formula (6). It is synonymous with.

  Hereinafter, preferable specific examples [Exemplary compounds 1 to 37 and (a) to (f)] of the oxetane ring-containing compound represented by the general formula (1-a) or (1-b) are listed. However, the present invention is not limited to these.

The synthesis of the oxetane ring-containing compound is described in (1) H. A. J. et al. Curless, "Synthetic Organic Photochemistry", Plenum, New York (1984), (2) M.M. Braun, Nachr. Chem. Tech. Lab. 33, 213 (1985), (3) S. et al. H. Schroeter, J.A. Org. Chem. , 34, 5, 1181 (1969), (4) D.M. R. Arnold, Adv. Photochem. , 6, 301 (1968), (5) "Heterocyclic Compounds with Three- and Four-membered Rings", Part Two, Chapter IX, Interscience Publishers, John W, Y & W Chem. Soc. Jpn. 61, 1653 (1988), (7) Pure Appl. Chem. A29 (10), 915 (1992), (8) Pure Appl. Chem. , A30 (2 &amp; 3), 189 (1993), (9) JP-A-6-16804, (10) German Patent No. 1,021,858, and the like.
In addition, the oxetane ring-containing compound represented by the general formula (1-b) can also be used in combination of two or more, in addition to being used alone.

  Of the oxetane ring-containing compounds, exemplary compound (a), exemplary compound (b), exemplary compound (d), and exemplary compound (f) are preferred.

<Oxirane group-containing compound>
The oxirane group-containing compound can be appropriately selected from compounds containing at least one oxirane group (oxiranyl group) having the following oxirane ring in the molecule, specifically those usually used as epoxy resins. , Any of monomer, oligomer and polymer.

  Specific examples of the oxirane group-containing compound include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Here, the epoxy resin refers to a monomer, an oligomer, or a polymer.

  Suitable examples of the aromatic epoxy resin include di- or poly-glycidyl ethers produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin. . For example, di- or poly-glycidyl ether of bisphenol A or its alkylene oxide adduct, di- or poly-glycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and novolak type epoxy resin. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxy resin, preferably, a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring is epoxidized with a suitable oxidizing agent such as hydrogen peroxide or peracid. The cyclohexene oxide or the cyclopentene oxide containing compound obtained by this is mentioned. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

  Suitable examples of the aliphatic epoxy resin include di- or poly-glycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. For example, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, di- or tri-glycidyl of glycerin or its alkylene oxide adduct Polyglycidyl ether of polyhydric alcohol such as ether, diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, diglycidyl ether of polyalkylene glycol such as polypropylene glycol or diglycidyl ether of its alkylene oxide adduct, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the oxirane group-containing compound, in addition to the above-mentioned compounds, monoglycidyl ethers of aliphatic higher alcohols that are monomers having one oxirane ring in the molecule, monoglycidyl ethers of phenols, cresols or alkylene oxide adducts thereof, etc. Also mentioned.
In addition, the said oxirane group containing compound can also use 2 or more types together besides using individually by 1 type.

  Hereinafter, preferred specific examples (exemplary compounds (i) to (viii)) of the oxirane group-containing compound are listed. However, the present invention is not limited to these.

  Of the oxirane group-containing compounds, the exemplified compound (i) and the exemplified compound (v) are preferable.

(Polymerization initiator)
The liquid in the present invention preferably contains a cationic polymerizable polymerization initiator in order to promptly accelerate the polymerization reaction.
Although the said polymerization initiator is not specifically limited, It is preferable to contain in liquid (I) and / or liquid (II), and it is more preferable to contain in either one from a viewpoint of low illumination stability.
The polymerization initiator more preferably contains a compound that generates an acid upon irradiation with radiation (also referred to as a photoacid generator as appropriate).
Examples of photoacid generators that can be used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and light used for microresists. (400-200 nm ultraviolet rays, far ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam, ion beam, etc. A compound capable of generating can be appropriately selected and used.

  Examples of such a photoacid generator include an onium salt compound such as a diazonium salt, a phosphonium salt, a sulfonium salt, and an iodonium salt that decomposes upon irradiation with radiation, an imide sulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, Examples thereof include sulfonate compounds such as o-nitrobenzyl sulfonate.

  Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, S.P. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal etal, Polymer, 21, 423 (1980), U.S. Pat. Nos. 4,069,055, 4,069,056, Re 27,992, JP-A-3-140140, etc. An ammonium salt according to claim 1, C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, and the like; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-296514 and the like,

  J. et al. V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al. PolymerSci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al., Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. Polymer Sci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, and 297,442. U.S. Pat.Nos. 3,902,114, 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patent 2, Nos. 904, 626, 3,604, 580, 3,604, 581, JP-A-7-28237, 8-27102 and the like,

  J. et al. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), etc., selenonium salts, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-55. -32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243 , Organic halogen compounds described in JP-A-63-298339 and the like; Meier et al, J.A. Rad. Curing, 13 (4), 26 (1986), T.A. P. Gill et al, Inorg. Chem. , 19, 3007 (1980), D.M. Astruc, Acc. Chem. Res. , 19 (12), 377 (1986), and organometallic / organic halides described in JP-A-2-161445, etc.

  S. Hayase et al. Polymer Sci. 25, 753 (1987), E.I. Reichmanis et al. Polymer Sci. , Polymer Chem. Ed. , 23, 1 (1985), Q.M. Q. Zhu etal, J. et al. Photochem. 36, 85, 39, 317 (1987), B.R. Amit etal, Tetrahedron Lett. , (24) 2205 (1973), D.M. H. R. Barton et al. Chem. Soc. , 3571 (1965), p. M.M. Collins et al, J.A. Chem. Soc. Perkin I, 1695 (1975), M .; Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), J. MoI. W. Walker et al. Am. Chem. Soc. 110, 7170 (1988), S.A. C. Busman et al. Imaging Technol. 11 (4), 191 (1985), H. et al. M.M. Houlihan et al, Macormolecules, 21, 2001 (1988), p. M.M. Collins et al. Chem. Soc. , Chem. Commun. 532 (1972), S.A. Hayase et al., Macromolecules, 18, 1799 (1985), E.I. Reichmanis et al. Electrochem. Soc. , Solid State Sci. Technol. , 130 (6), F.M. M.M. Houlihan et al, Macromolecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, US Patent No. 3 , 901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having an O-nitrobenzyl type protecting group,

  M.M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), G.M. Berner et al. Rad. Curing, 13 (4), W.M. J. et al. Mijs et al, Coating Technol. , 55 (697), 45 (1983), Akzo, H .; Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent No. 0199,672, No. 84515, No. 044,115, No. 618,564, No. 0101,122, US Pat. No. 4,371 , 605, 4,431,774, JP-A 64-18143, JP-A-2-245756, JP-A-3-140109, and the like. Compounds generating an acid, disulfone compounds described in JP-A-61-1166544 and JP-A-2-71270, diazo compounds described in JP-A-3-103854, JP-A-3-103856, and JP-A-4-210960 Examples thereof include ketosulfone and diazodisulfone compounds.

Further, a group which generates an acid by these light, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, E. Woodhouse et al., J. MoI. Am. Chem. Soc. 104, 5586 (1982), S .; P. Pappas et al. Imaging Sci. , 30 (5), 218 (1986), S .; Kondo et al, Makromol. Chem. , Rapid Commun. , 9, 625 (1988), Y. et al. Yamada et al, Makromol. Chem. 152, 153, 163 (1972), J. Am. V. Crivello et al, J.A. PolymerSci. , Polymer Chem. Ed. 17, 3845 (1979), U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, JP-A 63-26653, JP-A 55-164824, JP-A 62- 69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A 63-146029, and the like can be used. For example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, photoacid generators having o-nitrobenzyl type protecting groups Examples thereof include a compound capable of generating a sulfonic acid by photolysis represented by an agent, iminosulfonate, and the like, a disulfone compound, a diazoketosulfone, and a diazodisulfone compound.

