JP2006104185A - Triarylsulfonium salt compound, active energy ray-curable composition and active ray-curable inkjet ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cationically polymerizable compound capable of stably reproducing highly precise image under various printing environments without releasing benzene which is harmful to human bodies and to provide an inkjet ink composition containing the compound. <P>SOLUTION: A triarylsulfonium salt compound is represented by general formula (T-1). An active energy ray-curable composition comprises the triarylsulfonium salt compound and an epoxy compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a triarylsulfonium salt compound capable of stably reproducing a high-definition image on various recording materials under various printing environments, without any harmful benzene emission to the human body, and an actinic ray curable type containing the same. The present invention relates to an inkjet ink composition and an active energy ray curable composition.

  In recent years, the ink jet recording system can create images easily and inexpensively, and thus has been applied to various printing fields such as photographs, various printing, marking, and special printing such as color filters. In particular, a recording device that emits and controls fine dots, ink that has improved color reproduction gamut, durability, and emission suitability, and ink absorbability, coloring material color development, surface gloss, etc. have been dramatically improved. It is also possible to obtain image quality comparable to silver halide photography using special paper. The image quality improvement of today's ink jet recording system is achieved only when all of the recording apparatus, ink, and special paper are available.

  However, in an inkjet system that requires dedicated paper, the recording medium is limited, and the cost of the recording medium increases. Therefore, many attempts have been made to record on a transfer medium different from dedicated paper by an ink jet method. Specifically, a phase change ink jet method using a wax ink solid at room temperature, a solvent ink jet method using an ink mainly composed of a fast-drying organic solvent, a UV ink jet method in which crosslinking is performed by ultraviolet (UV) light after recording, etc. It is.

  Among them, the UV inkjet method has been attracting attention in recent years in that it has a relatively low odor compared to the solvent-based inkjet method and can be recorded on a recording medium having no quick drying and no ink absorption. No. 54667, JP-A-6-200204, and JP 2000-504778 disclose ultraviolet curable inkjet inks.

  However, even if these inks are used, the dot diameter after landing greatly changes depending on the type of recording material and the working environment, and it is not possible to form high-definition images on various recording materials. Is possible.

Among them, in particular, ultraviolet curable ink jet inks using cationically polymerizable compounds have been proposed (see, for example, Patent Documents 1 to 3), but these ultraviolet curable ink jet inks have an oxygen inhibiting action. Although it is not affected, there is a problem that it is easily affected by moisture (humidity) at the molecular level and releases harmful benzene. That is, the actinic ray curable inkjet ink composition using the cationically polymerizable compound described in Patent Documents 1 to 3 described above, for example, UVR6110 and UVR6105 manufactured by Dow Chemical Company, manufactured by Daicel Chemical Industries, Ltd. as the photopolymerizable compound. The ceroxide 2021 is often used, and these compounds release harmful benzene, the ejection stability and curability vary greatly depending on the printing environment (for example, temperature and humidity), and wrinkles occur due to curing shrinkage. I have a problem to do.
JP 2001-220526 A (Claims and Examples) JP 2002-188025 A (Claims and Examples) JP 2002-317139 A (Claims and Examples)

  The present invention has been made in view of the above-mentioned problems, and its purpose is to prevent the release of benzene that is harmful to the human body, and it has excellent character quality and color mixing for all recording materials even in various printing environments. There are provided a triarylsulfonium salt compound that can record a high-definition image very stably, an actinic ray curable inkjet ink composition and an active energy ray curable composition containing the triarylsulfonium salt compound.

  The above object of the present invention is achieved by the following configurations.

  (1) A triarylsulfonium salt compound, which is a compound represented by the following general formula (T-1).

[Wherein R ^T11 and R ^T12 represent an alkyl group or an aromatic group, Z ^T1 represents an oxygen atom or a sulfur atom, and R ^T13 and R ^T14 represent an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, respectively. , An alkylthio group and an arylthio group, mt1 represents an integer of 0 to 4, nt1 and pt1 each represents an integer of 1 to 5, and X ^T1 represents PF ₆ . ]
(2) The triarylsulfonium salt compound as described in 1 above, wherein the compound represented by the general formula (T-1) is a compound represented by the following general formula (T-2).

[Wherein R ^T21 , R ^T22 , R ^T23 and R ^T24 each represents an alkyl group or an aromatic group, Z ^T2 represents an oxygen atom or a sulfur atom, and R ^T25 and R ^T26 each represent an alkyl group or a fluorocarbon. hydrogen group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, mt2, nt 2 and pt2 each represents an integer of 0 to 4, X ^T2 represents PF _6. ]
(3) The triarylsulfonium salt compound as described in 2 above, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-3).