  Furthermore, V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al, J.A. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent No. 126,712, and the like, compounds that generate an acid by light can also be used.

Preferred compounds as photoacid generators that can be used in the present invention include the following formulas (b1) and (b2
) And (b3).

In the formula (b1), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represents an organic group. X ⁻ represents a non-nucleophilic anion, preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ or the following The organic anion which has a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following formula.

Rc ¹ represents an organic group.
Examples of the organic group in Rc ¹ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these are a single bond, —O—, —CO ₂ —, —S—. , —SO ₃ —, —SO ₂ N (Rd ¹ ) — and the like.

Rd ¹ represents a hydrogen atom or an alkyl group.
Rc ³ , Rc ⁴ and Rc ⁵ each independently represents an organic group.
Preferred examples of the organic group for Rc ³ , Rc ⁴ , and Rc ⁵ include the same organic groups as those for Rc ¹ , and most preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Rc ³ and Rc ⁴ may combine to form a ring.
Examples of the group formed by combining Rc ³ and Rc ⁴ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.

The organic group of Rc ¹ and Rc ^{3 to} Rc ⁵ is most preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.

The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is generally 1-30, preferably 1-20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ²⁰¹ to R ^203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ include corresponding groups in the compounds (b1-1), (b1-2) and (b1-3) described later.

In addition, the compound which has two or more structures represented by Formula (b1) may be sufficient. For example, at least one of R ^{201 to} R ²⁰³ of the compound represented by the general formula (b1) is directly or linked to at least one of R ^{201 to} R ²⁰³ in the other compound represented by the formula (b1). It may be a compound having a structure bonded through a group.

  Further preferred examples of the component (b1) include compounds (b1-1), (b1-2), and (b1-3) described below.

Compound (b1-1) is in which at least one aryl group R ²⁰¹ to R ²⁰³ in formula (b1), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R ^{201 to} R ²⁰³ may be an aryl group, or a part of R ^{201 to} R ²⁰³ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldicycloalkylsulfonium compounds, and the like.

  The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

As the alkyl group that the arylsulfonium compound has as necessary, a linear or branched alkyl group having 1 to 15 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A butyl group, a t-butyl group, etc. can be mentioned.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ²⁰¹ to R ^203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferred. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Substituents, of the three R ²⁰¹ to R ^203, may be substituted on any one, or may be substituted on all of three. When R ^{201 to} R ²⁰³ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (b1-2) will be described.
The compound (b1-2) is a compound in the case where R ^{201 to} R ²⁰³ in the formula (b1) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ²⁰¹ to R ²⁰³ each independently, preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R ²⁰¹ to R ²⁰³ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, a butyl group, a pentyl group), and a linear, branched 2-oxoalkyl group, and an alkoxycarbonylmethyl group are more preferable.

The cycloalkyl group as R ²⁰¹ to R ²⁰³ is preferably a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, a norbornyl group) can be exemplified, more preferably a cyclic 2-oxoalkyl group.

Linear R ²⁰¹ to R ^203, branched, or cyclic 2-oxoalkyl group, preferably, may be mentioned 2-position group having> C = O at the above-described alkyl or cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ²⁰¹ to R ^203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R ^{201 to} R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (b1-3) is a compound represented by the following formula (b1-3) and is a compound having a phenacylsulfonium salt structure.

In formula (b1-3), R ^{1c to} R ^5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R ^6c and R ^7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R ^x and R ^y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y may be bonded to each other to form a ring structure.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ^{− in} formula (b1).

The alkyl group as R ^{1c to} R ^7c may be either linear or branched, and for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).

Preferred examples of the cycloalkyl group represented by R ^{1c to} R ^7c include cycloalkyl groups having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R ^{1c to} R ^{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Examples of the group formed by combining any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y include a butylene group and a pentylene group. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

Preferably any one of R ^{1c to} R ^5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R ^1c to R ^5c is 2-15. Solvent solubility is further improved, and generation of particles during storage is suppressed, which is preferable.

^Examples of the alkyl group and cycloalkyl group as R ^x and R ^y include the same alkyl groups and cycloalkyl groups as R ^{1c to} R ^7c .
R ^x and R ^y are preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group.
Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R ^{1c to} R ^5c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R ^{1c to} R ^5c .

R ^x and R ^y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

Formula (b2), in (b3), R ²⁰⁴ ~R ²⁰⁷ each independently represents an aryl group, an alkyl group or a cycloalkyl group. X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (b1).

Phenyl group and a naphthyl group are preferred as the aryl group of R ²⁰⁴ to R ^207, more preferably a phenyl group.
The alkyl group as R ²⁰⁴ to R ²⁰⁷ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The cycloalkyl group as R ²⁰⁴ to R ²⁰⁷ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
The R ²⁰⁴ to R ²⁰⁷ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

Examples of the compound that generates an acid upon irradiation with actinic rays or radiation that may be used further include compounds represented by the following formulas (b4), (b5), and (b6).

In formulas (b4) to (b6), Ar ³ and Ar ⁴ each independently represents an aryl group.
R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Preferable examples of the photoacid generator include compounds represented by formulas (b1) to (b3).
Preferred compound examples [(b-1) to (b-96)] of the photoacid generator that can be used in the present invention are listed below, but the present invention is not limited thereto.

Further, oxazole derivatives and s-triazine derivatives described in JP-A No. 2002-122994, paragraph numbers [0029] to [0030] are also preferably used.
The onium salt compounds and sulfonate compounds exemplified in JP-A-2002-122994, paragraphs [0037] to [0063] can also be suitably used in the present invention.

  A polymerization initiator can be used individually by 1 type or in combination of 2 or more types. The content of the polymerization initiator in the liquid is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1 to 7% by weight in terms of the total solid content of the liquid. .

(Sensitizer)
It is preferable to contain a sensitizer in the liquid which does not contain a polymerization initiator among the liquids in this invention from a viewpoint of low illumination stability.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizer include compounds represented by the following general formulas (IX) to (XIII).

In formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.
In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (IX).
In the formula (XI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with the adjacent A ² and carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ^4, and adjacent carbon atoms; R ⁶⁰ and R ⁶¹ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.
In formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferred specific examples of the compounds represented by the general formulas (IX) to (XIII) include the exemplified compounds (A-1) to (A-20) shown below.

(Co-sensitizer)
Further, the liquid (I) and / or the liquid (II) in the present invention may be added with a known compound having a function of further improving sensitivity or suppressing polymerization inhibition by oxygen as a co-sensitizer. . Like the sensitizer, the co-sensitizer is preferably contained in the liquid (II) containing the photopolymerization initiator from the viewpoint of liquid stability.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56-75643. Examples thereof include disulfide compounds, and specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.
Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in JP-A-8-65779 H, Ge-H compound, etc. are mentioned.

(Coloring agent)
In the present invention, at least one of the liquid (I) and the liquid (II) preferably contains a colorant.
The colorant that can be used here is not particularly limited, and various publicly known pigments and dyes can be appropriately selected and used depending on the application, and are pigments from the viewpoint of particularly excellent light resistance. It is preferable.

The pigment preferably used in the present invention will be described.
The pigment is not particularly limited, and all commercially available organic pigments and inorganic pigments, and those obtained by dyeing resin particles with a dye can be used. Furthermore, commercially available pigment dispersions and surface-treated pigments, for example, pigments dispersed in an insoluble resin or the like as a dispersion medium, or those obtained by grafting a resin on the pigment surface, etc., impair the effects of the present invention. It can be used as long as it is not.
Examples of these pigments include, for example, “Pigment Dictionary” (2000), edited by Seijiro Ito. Herbst, K.M. Hunger “Industrial Organic Pigments”, JP 2002-12607 A, JP 2002-188025 A, JP 2003-26978 A, and JP 2003-342503 A3.