[Wherein, R ^T31 represents an alkyl group having 1 to 10 carbon atoms, R ^T32 and R ^T33 each represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and X ^T3 represents PF ₆ Represents. ]
(4) The triarylsulfonium salt compound as described in 2 above, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-4).

[Wherein, R ^T41 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^T42 represents a substituent, mt4 represents an integer of 0 to 4, and R ^T43 and R ^T44 each represent 1 to C carbon atoms. Represents 10 alkyl groups, and X ^T4 represents PF ₆ . ]
(5) The triarylsulfonium salt compound as described in 2 above, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-5).

[Wherein, R ^T51 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^T52 represents a substituent, mt5 represents an integer of 0 to 4, and R ^T53 and R ^T54 each represents 1 to C carbon atoms. Represents 10 alkyl groups, and X ^T5 represents PF ₆ . ]
(6) An active energy ray-curable composition comprising the triarylsulfonium salt compound according to any one of 1 to 5 above and an epoxy compound.

  (7) The active energy ray-curable composition according to (6) above, wherein the epoxy compound is an alicyclic epoxy compound represented by the following general formula (A).

Wherein, R ₁₀₀ represents a substituent, m0 represents an integer of 0 to 2. r0 represents an integer of 1 to 3. L ₀ represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
(8) The active energy ray-curable composition according to (6) above, wherein the epoxy compound is at least one selected from alicyclic epoxy compounds represented by the following general formulas (I) to (VI): object.

Wherein, R ₁₀₁ represents a substituent, m1 represents an integer of 0 to 2. p1 and q1 each represents 0 or 1. r1 represents an integer of 1 to 3. L ₁ represents a C 1-15 r 1 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

Wherein, R ₁₀₂ represents a substituent, m2 represents an integer of 0 to 2. p2 and q2 each represents 0 or 1. r2 represents an integer of 1 to 3. L ₂ represents an r2 + 1-valent linking group or a single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₃ represents a substituent, and m3 represents an integer of 0 to 2. p3 represents 0 or 1. L ₃ represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₄ represents a substituent, and m4 represents an integer of 0 to 2. p4 represents 0 or 1. L ₄ represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₅ represents a substituent, and m5 represents 1 or 2. ]

[Wherein, R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2. ]
(9) An actinic ray curable inkjet ink composition comprising the active energy ray-curable composition according to any one of 6 to 8 above.

  According to the present invention, the object of the present invention is to prevent the release of benzene that is harmful to the human body, and is excellent in character quality, no color mixing, and high in any recording material even under various printing environments. A triarylsulfonium salt compound capable of recording a fine image very stably, an actinic ray curable inkjet ink composition and an active energy ray curable composition containing the triarylsulfonium salt compound can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The inventor of the present invention contains an onium salt that does not generate benzene by actinic ray irradiation as a photoacid generator in an actinic ray curable inkjet ink composition (hereinafter also referred to as actinic ray curable ink or simply ink), The actinic ray curable inkjet ink composition containing a compound having an oxetane ring as a polymerizable compound dramatically improves ejection stability and curability, and is not affected by the printing environment (eg, temperature, humidity). It was found that good ejection stability and curability can be obtained.

  Conventionally, a cationically polymerizable ink composition has been prepared using UVI6992 (manufactured by Dow Chemical Co., Ltd., triarylsulfonium salt), a photoacid generator that generates benzene as a decomposition product upon irradiation with actinic rays. . However, this ink composition is not only used in the food field because it generates benzene, but also has the problem of unstable ejection due to the environment (temperature, humidity). It was impossible to form a high-definition image by inkjet recording. Further, as onium salts (photoacid generators) that do not generate benzene, IRGACURE250 (Ciba Specialty Chemicals, diaryl iodonium salt) and CI 5102 (Nihon Soda Co., diaryl iodonium salt) are known. Including these, there has been no practical example of an inkjet ink composition that can be stably ejected using an onium salt that does not generate benzene by irradiation with actinic rays.

  In particular, when used in combination with a compound containing an oxetane ring, the ejection stability, which is an important characteristic for ink jet recording, becomes very good, and the ink lands on the recording material regardless of the curing environment. This is an epoch-making configuration in which the Dot diameter can be easily controlled and a high-quality image can be formed with high reproducibility.