  Specific examples of organic pigments and inorganic pigments that can be used in the present invention include C.I. I. Pigment Yellow 1 (Fast Yellow G etc.), C.I. I. A monoazo pigment such as C.I. Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Yellow 115 (quinoline yellow lake, etc.); I. Basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavantron Yellow (Y-24), isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110), and quinophthalone yellow Quinophthalone pigments such as (Y-138), isoindoline pigments such as isoindoline yellow (Y-139), C.I. I. Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.); I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).

  C. As a thing which exhibits red or magenta color, C.I. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I. I. Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I. Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.).

  As a pigment exhibiting blue or cyan, C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (Peacock Blue Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkali blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).

As a pigment exhibiting green, C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Phthalocyanine pigments such as C.I. Pigment Green 36 (phthalocyanine green); I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green).
As a pigment exhibiting an orange color, C.I. I. An isoindoline pigment such as C.I. Pigment Orange 66 (isoindoline orange); I. And anthraquinone pigments such as CI Pigment Orange 51 (dichloropyrantron orange).

Examples of the black pigment include carbon black, titanium black, and aniline black.
Specific examples of the white pigment include basic lead carbonate (2PbCO ₃ Pb (OH) ₂ , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO 2, so-called titanium white), titanium Strontium acid (SrTiO ₃ , so-called titanium strontium white) can be used.

  Here, titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable, so that it has a large hiding power and coloring power as a pigment. Excellent durability against other environments. Therefore, it is preferable to use titanium oxide as the white pigment. Of course, other white pigments (may be other than the listed white pigments) may be used as necessary.

For dispersing the colorant, for example, a dispersing device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used. be able to.
When dispersing the colorant, it is particularly preferable to add the dispersant.
Moreover, when adding a coloring agent, it is also possible to use the synergist according to various coloring agents as a dispersing aid as needed. The dispersing aid is preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the colorant.

  When the liquid (I) or (II) contains a colorant, a solvent may be added as a dispersion medium for various components such as a colorant, and the polymerization is a low molecular weight component without a solvent. The liquids (I) and (II) are preferably active energy ray-curable liquids, and the liquids (I) and (II) are placed on the recording medium. In order to cure after application, it is preferably solventless. This is because if the solvent remains in the image formed from the cured liquids (I) and (II), the solvent resistance deteriorates, and the problem of VOC (Volatile Organic Compound) of the remaining solvent arises. It is. From such a viewpoint, a polymerizable compound is used as the dispersion medium, and in particular, it is possible to select a polymerizable compound having the lowest viscosity to improve dispersion suitability and handling properties of the liquids (I) and (II). To preferred.

The average particle diameter of the colorant used here is preferably from 0.01 to 0.4 μm, more preferably from 0.02 to 0.2 μm, because the finer the particle, the better the color developability. (A) Selection of colorant, dispersant, dispersion medium, dispersion conditions, and filtration conditions are set so that the maximum particle size is 3 μm or less, preferably 1 μm or less. By controlling the particle size, clogging of the head nozzle can be suppressed, and the storage stability, transparency, and curing sensitivity of the liquids (I) and (II) can be maintained. In the present invention, even when a fine particle colorant is used by using the dispersant having excellent dispersibility and stability, a uniform and stable dispersion can be obtained.
The particle size of the colorant in the liquid (I) or (II) can be measured by a known measurement method. Specifically, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, and a dynamic light scattering method. In the present invention, a value obtained by measurement using a laser diffraction / scattering method is employed.
The concentration of the colorant used in the liquid (I) or (II) is preferably 50% by mass or less, more preferably 1 to 50% by mass from the viewpoint of dispersion stability or solubility. It is especially preferable that it is 2-50 mass%.
In the present invention, a liquid containing a colorant serves as a recording liquid, and the other liquid serves as a processing liquid. That is, when the liquid (I) contains a colorant, the liquid (I) is a recording liquid and the liquid (II) is a processing liquid. However, the treatment liquid may contain a colorant, but it is necessary that the content of the colorant in the recording liquid is not exceeded. When the colorant is included in the treatment liquid, the content is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably no colorant is contained in the treatment liquid.

In the present invention, as described above, it is preferable that one of the liquid (I) and the liquid (II) is a recording liquid containing a colorant, and the other is a processing liquid.
When the recording liquid and the processing liquid are mixed on a recording medium to form an image, a distorted image may be obtained due to bleeding of recording droplets or enlargement of the droplet size. Thus, in order to form an excellent high-definition image free from image disturbance due to recording liquid bleeding or enlargement, the relationship between the surface tension γ1 of the recording liquid and the surface tension γ2 of the processing liquid is expressed as γ2 <γ1 ( mN / m), preferably γ2 <γ1-3 (mN / m), and more preferably γ2 <γ1-5 (mN / m).
Here, the surface tension is a value measured at a liquid temperature of 20 ° C. using a generally used surface tension meter (for example, surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.). .

In order to obtain the surface tension values of the recording liquid and the processing liquid, it is necessary to select the composition of the recording liquid and the processing liquid, and it is preferable to use a surfactant for the preparation of these surface tensions.
Among the above, it is preferable to add a surfactant to the treatment liquid from the viewpoint of obtaining a high-definition image.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. Specifically, for example, anionic surfactants such as dialkylsulfosuccinates (such as di-2-ethylhexyl sodium sulfosuccinate), alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl Nonionic surfactants such as allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, silicone surfactants (poly Oxyethylene-methylpolysiloxane copolymer, etc.).
In addition, it is also preferable to use an organic fluoro compound instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include fluorine-based surfactants (eg, MegaFuck series (F444, F445, F446).
F470, F471, F475, F477, etc.) manufactured by Dainippon Ink Co., Ltd.), oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin), Examples described in JP-B-57-9053 (columns 8 to 17) and JP-A-62-135826 (p.3, upper right column, line 13 to p.6, lower left column, line 13). It is done.
In particular, the surfactant that can be used in the present invention is not limited to the above-mentioned surfactant, and may be any additive capable of effectively reducing the surface tension of the recording liquid and the processing liquid with respect to the added concentration. It ’s fine.
The addition amount of the surfactant in the present invention is not particularly limited because it needs to be added so as to satisfy the surface tension value, but is preferably 0.01% by mass to 10% by mass, and more preferably Is 0.05% by mass to 5% by mass, and particularly preferably 0.1% by mass to 3% by mass.

In addition to the sensitizer and co-sensitizer used together with the polymerization initiator component and the polymerization initiator component which are essential components and optional components, the liquid (I) and / or the liquid (II) in the present invention are used for the purpose. Depending on the case, various additives can be used in combination. For example, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration. Moreover, antioxidant can be added for the stability improvement of liquid (I) and / or liquid (II).
The liquid (I) and / or liquid (II) in the present invention further includes various organic and metal complex antifading agents, potassium thiocyanate, lithium nitrate, and ammonium thiocyanate for the purpose of controlling ejection properties. In order to improve the adhesion with conductive salts such as dimethylamine hydrochloride and the recording medium, a trace amount of organic solvent can be added.

Various polymer compounds can be added to the liquid (I) and / or the liquid (II) in order to adjust film physical properties. Examples of polymer compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination.
In addition, nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties. In addition, for example, leveling additives, matting agents, In order to improve the adhesion to the recording medium such as waxes for adjusting film physical properties, polyolefin, PET, etc., a tackifier that does not inhibit the polymerization can be contained.

(High boiling point organic solvent)
In the present invention, a high-boiling organic solvent can be contained, but as described above, a high-boiling organic solvent is preferable from the viewpoint of suppressing emission of volatile organic compounds (VOC).
As the high boiling point organic solvent, (1) a viscosity at 25 ° C. of 100 mPa · s or less or a viscosity at 60 ° C. of 30 mPa · s or less and (2) a boiling point higher than 100 ° C. is preferable.

  In a high boiling point organic solvent that does not satisfy any of the viscosity conditions of (1), the viscosity becomes high, which may hinder application on a recording medium, and the boiling point condition of (2) is satisfied. If the organic solvent has a high boiling point, the boiling point becomes too low and the solvent evaporates during image recording, which may reduce the effect of the present invention.

  Among the conditions (1), the viscosity at 25 ° C. is further preferably in the range of 70 mPa · s or less, more preferably in the range of 40 mPa · s or less, and particularly preferably in the range of 20 mPa · s or less. The viscosity at 60 ° C. is more preferably in the range of 20 mPa · s or less, and particularly preferably in the range of 10 mPa · s or less. Regarding the condition (2), the boiling point is more preferably in the range of 150 ° C. or higher, and particularly preferably in the range of 170 ° C. or higher. Moreover, as a lower limit of melting | fusing point, the range of 80 degrees C or less is preferable. Furthermore, the solubility (25 ° C.) of water is preferably 4 g or less, more preferably 3 g or less, further preferably 2 g or less, and particularly preferably 1 g or less.

  The “viscosity” here is a viscosity determined using a RE80 viscometer manufactured by Toki Sangyo Co., Ltd. The RE80 type viscometer is a conical rotor / flat plate type viscometer corresponding to the E type, and the rotor code No. 1 rotor was used and the measurement was performed at a rotation speed of 10 rpm. However, for those having a viscosity higher than 60 mPa · s, the rotational speed is 5 r.p.m., 2.5 r.p.m., 1 r.p.m., 0.5 r.p.m. The measurement was performed by changing to.

  The “water solubility” is the saturation concentration of water in a high boiling point organic solvent at 25 ° C., and means the mass (g) of water that can be dissolved in 100 g of the high boiling point organic solvent at 25 ° C.

  As the high boiling organic solvent, compounds represented by the following formulas [S-1] to [S-9] are preferable.

In the formula [S-1], R ₁ , R ₂ and R ₃ each independently represents an aliphatic group or an aryl group. A, b and c each independently represent 0 or 1;

In the formula [S-2], R ₄ and R ₅ each independently represents an aliphatic group or an aryl group, and R ₆ represents a halogen atom (F, Cl, Br, I and so on), an alkyl group, an alkoxy group, Represents an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and d represents an integer of 0 to 3. When d is plural, plural R ₆ may be the same or different.

In the formula [S-3], Ar represents an aryl group, e represents an integer of 1 to 6, and R ₇ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-4], R ₈ represents an aliphatic group, f represents an integer of 1 to 6, and R ₉ represents an f-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-5], g represents an integer of 2 to 6, R ₁₀ represents a g-valent hydrocarbon group (excluding an aryl group), and R ₁₁ represents an aliphatic group or an aryl group.

In the formula [S-6], R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an aliphatic group or an aryl group. X represents —CO— or —SO ₂ —. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may be bonded to each other to form a ring.

In the formula [S-7], R ₁₅ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group, and R ₁₆ represents a halogen atom, an aliphatic group or an aryl group. Represents a group, an alkoxy group or an aryloxy group, and h represents an integer of 0 to 3. When h is plural, plural R ₁₆ may be the same or different.

In the formula [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group or an aryl group, R ₁₉ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group, and i Represents an integer of 0 to 5. When i is plural, plural R ₁₉ may be the same or different.

In the formula [S-9], R ₂₀ and R ₂₁ each independently represents an aliphatic group or an aryl group. j represents 1 or 2; R ₂₀ and R ₂₁ may be bonded to each other to form a ring.

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are an aliphatic group or a group containing an aliphatic group, the aliphatic group is a straight chain, It may be branched or cyclic, and may contain an unsaturated bond or may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the formulas [S-1] to [S-9], R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are cyclic aliphatic groups, that is, cycloalkyl groups, or groups containing cycloalkyl groups. Sometimes, the cycloalkyl group may contain an unsaturated bond in the 3- to 8-membered ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, and an epoxy group, and examples of the crosslinking group include methylene, ethylene, isopropylidene, and the like.

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ , R _{11 to} R ₂₁ , Ar is an aryl group or a group containing an aryl group, the aryl group is a halogen atom, aliphatic It may be substituted with a substituent such as a group, an aryl group, an alkoxy group, an aryloxy group, or an alkoxycarbonyl group.

In the formulas [S-3], [S-4], and [S-5], when R ₇ , R _9, or R ₁₀ is a hydrocarbon group, the hydrocarbon group is a cyclic structure (for example, a benzene ring, a cyclopentane ring, A cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Hereinafter, among the high boiling point organic solvents represented by the formulas [S-1] to [S-9], particularly preferred high boiling point organic solvents will be described.
In the formula [S-1], R ₁ , R ₂ and R ₃ are each independently an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms (for example, n-butyl, n-hexyl, n -Octyl, EH-octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, 3,5,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2,3-dichloro Propyl, 2-butoxyethyl, 2-phenoxyethyl, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, phenyl, Cresyl, p-nonylphenyl, xylyl, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl) are preferred Yes. Among these, R ₁ , R ₂ and R ₃ are particularly n-hexyl, n-octyl, EH-octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, n-dodecyl, 2-chloroethyl, 2- Butoxyethyl, cyclohexyl, phenyl, cresyl, p-nonylphenyl and cumenyl are preferred.
a, b and c are each independently 0 or 1, and more preferably a, b and c are all 1.

In the formula [S-2], R ₄ and R ₅ are each independently an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms (for example, the same group as the aliphatic group mentioned for R ₁ above). , Heptyl, ethoxycarbonylmethyl, 1,1-diethylpropyl, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl, 3,5,5-trimethylcyclohexyl, menthyl, bornyl, 1-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, the aryl group mentioned for R ₁ , 4-t-butylphenyl, 4-t-octylphenyl, 1, 3,5-trimethylphenyl, 2,4, -di-t-butylphenyl, 2,4, -di-t-pentylphenyl) are preferred. Among these, R ₄ and R ₅ are more preferably aliphatic groups, and particularly preferably n-butyl, heptyl, 2-ethylhexyl, n-dodecyl, 2-butoxyethyl, and ethoxycarbonylmethyl.
R ₆ is a halogen atom (preferably a chlorine atom), an alkyl group having 1 to 18 carbon atoms (eg, methyl, isopropyl, t-butyl, n-dodecyl), an alkoxy group having 1 to 18 carbon atoms (eg, methoxy, n -Butoxy, n-octyloxy, methoxyethoxy, benzyloxy), an aryloxy group having 6 to 18 carbon atoms (for example, phenoxy, p-tolyloxy, 4-methoxyphenoxy, 4-t-butylphenoxy) or 2 carbon atoms A C-19 alkoxycarbonyl group (for example, methoxycarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl) or an aryloxycarbonyl group having 6 to 25 carbon atoms is preferred. Among these, R ₆ is further preferably an alkoxycarbonyl group, and particularly preferably n-butoxycarbonyl.
d is 0 or 1.