  Further, when an onium salt that does not generate benzene by irradiation with actinic rays is used as a photoacid generator, it is preferable to use a basic compound or a nonionic surfactant in combination because the ejection stability is further improved.

  More preferably, the photopolymerizable compound contains 25 to 90% by mass of a compound having an oxetane ring, 10 to 70% by mass of a compound having an oxirane group, and 0 to 40% by mass of a vinyl ether compound. Both the performance and the discharge stability are improved.

  Moreover, it discovered that both the said sclerosis | hardenability and discharge stability improved markedly by using the oxetane compound represented by the following general formula (E). When only the oxetane compound is used as the photopolymerizable compound, it is more preferable to use a monofunctional oxetane compound and a polyfunctional oxetane compound having two or more oxetane rings in combination.

[Wherein, R _{1 to} R ₆ each represents a hydrogen atom or a substituent. However, at least one of the groups represented by R _{3 to} R ₆ is a substituent. ]
Here, an onium salt (photoacid generator) that does not generate benzene by actinic ray irradiation contained in the ink will be described.

“Does not generate benzene by actinic ray irradiation” means that benzene is not substantially generated. Specifically, an ink containing 5% by mass of an onium salt (photoacid generator) in the ink composition. Is used to print an image of about 100 m ² with a thickness of 15 μm, and the amount of benzene generated when irradiated with actinic rays in an amount sufficient to decompose the photoacid generator with the ink film surface kept at 30 ° C. Indicates a trace amount of 5 μg or less or none. The onium salt is preferably a sulfonium salt or an iodonium salt, and satisfies the above condition as long as it has a substituent on the benzene ring bonded to S ⁺ or I ⁺ .

The sulfonium salt is preferably a sulfonium salt compound represented by the following general formulas [1] to [4], and satisfies the above conditions as long as it has a substituent on the benzene ring bonded to S ⁺ .

In the general formulas [1] to [4], R _{1 to} R ₁₇ each represent a hydrogen atom or a substituent, R _{1 to} R ₃ do not simultaneously represent a hydrogen atom, and R _{4 to} R ₇ represent simultaneously. It does not represent a hydrogen atom, R _{8 to} R ₁₁ do not represent a hydrogen atom at the same time, and R _{12 to} R ₁₇ do not represent a hydrogen atom at the same time. However, R _{1 to} R ₃ in the general formula [1] are not phenylthio groups or phenoxy groups.

The substituent represented by R _{1 to} R ₁₇ is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, or a hexyl group, Alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, decyloxy group, dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, ethoxycarbonyl Group, carbonyl group such as benzoyloxy group, halogen atom such as fluorine, chlorine, bromine and iodine, cyano group, nitro group and hydroxy group.

X represents a non-nucleophilic anion residue, for example, a halogen atom such as F, Cl, Br, or I, B (C ₆ F ₅ ) ₄ , R ₁₈ COO, R ₁₉ SO ₃ , SbF ₆ , AsF ₆ , PF ₆ , BF _{4 and the} like. However, R ₁₈ and R ₁₉ are each an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a halogen atom such as fluorine, chlorine, bromine or iodine, a nitro group, a cyano group, a methoxy group or an ethoxy group. Represents an alkyl group or a phenyl group which may be substituted with an alkoxy group or the like. Among these, B (C ₆ F ₅ ) ₄ and PF ₆ are preferable from the viewpoint of safety.

  The above compounds can be obtained from THE CHEMICAL SOCIETY OF JAPAN Voi. 71 no. 11, 1998, as well as the photoacid generator described in “Organic Materials for Imaging”, edited by Organic Electronics Materials Research Group, Bunshin Publishing (1993), can be easily synthesized by a known method.

  In the present invention, the sulfonium salt represented by the general formulas [I] to [4] is particularly preferably at least one sulfonium salt selected from the following formulas [5] to [13]. X represents a non-nucleophilic anion residue and is the same as described above.

Illustrative compounds including iodonium salts include the following compounds in addition to the formulas [5] to [13] where X is B (C ₆ F ₅ ) ₄ , PF ₆ , Br, BF ₄ .

  Hereinafter, the present invention will be described in detail.

[Triarylsulfonium salt compound]
In the present invention, the onium salt that does not generate benzene is a triarylsulfonium salt compound represented by the general formula (T-1).

  In the present invention, the triarylsulfonium salts represented by the general formulas (T-2) to (T-5) are particularly preferable, and among them, the triarylsulfonium represented by the general formula (T-3) Salts are particularly preferably used, and these compounds are particularly excellent with respect to photocurability, safety and humidity influence.