In the formula [S-3], Ar is an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, phenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, 1-naphthyl, 4- n-butoxyphenyl, 1,3,5-trimethylphenyl, 2- (2-n-butoxycarbonylphenyl) phenyl) are preferable, and among these, Ar is phenyl, 2,4-dichlorophenyl, 2- (2 -N-Butoxycarbonylphenyl) phenyl is preferred.
e is an integer of 1 to 4 (preferably 1 to 3).
R ₇ is an e-valent hydrocarbon group having 2 to 24 (preferably 2 to 18) carbon atoms [for example, the aliphatic group mentioned above for R ₄ , n-octyl, the aryl group mentioned for R ₄ ,-( CH _{2) 2} -,

] Or an e-valent hydrocarbon group having 4 to 24 (preferably 4 to 18) carbon atoms and bonded to each other by an ether bond [for example, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ (OCH _{2 CH 2) 3 -, - CH} 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -,

] Is preferable. Among these, R ₇ is more preferably an alkyl group, and particularly preferably n-butyl, n-octyl and 2-ethylhexyl.

In the formula [S-4], R ₈ is an aliphatic group having 1 to 24 (preferably 1 to 17) carbon atoms (for example, methyl, n-propyl, 1-hydroxyethyl, 1-ethylpentyl, n-heptyl, n - undecyl, n- tridecyl, pentadecyl, 8,9-epoxy heptadecyl, cyclopropyl, cyclohexyl, 4-methylcyclohexyl). among them, R ₈ in particular, n- heptyl, n- tridecyl, 1-hydroxy Ethyl, 1-ethylpentyl, and 8,9-epoxyheptadecyl are preferred.
f is an integer of 1 to 4 (preferably 1 to 3).
R ₉ is a hydrocarbon group having 2 to 24 (preferably 2 to 18) f-valent carbon atoms or a hydrocarbon group linked to each other by an ether bond having 4 to 24 (preferably 4 to 18) f-valent carbon atoms. (For example, the groups mentioned for R ₇ , 1-methyl-2-methoxyethyl, 2-hexyldecyl) are preferable, and among these, R ₉ is particularly 2-ethylhexyl, 2-hexyldecyl, 1-methyl-2 -Methoxyethyl,

Is preferred.

In the formula [S-5], g is 2 to 4 (preferably 2 or 3).
R ₁₀ represents a g-valent hydrocarbon group [for example, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₇ —, — (CH ₂ ) ₈ —,

Among these, R ₁₀ is particularly — (CH ₂ ) ₄ —, — (CH ₂ ) ₈ —,

Is preferred.
R ₁₁ is an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms, or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, the aliphatic groups mentioned for R ₄ above, Aryl group). Among these, R ₁₁ is more preferably an alkyl group, and n-butyl, n-octyl, and 2-ethylhexyl are particularly preferable.

In the formula [S-6], R ₁₂ is a hydrogen atom, an aliphatic group having 1 to 24 carbon atoms (preferably 3 to 20) [for example, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2,4-di-t-pentylphenoxymethyl, 4-t-octylphenoxymethyl, 3- (2,4-di-t-butylphenoxy) propyl, 1- (2,4-di-t-butylphenoxy) propyl Cyclohexyl, 4-methylcyclohexyl, 8-N, N-diethylcarbamoyloctyl], or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, the aryl group mentioned for Ar, 3-methylphenyl) , 2-(N, N-di -n- octylcarbamoyl) phenyl). among them, R ₁₂ is especially, n- undecyl, 8-N, N-di Ji carbamoyl octyl, 3-methylphenyl, 2-(N, N-di -n- octylcarbamoyl) phenyl are preferred.
R ₁₃ and R ₁₄ are each a hydrogen atom or an aliphatic group having 1 to 24 (preferably 1 to 18) carbon atoms (eg, methyl, ethyl, isopropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl). , N-dodecyl, n-tetradecyl, cyclopentyl, cyclopropyl) or an aryl group having 6 to 18 carbon atoms (preferably 6 to 15) (for example, phenyl, 1-naphthyl, p-tolyl), among these, R ₁₃ and R ₁₄ are particularly preferably methyl, ethyl, n-butyl, n-octyl, n-tetradecyl and phenyl.
R ₁₃ and R ₁₄ may be bonded to each other to form a pyrrolidine ring, piperidine ring or morpholine ring together with N, and R ₁₂ and R ₁₃ may be bonded to each other to form a pyrrolidone ring or piperidine ring together with N. Also good.
X is —CO— or —SO ₂ —, and preferably X is —CO—.

In the formula [S-7], R ₁₅ is an aliphatic group having 1 to 24 (preferably 3 to 18) carbon atoms (for example, methyl, isopropyl, t-butyl, t-pentyl, t-hexyl, t-octyl, 2 -Butyl, 2-hexyl, 2-octyl, 2-dodecyl, 2-hexadecyl, t-pentadecyl, cyclopentyl, cyclohexyl), an alkoxycarbonyl group having 2 to 24 (preferably 5 to 17) carbon atoms (for example, n-butoxy) Carbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl), aryloxycarbonyl group having 7 to 24 carbon atoms (preferably 7 to 18) (for example, phenoxycarbonyl group, naphthoxycarbonyl group, cresyloxycarbonyl group) An alkylsulfonyl group having 1 to 24 (preferably 1 to 18) carbon atoms ( For example, methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), arylsulfonyl groups having 6 to 30 carbon atoms (preferably 6 to 24) (for example, p-tolylsulfonyl, p-dodecylphenylsulfonyl, p-hexadecyloxy) Phenylsulfonyl), an aryl group having 6 to 32 carbon atoms (preferably 6 to 24 carbon atoms) (for example, phenyl, p-tolyl), or a cyano group is preferable, and among these, R ₁₅ is further having 1 to 24 carbon atoms. An aliphatic group and an alkoxycarbonyl group having 2 to 24 carbon atoms are more preferable, and an aliphatic group having 1 to 24 carbon atoms is particularly preferable.
R ₁₆ is a halogen atom (preferably Cl), an aliphatic group having 1 to 24 carbon atoms (preferably 1 to 18 carbon atoms) {more preferably an alkyl group (for example, the alkyl groups mentioned for R ₁₅ above), carbon atoms 3-18 (more preferably 5-17) cycloalkyl group (for example, cyclopentyl, cyclohexyl)}, aryl group having 6-32 (preferably 6-24) carbon atoms (for example, phenyl, p-tolyl), carbon atom An alkoxy group of 1 to 24 (preferably 1 to 18) (for example, methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n-hexadecyloxy) or 6 to 32 carbon atoms (preferably Is an aryloxy group (for example, phenoxy, pt-butylphenoxy, pt-octylphenoxy, m-pen) Decylphenoxy, a p- dodecyloxy-phenoxy) Of these, R ₁₆ is further more preferably an aliphatic group having 1 to 24 carbon atoms, particularly preferably an aliphatic group having 1 to 12 carbon atoms.
h is an integer of 1-2.

In the formula [S-8], preferred examples of R ₁₇ and R ₁₈ are the same as the examples other than the hydrogen atom in R ₁₃ and R ₁₄ , and among these, R ₁₇ and R ₁₈ further have an aliphatic group. More preferred are n-butyl, n-octyl and n-dodecyl. However, R ₁₇ and R ₁₈ are not bonded to each other to form a ring.
Preferred examples of R ₁₉ are the same as R ₁₆ described above, and among these, R ₁₉ is more preferably an alkyl group and an alkoxy group, and particularly preferably n-octyl, methoxy, n-butoxy and n-octyloxy. .
i is an integer of 1-5.

In the formula [S-9], preferred examples of R ₂₀ and R ₂₁ are the same as those of R ₁ , R ₂ and R ₃ when they are not bonded to form a ring. Among these, R ₂₀ and R ₂₁ Is particularly preferably a substituted or unsubstituted aliphatic group having 1 to 24 carbon atoms.
R ₂₀ and R ₂₁ may be bonded to each other to form a ring, and the formed ring is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring.
j represents 1 or 2, and preferably j is 1.

Hereinafter, specific examples of high-boiling organic solvents (Exemplary Compounds S-1 to S-53) and viscosities of the respective high-boiling organic solvents (values measured by the above means in an environment at 25 ° C. and 60 ° C .; mPa · s) And the boiling point (° C.).
Here, the boiling point of the high-boiling organic solvent is a value converted from the boiling point during vacuum distillation to normal pressure. In the following specific examples, those having no boiling point are confirmed not to boil at 170 ° C., and those having no viscosity at 25 ° C. are solid at 25 ° C.

  Even if one kind of high-boiling organic solvent is used alone, two or more kinds [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (Nt- Butylacrylamide)]] may be used in combination.

  Examples of other high boiling point organic solvents and / or methods for synthesizing these high boiling point organic solvents include, for example, U.S. Pat. Nos. 2,322,027, 2,533,514, and 2, 772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004 , 928, 4,080,209, 4,127,413, 4,193,802, 4,207,393, 4,220,711, No. 4,239,851, No. 4,278,757, No. 4,353,9 No. 9, No. 4,363,873, No. 4,430,421, No. 4,430,422, No. 4,464,464, No. 4,483,918, No. 4,540,657, 4,684,606, 4,728,599, 4,745,049, 4,935,321, 5,013,639 European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A No. 510,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A, etc. Description, JP-A-48-47335, 50 No. 26530, No. 51-25133, No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149028, No. 52-46816, No. 53-1520, No. 53-1521 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84641, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 63-94552, 64-945 9454, 64-68745, JP-A-1-101543, 1-102454, 2-792, and 2 No. 4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338, and the like.

  In the present invention, a high boiling organic solvent having a boiling point higher than 100 ° C. is preferable, and a high boiling organic solvent having a boiling point higher than 170 ° C. is more preferable.

  The amount of the high-boiling organic solvent added in the liquid (II) is preferably in the range of 50% to 100% by mass, more preferably 70% to 100% by mass with respect to the total mass of the liquid, 90 mass% or more and 100 mass% or less are especially preferable.

<Other ingredients>
In addition to the components described above, known additives can be used in combination according to the purpose.
~ Storage stabilizer ~
A storage stabilizer can be added to the liquid in the present invention for the purpose of suppressing undesirable polymerization during storage. The storage stabilizer is preferably used in the coexistence with the polymerizable compound, and it is preferable to use a storage stabilizer that is soluble in the contained droplets or liquid or other coexisting components.

  Storage stabilizers include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinones, hydroquinone monoethers, organic phosphines, copper compounds, and the like. Specific examples include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monomethyl ether, hydroquinone monobutyl ether, and copper naphthenate. It is done.

  The addition amount of the storage stabilizer is preferably adjusted as appropriate based on the activity of the polymerization initiator, the polymerizability of the polymerizable compound, and the type of the storage stabilizer, but in terms of the balance between storage stability and curability. In terms of solid content in the liquid, 0.005 to 1% by mass is preferable, 0.01 to 0.5% by mass is more preferable, and 0.01 to 0.2% by mass is more preferable.

~ Conductive salts ~
Conductive salts are solid compounds that improve conductivity. In the present invention, it is preferable not to use it substantially because there is a great concern of precipitation during storage, but it is possible to increase the solubility of conductive salts or use a highly soluble liquid component. If it is good, an appropriate amount may be added.
Examples of the conductive salts include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like.

~solvent~
In the present invention, a solvent other than the high-boiling solvent described above can be used. The solvent can be used for the purpose of improving the polarity and viscosity of liquid (ink), surface tension, solubility and dispersibility of coloring materials, adjusting conductivity, and adjusting printing performance.
Note that the solvent is a water-insoluble liquid and does not contain an aqueous solvent because it is preferable in terms of recording a high-quality image with quick drying and uniform line width. The configuration used is desirable.

  A low boiling point organic solvent that is an organic solvent at 100 ° C. or lower is also exemplified, but there is a concern that the curability is affected, and it is desirable not to use the low boiling point organic solvent in consideration of environmental pollution. When used, it is preferable to use a highly safe solvent, and a highly safe solvent is a solvent having a high management concentration (an index indicated by the work environment evaluation criteria), preferably 100 ppm or more, More preferably, it is 200 ppm or more. Specific examples include alcohols, ketones, esters, ethers, hydrocarbons, and the like, and specific examples include methanol, 2-butanol, acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran.

  Solvents can be used in combination other than one kind alone, but when water and / or a low-boiling organic solvent is used, the amount of both used is preferably 0 to 20% by mass in each solution. 10 mass% is still more preferable, and it is preferable not to contain substantially. When water is contained in the liquid (I) and the liquid (II) according to the present invention, the stability over time such as non-uniformity over time, turbidity of the liquid due to dye precipitation, etc., and non-permeability or This is not preferable in terms of dryness when a slow-penetrating recording medium is used. In addition, it does not contain substantially means accepting presence of an inevitable impurity.

~ Other additives ~
Furthermore, known additives such as polymers, surface tension adjusters, ultraviolet absorbers, antioxidants, anti-fading agents and pH adjusters can be used in combination.
Regarding the surface tension adjusting agent, ultraviolet absorber, antioxidant, anti-fading agent, and pH adjusting agent, known compounds may be appropriately selected and used. For example, JP-A-2001-181549 discloses a specific example. The additives described can be used.

In addition to the above, a set of compounds that react by mixing to form aggregates or thicken can be separately contained in the liquid (I) and the liquid (II) according to the present invention. . The set of compounds has a feature of rapidly forming aggregates or rapidly thickening the liquid, thereby more effectively suppressing coalescence between adjacent droplets. Can do.
Examples of the reaction of the set of compounds include an acid / base reaction, a hydrogen bonding reaction with a carboxylic acid / amide group-containing compound, a crosslinking reaction represented by boronic acid / diol, and a reaction by electrostatic interaction with a cation / anion. Etc.

[Inkjet recording method]
Next, the ink jet recording method of the present invention will be described.
The ink jet recording method of the present invention includes a step of forming an image by ejecting at least two or more kinds of liquids contained in the ink set for ink jet recording of the present invention onto a recording medium, and applying energy to the formed image. And a step of curing.

  As described above, at least two kinds of liquids of the ink set for ink jet recording are mixed on the recording medium, and an image is formed by a polymerization and curing reaction of the polymerizable compound. At this time, energy is applied. Thus, the polymerization and curing reaction can be promoted, and a stronger image can be formed more efficiently. Such energy application is preferably performed by light irradiation or heating.

-Image formation process-
In the image forming step, an image is formed by ejecting onto a recording medium using at least two liquids contained in the ink set for ink jet recording.

Any ink jet recording method using an ink jet nozzle can be applied as a method of ejecting at least two kinds of liquids contained in the ink set for ink jet recording onto a recording medium. For example, a charge control method that ejects ink using electrostatic attraction force, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezo element, and an electrical signal that is converted into an acoustic beam and irradiates the ink with radiation pressure It is suitably used for an acoustic ink jet system that ejects ink using a thermal ink jet, a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating ink.
The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink is included.

In the image forming process, the liquid (I) and the liquid (II) are ejected and ejected onto the recording medium by the ink jet recording method, but are ejected simultaneously or sequentially.
That is, droplets based on the liquid (I) and the liquid (II) are ejected simultaneously or sequentially from the ink ejection port (head) in the ink jet printer onto the recording medium, and each of them is ejected on the recording medium. The droplets mix to form the desired image.
However, when one of the liquid (I) and the liquid (II) is a recording liquid containing a colorant and the other is a processing liquid, it is more preferable to eject the recording liquid after the processing liquid. .
That is, the recording liquid is discharged after the treatment liquid from the ink discharge port (head) in the ink jet printer on the recording medium, and the respective droplets are mixed on the recording medium to form a desired image. In this case, it is preferable that after the droplets of the treatment liquid are ejected, the droplets of the recording liquid are ejected with overlapping portions of the droplets of the treatment liquid.