(Compound represented by formula (T-1))
R ^T11 and R ^{T12 each} represents an alkyl group or an aromatic group.

  The alkyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, and the like.

  The aromatic group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may have a condensed ring, such as an aromatic hydrocarbon group (for example, phenyl group, naphthyl group, etc.), aromatic Group heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group) Group) and the like.

  The alkyl group or aromatic group described above may further have a substituent, and a plurality of these substituents may be bonded to each other to form a ring, or may have a condensed ring. . Examples of the substituent include, in addition to the alkyl group described above, an alkenyl group (for example, vinyl group, allyl group, etc.), an alkynyl group (for example, ethynyl group, propargyl group, etc.), an aromatic hydrocarbon group (for example, Phenyl group, naphthyl group, etc.), heteroaromatic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzooxa Zolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group) Hexyloxy group, octyloxy group, dodecyloxy group, etc.), cyclo Lucoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, Octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxy) Carbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarboni) Group), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylamino) Sulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbo group) Nyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, Pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylamino) Carbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octyl Minocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group) Cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkyl sulfo Group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group) Etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.) , Halogen atoms (eg, fluorine atom, chlorine atom, bromine atom), fluorinated hydrocarbon groups (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group), cyano group, nitro Group, hydroxy Si group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.). These substituents may be further substituted with the above substituents, and a plurality of these substituents may be bonded to each other to form a ring.

The alkyl group or aromatic group represented by R ^T11 or R ^T12 may or may not have a substituent, but is preferably an unsubstituted alkyl group or aromatic group? Or an aromatic group substituted with an alkyl group or alkoxy group substituted with a halogen atom, more preferably an unsubstituted alkyl group or aromatic group, or an alkyl group substituted with a fluorine atom, or an alkoxy group Examples of the alkyl group substituted with fluorine atom include fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group and the like.

Z ^T1 represents an oxygen atom or a sulfur atom, and Z ^T1 is preferably bonded to the ortho-position or para-position, and more preferably bonded to the para-position, with respect to the benzene ring to which the sulfonium ion is bonded.

R ^T13 and R ^T14 each represents an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

As the alkyl group and the aromatic group, the same groups as R ^T11 and R ^T12 described above are represented.

The alkoxy group and the aryloxy group are groups in which a group having the same meaning as R ^T11 and R ^T12 described above is bonded to an oxygen atom at one position. Examples include alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group). , Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) Group), an aryloxy group (for example, phenoxy group, naphthyloxy group, etc.) and the like.

The alkylthio group and the arylthio group are groups in which a group having the same meaning as R ^T11 and R ^T12 described above is bonded to a sulfur atom at one position. Examples thereof include an alkylthio group (for example, a methylthio group, an ethylthio group, a propylthio group, a pentylthio group). Group, hexylthio group, octylthio group, dodecylthio group and the like), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group and the like), arylthio group (for example, phenylthio group, naphthylthio group and the like) and the like. The aromatic group, aryloxy group, and arylthio group described above may have a condensed ring.

The alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, and arylthio group described above may further have a substituent, and a plurality of these substituents are bonded to each other to form a ring. Or may have a condensed ring. Examples of the substituent include the same groups as the examples of the substituent of R ^T11 described above, and these substituents may be further substituted with a substituent, and these substituents May be bonded to each other to form a ring. The alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group and arylthio group represented by R ^T13 and R ^T14 may or may not have a substituent, but preferably An unsubstituted alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group substituted with a halogen atom, or an aromatic group substituted with an alkoxy group, more preferably An unsubstituted alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group substituted with a fluorine atom, or an aromatic group substituted with an alkoxy group, and a fluorine atom Examples of alkyl groups substituted by are fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pen Fluorophenyl group and the like.

  mt1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, nt1 and pt1 each represents an integer of 1 to 5, and preferably each of 1 to 3 It is an integer, More preferably, it is an integer of 1-2 each.

A plurality of R ^T12, R ^T13, R ^T14, each of which may be the same or different, R ^T11 and R ^T12, or a plurality of R ^T12 each other may bond together to form a ring, R ^T12 and R ^T13 or a plurality of R ^T13 may combine to form a ring, R ^T12 and R ^T14 or a plurality of R ^T14 may combine to form a ring, and R ^T12 and R ^T14 may They may combine to form a ring. At least one of R ^T13 is preferably bonded to the ortho position or the para position, and more preferably bonded to the para position, with respect to the benzene ring to which the sulfonium ion is bonded. At least one of R ^T14 is preferably bonded to the ortho or para position, and more preferably bonded to the para position, with respect to the benzene ring to which the sulfonium ion is bonded. X ^T1 is PF ₆ ^- represents a.

(Compound represented by formula (T-2))
In the general formula (T-2), R ^T21 , R ^T22 , R ^T23 and R ^T24 each represents an alkyl group or an aromatic group. The alkyl group and an aromatic group, a group having the same meaning as R ^T11 described above, a plurality of ^{R T21, R T22, R T23} , R T24 may be the same or different and each, R ^T21 and R ^T22 or more R ^T22 may be bonded to each other to form a ring, R ^T23 and R ^T25 or a plurality of R ^T23s may be bonded to each other to form a ring, R ^T24 and R ^T26 or a plurality of R ^T24s may combine to form a ring, R ^T22 and R ^T23 may combine to form a ring, R ^T23 and R ^T24 may combine to form a ring, ^T22 and R ^T24 may combine to form a ring.

Z ^T2 represents an oxygen atom or a sulfur atom, and R ^T25 and R ^T26 each represents an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. As the alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, the above-mentioned R ^T13 represents the same group, mt2, nt2, and pt2 each represents an integer of 0-4, preferably Each is an integer of 0 to 2, more preferably 0 or 1. X ^T2 is PF ₆ ^- represents a.

(Compound represented by formula (T-3))
In General Formula (T-3), R ^T31 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, tert-amyl group, cyclopentyl group, cyclohexyl group and the like, and these may further have a substituent. An example of the substituent is a group having the same ^{meaning as} the substituent of R ^T11 described above. R ^T31 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

R ^T32 and R ^T33 each represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The alkyl group is a group having the same meaning as R ^T31 described above, and the alkoxy group is a group in which a group having the same meaning as R ^T31 described above is bonded to an oxygen atom at one position. Examples include a methoxy group, an ethoxy group, and a propyloxy group. Isopropyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like. R ^T32 and R ^T33 are each preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. And most preferably a methyl group or a methoxy group. X ^T3 is PF ₆ ^- represents a.

(Compound represented by formula (T-4))
In General Formula (T-4), R ^T41 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, A heptyl group, an octyl group, a tert-amyl group, a cyclopentyl group, a cyclohexyl group and the like may be mentioned, and these may further have a substituent. An example of the substituent is a group having the same ^{meaning as} the substituent of R ^T11 described above. R ^T41 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

R ^T42 represents a substituent, and the substituent is the same as the substituent for R ^T11 described above.

  mt4 represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

R ^T43 and R ^T44 each represent an alkyl group having 1 to 10 carbon atoms. The alkyl group has the same meaning as RT ³¹ described above. R ^T43 and R ^T44 are each preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. X ^T4 is PF ₆ ^- represents a.

(Compound represented by formula (T-5))
In General Formula (T-5), R ^T51 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group has the same ^{meaning as} the substituent for R ^T31 described above. R ^T51 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ^T52 represents a substituent. The substituent is the same group as the substituent for R ^T11 described above.

  mt5 represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

R ^T53 and R ^T54 each represent an alkyl group having 1 to 10 carbon atoms. The alkyl group has the same meaning as RT ³¹ described above. R ^T53 and R ^T54 are each preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. X ^T5 is PF ₆ ^- represents a.

  Specific examples of the triarylsulfonium salt compounds represented by the general formulas (T-1) to (T-5) used in the present invention are shown below, but the present invention is not limited thereto.

  These compounds are described in Bull. Chem. Soc. Jpn. 42, 312 (1969). J. et al. Polym. Sci. , Poly. m. Chem. Ed. 17, 2877 (1979). Can be synthesized according to the methods described in JP-A-11-80118, JP-A-2002-241474, and US Pat. No. 4,404,459. Synthesis examples of the exemplified compounds are shown below.