The at least two liquids include at least the liquid (I) containing the aforementioned oxetane ring-containing compound and the liquid (II) containing the oxirane group-containing compound, and may further include other liquids.
The ratio (mass ratio) p / q of the total amount (p) of the compound having an oxetane ring contained in the two liquids and the total amount (q) of the compound having an oxirane group is 10/90 or more and 90/10 or less. In addition, it is preferable to form an image by ejecting the two kinds of liquids onto the recording medium.
The mass ratio p / q is more preferably from 15/85 to 85/15, and particularly preferably from 20/80 to 80/20, from the viewpoint of further improving curability.

As will be described later, the recording medium is not particularly limited, and even a non-permeable or slowly permeable recording medium can be used.
Here, the non-permeable recording medium refers to a medium in which droplets do not substantially penetrate. “Substantially does not penetrate” means that the penetration rate of a droplet after 1 minute is 5% or less. Further, the slow penetrable recording medium refers to a medium in which when a 10 pl (picoliter) droplet is dropped on a recording medium, the time until the entire liquid amount permeates is 100 milliseconds or more. Examples include art paper. Details of the non-permeable or slowly permeable recording medium will be described later.
Note that the permeable recording medium is a medium in which the time until the total liquid amount penetrates when a 10 pl droplet is dropped on the recording medium is 100 ms or less, specifically, plain paper, porous For example, quality paper.

  The liquid (I) and (II) droplets in image formation are preferably ejected at a droplet size of 0.1 pL (picoliter; the same applies hereinafter) to 100 pL (preferably by an inkjet nozzle). . When the droplet size is within the above range, it is effective in that an image having a high sharpness can be drawn with a density. More preferably, it is 0.5 pL or more and 50 pL or less.

  The liquid (I) application amount when the liquid (II) droplet is 1 is used as the balance of the liquid (I) application amount per droplet of the liquid (II) during image recording. The (mass ratio) is preferably in the range of 0.05 to 5, more preferably in the range of 0.07 to 1, and particularly preferably in the range of 0.1 to 1.

  In addition, after the application of the liquid (II), the droplet ejection interval until the liquid (I) droplet is ejected, or after the application of the liquid (I), until the liquid (II) droplet is applied. The droplet ejection interval is preferably in the range of 5 μsec or more and 400 msec or less. It is effective in that the effect of the present invention can be remarkably exhibited when the droplet ejection interval is within the above range. The droplet ejection interval is more preferably 10 μs or more and 300 ms or less, and particularly preferably 20 μs or more and 200 μs or less.

  Further, the liquid (I) and the liquid (II) are jetted onto the recording medium, and other liquids other than the liquids (I) and (II) are used depending on the purpose of the other liquids. Then, it may be applied onto the recording medium by any method such as coating by a coating apparatus described later or spraying by the inkjet nozzle. Also, the timing of application is not particularly limited. In the case of containing a colorant, it is preferable to eject the ink by an ink jet nozzle, and it is preferable that the liquid (I) is further sprayed and then applied.

(Coating using a coating device)
The coating apparatus is not particularly limited and can be appropriately selected from known coating apparatuses according to the purpose, for example, an air doctor coater, a blade coater, a lot coater, a knife coater, a squeeze coater, an impregnation coater, Examples include reverse roll coaters, transfer roll coaters, gravure coaters, kiss roll coaters, cast coaters, spray coaters, curtain coaters, and extrusion coaters. For details, see Yuji Harasaki's “Coating Engineering”.

-Immobilization process-
In the present invention, from the viewpoint of obtaining excellent fixability, there is provided a step of immobilizing the recorded image by applying energy to the recorded image after application of liquid (I) and liquid (II) droplets.
By applying energy, the curing reaction by polymerization of the polymerizable compound contained therein can be promoted, and a stronger image can be formed more efficiently. For example, in a system including a polymerization initiator, generation of active species due to decomposition of the polymerization initiator is promoted by application of active energy such as actinic light and heating, and due to the increase of active species and temperature rise, the result is due to the active species. The curing reaction by polymerization of the polymerizable compound is accelerated.
The application of energy can be suitably performed by irradiation with active light or heating.

Examples of the active light include ultraviolet rays and visible rays, as well as α rays, γ rays, X rays, electron rays, and the like. Among these, ultraviolet rays and visible rays are preferably used from the viewpoint of cost and safety, and ultraviolet rays are particularly preferred.
The amount of energy required for the curing reaction varies depending on the type and content of the polymerization initiator, but is generally about 1 to 500 mJ / cm ² .

In addition, when energy is applied by heating, it is preferable to heat for 0.1 to 1 second under the condition that the surface temperature of the recording medium is in a temperature range of 40 to 80 ° C.
Heating can be performed using a non-contact type heating means, such as a heating means for passing through a heating furnace such as an oven, a heating means by full exposure of ultraviolet light to visible light to infrared light, etc. are suitable. It is. Examples of light sources suitable for exposure as the heating means include metal halide lamps, xenon lamps, tungsten lamps, carbon arc lamps, mercury lamps and the like.

-Recording medium-
The recording medium is not particularly limited and can be used. However, it is preferable to use a non-permeable or slowly permeable recording medium from the viewpoint of remarkable effects of the invention.
Examples of the non-permeable recording medium include synthetic resin, rubber, resin-coated paper, glass, metal, earthenware, and wood. In addition, for the purpose of adding a function, a base material obtained by combining a plurality of these materials can be used.

  As the synthetic resin, any synthetic resin can be used. For example, polyesters such as polyethylene terephthalate and polybutadiene terephthalate, polyolefins such as polyvinyl chloride, polystyrene, polyethylene, polyurethane, and polypropylene, acrylic resins, polycarbonates, and acrylonitrile-butadiene. -Styrene copolymer etc., Diacetate, Triacetate, Polyimide, Cellophane, Celluloid etc. are mentioned. When the synthetic resin is used, the thickness and shape may be any of a film shape, a card shape, and a block shape, and are not particularly limited, and may be either transparent or opaque.

  The synthetic resin is preferably used in the form of a film used for so-called soft packaging, and various non-absorbable plastics and films thereof can be used. Examples of the plastic film include a PET film, an OPS film, an OPP film, a PNy film, a PVC film, a PE film, and a TAC film. Other plastics that can be used include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers.

  Examples of the resin-coated paper include a transparent polyester film, an opaque polyester film, an opaque polyolefin resin film, and a paper support in which both sides of paper are laminated with a polyolefin resin. Particularly preferred is a paper support in which both sides of the paper are laminated with a polyolefin resin.

  There is no restriction | limiting in particular as said metal, For example, aluminum, iron, gold | metal | money, silver, copper, nickel, titanium, chromium, molybdenum, silicon | silicone, lead, zinc etc., or stainless steel etc., and these composite materials are suitable. .

  Further, a read-only optical disk such as a CD-ROM or DVD-ROM, a write-once optical disk such as a CD-R or DVD-R, a rewritable optical disk, or the like can also be used. And a gloss-imparting layer.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these.

<Preparation of cyan pigment dispersion>
PB15: 3 (IRGALITE BLUE GLO; manufactured by Ciba Specialty Chemicals) 16 g, bis {[1-ethyl (3-oxetaniel)] methyl} ether (OXT-221; manufactured by Toagosei Co., Ltd.) 48 g, and BYK- 16 g of 168 (manufactured by Big Chemie) was mixed and stirred with a stirrer for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain Pigment Dispersion A.
PB15: 3 (IRGALITE BLUE GLO; manufactured by Ciba Specialty Chemicals) 16 g, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (Cel3000 Daicel 48 g of Cytec Co., Ltd.) and 16 g of BYK-168 (Bic Chemie) were mixed and stirred with a stirrer for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain Pigment Dispersion B.
Here, dispersion conditions were such that zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 1 hour.