(Synthesis of TAS-1)
In a flask equipped with a calcium chloride tube, a thermometer, and a mechanical stirrer, 209 g of anisole and 112 g of aluminum chloride were mixed under ice cooling. Under ice-cooling, 50 g of thionyl chloride was added dropwise over 3 hours while keeping the internal temperature of the flask at 10 ° C. or lower. Thereafter, the mixture was stirred for 1 hour under ice cooling and 2 hours at room temperature. The reaction solution was poured into ice water, and 600 ml of ethyl acetate was added for liquid separation, and the aqueous layer was separated. A solution of 90 g of potassium hexafluorophosphate / 600 ml of pure water was added little by little to the aqueous layer, and the produced crystals were collected by filtration to obtain 222.7 g of crude crystals (106.3%). After adding 500 ml of methylene chloride to the crude crystals and dissolving, the column was purified with activated alumina and the solvent was concentrated under reduced pressure to obtain 192.2 g of a transparent viscous liquid. After adding 600 ml of methanol and dissolving by heating, the mixture was allowed to cool to near room temperature and further stirred for 1 hour, followed by cooling with ice water and stirring for 2 hours. Crystals were separated by filtration, washed with cold methanol, and air-dried to obtain TAS-1. Yield 168.3 g (80% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

(Synthesis of TAS-2)
25 g of phosphorus oxide and 160 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of about 80 ° C. for 3 hours. After allowing to cool to room temperature, 44 g of bis (4-methoxyphenyl) sulfoxide and 43 g of phenyl ether were added and stirred for 3 hours under water cooling. When 31 g of potassium hexafluorophosphate was dissolved in 1 L of ice water in a 2 L conical beaker and the above reaction solution was added little by little while stirring with a mechanical stirrer, a soft white amorphous was formed. Stirring was stopped, the supernatant was removed by decantation, 1 L of methylene chloride was added to the residue, and after washing with water, the methylene chloride layer was concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment, the solvent was concentrated under reduced pressure to obtain a light brown oil component. Crystals produced by adding 1000 ml of hexane were collected by filtration to obtain TAS-2. Yield 72.4 g (77% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

(Synthesis of TAS-4)
32 g of phosphorus oxide and 150 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of about 80 ° C. for 3 hours. After allowing to cool to room temperature, 54 g of bis (4-methoxyphenyl) sulfoxide and 46.8 g of 1-tert-butyl-4-phenoxybenzene were added and stirred for 3 hours under water cooling. When 42 g of potassium hexafluorophosphate was dissolved in 1 L of ice water in a 2 L conical beaker and the above reaction solution was added little by little while stirring with a mechanical stirrer, a soft white amorphous was formed. Stirring was stopped, the supernatant was removed by decantation, 1 L of methylene chloride was added to the residue, and after washing with water, the methylene chloride layer was concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment, the solvent was concentrated under reduced pressure to obtain a light brown oil component. Add about 100 ml of methanol and concentrate under reduced pressure again to completely remove methylene chloride, and then dry under reduced pressure with a rotary pump. TAS-4 was obtained by crushing the amorphous foamed into a bowl-like firmness. Yield 60.9 g (49% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

(Synthesis of TAS-6)
36 g of phosphorus oxide and 180 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of about 80 ° C. for 3 hours. After allowing to cool to room temperature, 60.6 g of bis (4-methoxyphenyl) sulfoxide and 21.3 g of toluene were added. Since the temperature began to rise violently, it was immediately cooled with water and stirred for 3 hours. When 49 g of potassium hexafluorophosphate was dissolved in 1 L of ice water in a 2 L conical beaker and the previous reaction solution was added little by little while stirring with a mechanical stirrer, a brown nougat amorphous was produced. Stirring was stopped, the supernatant was removed by decantation, 800 ml of methylene chloride was added to the residue, and a solution of 25 g of potassium hexafluorophosphate / pure 500 ml was added and dispersed for 1 hour. After separation of the aqueous layer, the methylene chloride layer was concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment, the solvent was concentrated under reduced pressure to obtain a light brown oil component. Add about 100 ml of methanol and concentrate under reduced pressure again to completely remove methylene chloride, and then dry under reduced pressure with a rotary pump. TAS-6 was obtained by crushing the amorphous foamed into a bowl-like firmness. Yield 78.5 g (70% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

(Synthesis of TAS-11)
32 g of phosphorus oxide and 288 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of 80 ° C. to 90 ° C. for 3 hours. After allowing to cool to room temperature, 78.7 g of bis (4-methoxyphenyl) sulfoxide and 60.1 g of 1-methyl-4-phenylsulfanylbenzene were added and stirred at room temperature for 3 hours. . When 55.2 g of potassium hexafluorophosphate was dissolved in 3 L of pure 5 L in a 5 L conical beaker and the above reaction solution was added little by little while stirring with a mechanical stirrer, a soft white amorphous was formed. Stirring was stopped, the supernatant was removed by decantation, 600 ml of methylene chloride was added to the residue, and a 25 g potassium hexafluorophosphate / pure 500 ml solution was added and dispersed for 1 hour. After separation of the aqueous layer, the methylene chloride layer was concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment, the solvent was concentrated under reduced pressure to obtain a light brown oil component. Hexane was added and suspended, and TAS-11 was obtained after reprecipitation while vigorously stirring with a mechanical stirrer. Yield 166.0 g (94% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

(Synthesis of TAS-13)
To a 1 L flask equipped with a calcium chloride tube and a thermometer, 32 g of phosphorus oxide and 288 g of methanesulfonic acid were added, and the mixture was heated and stirred at an internal temperature of 80 to 90 ° C. for 3 hours. After allowing to cool to room temperature, 69.1 g of p-toluyl sulfoxide and 33 g of anisole were added and stirred at room temperature for 3 hours. When 55.2 g of potassium hexafluorophosphate was dissolved in 3 L of pure beaker in a 5 L beaker, and the above reaction solution was added little by little while stirring with a mechanical stirrer, a nougat amorphous was formed. Stirring was stopped, the supernatant was removed by decantation, 600 ml of methylene chloride was added to the residue, and a 25 g potassium hexafluorophosphate / pure 500 ml solution was added and dispersed for 1 hour. After separation of the aqueous layer, the methylene chloride layer was decolorized by adding activated carbon, and the activated carbon was filtered off and concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment and concentration of the solvent under reduced pressure, 132.6 g of crude crystals were obtained. Add 300 ml of isopropyl alcohol and 10-30 ml of methylene chloride, heat and disperse in a 60-70 ° C. water bath, allow to cool to near room temperature, add 200 ml of isopropyl alcohol, and stir at room temperature for 1 hour. -13 was obtained. Yield 123.7 g (88% yield). It identified with the target object by < ¹ > H-NMR and a mass spectrum.

  The triarylsulfonium salt (polymerization initiator) used in the present invention is preferably contained at a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass of the compound having cationic polymerizability. If the content of the polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, there is no further effect of improving curability. These triarylsulfonium salts can be used alone or in combination of two or more.

  In the present invention, it is preferable to use a basic compound in combination for further improving the ejection stability. This is particularly effective when the iodonium salt as described above is used as the photoacid generator.

  As the basic compound, any known compounds can be used, and typical examples include basic alkali metal compounds, basic alkaline earth metal compounds, and basic organic compounds such as amines.

  Examples of basic alkali metal compounds include alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.), Examples include alkali metal alcoholates (for example, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and the like).

  As the basic alkaline earth metal compound, similarly, an alkaline earth metal hydroxide (eg, magnesium hydroxide, calcium hydroxide, etc.), an alkali metal carbonate (eg, magnesium carbonate, calcium carbonate, etc.), Examples include alkali metal alcoholates (eg, magnesium methoxide).

  Examples of the basic organic compound include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine. Among these, amines are preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, Xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine, etc. Is mentioned.

  The concentration in the presence of the basic compound is preferably in the range of 10 to 1000 ppm, particularly 20 to 500 ppm, based on the total mass of the photopolymerizable monomer. In addition, a basic compound may be used individually or may be used in combination of multiple.

  In the present invention, it is preferable to use a nonionic surfactant in combination for further improving the ejection stability.

  The nonionic surfactant used in the present invention is not particularly limited, and examples thereof include polyoxyethylene-polyoxypropylene condensate, polyoxyethylene lauryl ether, secondary alcohol ethoxylate, and primary alcohol ethoxylate. , Nonylphenol ethoxylate, octylphenol ethoxylate, oleyl alcohol ethoxylate, lauryl alcohol ethoxylate, polyethylene glycol, polyoxyethylene glycol oleate, sorbitan stearyl ester, sorbitan oleyl ester, polyoxyethylene sorbitan oleyl ester, 2-hydroxyethyl methacrylate, Hydroxyl-containing unsaturated monomers such as 4-hydroxybutyl acrylate and polyethylene glycol monomethacrylate are copolymerized Acrylic resin, etc. may be exemplified. Furthermore, alcohols such as isopropyl alcohol, n-butyl alcohol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, or glycol ethers can be exemplified. The nonionic surfactant may be used alone or as a mixture of two or more.