<Preparation of ink>
The components shown in Tables 1 and 2 below were stirred, mixed, and dissolved to obtain inks 1 to 20. In addition, the surface tension of inks 1 to 20 was measured at 20 ° C. and 60% RH by the Wilhelmy method (surface tension meter CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.). It was.

≪Explanation of symbols in Tables 1 and 2≫
OXT-221: Bis {[1-ethyl (3-oxetaniel)] methyl} ether (manufactured by Toagosei Co., Ltd., a compound having an oxetane ring)
Cel3000: 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (a compound having an oxirane group, manufactured by Daicel-Cytec Corp.)
Initiator A: Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.)
Sensitizer A: 9,10-dibutoxyanthracene Surfactant A: Megafac F475 (manufactured by Dainippon Ink & Chemicals, Inc.)

<Stability against low illumination light>
The cyan ink recording liquid (liquid (I)) and the processing liquid (liquid (II) (inks 1 to 20) prepared above were used in an inkjet printer (experimental machine equipped with a head manufactured by Toshiba TEC; nozzle density 300 dpi). Two ink heads (ink head 1 and ink head 2) are filled, and an ultraviolet light source (a metal halide lamp with a wavelength of 365 nm; irradiation illuminance is 1000 mJ / cm ² on the recording medium) is irradiated, and after a certain time In this state, the ejection performance was evaluated according to the following evaluation criteria, and the results are shown in Table 3. The illuminance of leakage light on the nozzle surfaces of the ink heads 1 and 2 was about 0.1 mW. The ink head 1 was filled with liquid (I), and the ink 2 was filled with liquid (II).

<Evaluation criteria>
◎: 50% or more of nozzles can be discharged even when the standby state exceeds 100,000 seconds. ○: Non-discharge occurs from 50% of the nozzles when the standby state exceeds 1500 seconds and within 100,000 seconds. △: The standby state is 1000 seconds. No discharge occurs from 50% of nozzles within 1500 seconds exceeding X: Non-discharge occurs from 50% of nozzles in standby state within 1000 seconds

≪Explanation of symbols in Tables 1 and 2≫
P1 / q1: “> 90/10” when the mass ratio of the oxetane compound (p1) to the oxirane compound (q1) in the liquid (I) exceeds 90/10, and “<90 when the mass ratio is less than 90/10. / 10 ”, and if equal to 90/10,“ = 90/10 ”.
P2 / q2: “> 10/90” when the mass ratio of the oxetane compound (p2) and the oxirane compound (q2) in the liquid (II) exceeds 10/90, and “<10 when the ratio is less than 10/90. / 90 is “”, and if it is equal to 10/90, “= 10/90”.

From the results of the ink sets 1 to 29 in Table 3 above, it is understood that the light stability is deteriorated when the oxetane compound and the oxirane compound contained in the liquid (I) or the liquid (II) are mixed within a certain range. It was. That is, the mass ratio (p1 / q1 or p2 / q2) of the oxetane compound (p1 or p2) and the oxirane compound (q1 or q2) contained in the liquid (I) or liquid (II) is 90/10 or more or 10 / If it is 90 or less, the light stability at low illuminance is good, but at a mass ratio of 90/10 or 10/90 (p1 / q1 or p2 / q2), deterioration of the light stability can be confirmed, and the mass ratio (p1 / Q1 or p2 / q2) is in the range of more than 10/90 and less than 90/10, the light stability is very poor, and it has been found that non-ejection occurs from 50% of the nozzles in the standby state within 1000 seconds.
In addition, it has been clarified that when no initiator is added (inks 12, 13, and 16), ejection failure does not occur even when the standby state exceeds 100,000 seconds.

<Evaluation of curability>
The recording liquid (inks 1, 2, 12) and the processing liquids (inks 14, 15, 16) prepared above were tested using an inkjet printer (Toshiba TEC head (CA3), image resolution 300 × 300 dpi ( 2 heads per color), printing range: 53.583 mm, number of nozzles: 636/2 heads, printing speed: 0.41 m / sec, printing method: single pass method), processing liquid droplets on the recording medium A solid image was printed so that the droplets of the recording liquid overlapped.
After printing, a metal halide lamp (having a wavelength of 365 nm) was used to change the integrated light amount, and ultraviolet irradiation was performed to cure the solid image.
The droplet ejection densities of the treatment liquid and the recording liquid are as shown in Table 4. Further, a polyethylene terephthalate (PET) sheet having a thickness of 60 μm was used as a recording medium.

The curability is determined by superimposing the print surface of the print sample on plain paper (Fuji Xerox Co., Ltd. copy paper C2) and pressing it with a roller, and then peeling the print sample and plain paper and transferring it to the plain paper side. If there was ink, it was uncured, and if it was not transferred, it was judged that it was cured.
The evaluation of curability was performed according to the following criteria. The results are shown in Table 4.
<Evaluation criteria>
○: cured cumulative amount of light 50mJ / cm ² within △: cumulative amount of light 50mJ / cm ² ultra 100mJ / cm ² within the cured ×: not cured within a cumulative amount of light 100mJ / cm ²

From the results shown in Table 4 above, the integrated light quantity 100 mJ / cm when the mass ratio (p / q) of the oxetane compound (p) and the oxirane compound (q) on the recording medium is 90/10 or less and 10/90 or more. It hardened | cured within ^{2 and} it turned out that sclerosis | hardenability deteriorates in the range whose mass ratio (p / q) exceeds 90/10 or is smaller than 10/90.
Further, from the results of ink sets 3 and 20 in Table 4, it was found that good curability can be obtained by mixing the liquid not added with the initiator and the liquid added with the initiator on the non-recording medium. .

Claims (8)

An ink set for ink jet recording having at least two kinds of liquids, liquid (I) containing at least a compound having an oxetane ring and liquid (II) containing at least a compound having an oxirane group, The ratio (mass ratio) p1 / q1 of the total amount (p1) of the compound having an oxetane ring to the total amount (q1) of the compound having an oxirane group is 90/10 or more even if the compound having an oxirane group is not included or is included. In addition, the liquid (II) does not contain a compound having an oxetane ring, or the liquid (II) has a ratio (mass ratio) of the total amount (p2) of the compound having an oxetane ring and the total amount (q2) of the compound having an oxirane group. An ink set for ink-jet recording, wherein p2 / q2 is 10/90 or less. The ink set for inkjet recording according to claim 1, wherein the liquid (I) or (II) contains a polymerization initiator. The ink set for inkjet recording according to claim 2, wherein the liquid not containing the polymerization initiator contains a sensitizer. 4. The inkjet according to claim 1, wherein one of the liquid (I) and the liquid (II) is a recording liquid containing a colorant, and the other is a processing liquid. Ink set for recording. The ink set for inkjet recording according to claim 4, wherein the treatment liquid contains a surfactant. A step of forming an image by ejecting at least two or more liquids contained in the ink set for ink jet recording according to any one of claims 1 to 5 onto a recording medium, and imparting energy to the formed image And curing the ink jet recording method. The inkjet recording method according to claim 6, wherein the energy is applied by light irradiation or heating. In the step of forming the image, the ratio (mass ratio) p / q of the total amount (p) of the compound having an oxetane ring contained in two or more liquids and the total amount (q) of the compound having an oxirane group is 10/90. The ink jet recording method according to claim 6 or 7, which is a step of forming an image by applying the two or more kinds of liquids on the recording medium at 90/10 or less.