  In the present invention, the nonionic surfactant is particularly preferably a fluorosurfactant having a perfluoroalkyl group in the molecule. As the fluorine-based surfactant having a perfluoroalkyl group in the molecule used in the present invention, a perfluoroalkylethylene oxide adduct, a perfluoroalkylamine oxide, a perfluoroalkyl-containing oligomer, specifically, for example, “ “Surflon S-141”, “Surflon S-145”, “Surflon S-381”, “Surflon S-383”, “Surflon S-393”, “Surflon SC-101”, “Surflon SC-105” , “Surflon KH-40”, “Surflon SA-100” (product of Seimi Chemical Co., Ltd.), “Megafuck F-171”, “Megafuck F-172”, “Megafuck F-173”, “Megafuck F-177”, “Megafuck F-178A”, “Megafa” "F-178K", "Mega-F-F-179", "Mega-F-F-183", "Mega-F-F-184", "Mega-F-F-815", "Mega-F-F-470", "Mega-F-F" -471 "(the product of Dainippon Ink & Chemicals, Inc.), etc. (Reference:" 13700 Chemical Products ", p1239-p1242, Chemical Industries Daily (2000)). In the ink of the present invention, the fluorosurfactant having a perfluoroalkyl group may be used alone or as a mixture of two or more.

  The ink of the present invention is characterized by containing a compound having an oxetane ring as the photopolymerizable compound.

  The oxetane compound that can be used in the present invention is a compound having an oxetane ring. For example, any known oxetane compound as disclosed in JP-A Nos. 2001-220526 and 2001-310937 can be used.

  Moreover, in this invention, it is preferable to contain the compound which has an at least 1 sort (s) of oxirane group from a viewpoint of the further sclerosis | hardenability and discharge stability improvement.

  Various known cationic polymerizable monomers can be used as the photopolymerizable monomer. For example, JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, JP-A-2001-220526 Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like.

  Examples of the epoxy compound include the following aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

  A preferable aromatic epoxide is a di- or polyglycidyl ether produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, such as bisphenol A or an alkylene thereof. Examples thereof include di- or polyglycidyl ethers of oxide adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is preferable.

  Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers, polypropylene glycols or diglycidyl ethers of adducts thereof Tel and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Among these epoxides, in view of fast curability, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable. In the present invention, one of the epoxides may be used alone, or two or more may be used in appropriate combination.

  In the present invention, the alicyclic epoxy compound is preferably a compound represented by the general formulas (A) and (I) to (VI).

In the general formulas (A) and (I) to (VI), R ₁₀₀ , R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , R ₁₀₄ , R ₁₀₅ , and R ₁₀₆ each represent a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group). Etc.), an alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group) , Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) ) And the like. Among the above substituents, an alkyl group, an alkoxy group, or an alkoxycarbonyl group is preferable.

  In the general formulas (A) and (I) to (VI), m0, m1, m2, m3, m4, and m6 each represents an integer of 0 to 2, and 0 or 1 is preferable. M5 represents 1 or 2.

In the general formula (A), L ₀ is the main chain an oxygen atom or a sulfur atom which may contain an r0 + 1 valent connecting group or a single bond the carbon number of 1 to 15, wherein the general formula (I), L ₁ Is an R1 + 1 valent linking group or a single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. In the general formula (II), L ₂ contains an oxygen atom or a sulfur atom in the main chain. Or an R2 + 1 valent linking group or a single bond having 1 to 15 carbon atoms, in the general formula (III) and the general formula (IV), L ₃ and L ₄ each contain an oxygen atom or a sulfur atom in the main chain. Or a divalent linking group having a carbon number of 8 or a single bond.

  Examples of the divalent linking group that may contain an oxygen atom or a sulfur atom in the main chain include the following groups, and these groups and —O— group, —S— group, —CO— group, —CS -The group formed by combining a plurality of groups can be mentioned.

Methylene group: [—CH ₂ —],
Ethylidene group: [> CHCH ₃ ],
Isopropylidene group: [> C (CH ₃ ) ₂ ]
1,2-ethylene group: [—CH ₂ CH ₂ —],
1,2-propylene group: [—CH (CH ₃ ) CH ₂ —],
1,3-propanediyl group: [—CH ₂ CH ₂ CH ₂ —],
2,2-dimethyl-1,3-propanediyl group: [—CH ₂ C (CH ₃ ) ₂ CH ₂ —],
2,2-dimethoxy-1,3-propanediyl group: [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —],
2,2-dimethoxymethyl-1,3-propanediyl group: [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —],
1-methyl-1,3-propanediyl group: [—CH (CH ₃ ) CH ₂ CH ₂ —],
1,4-butanediyl group: [—CH ₂ CH ₂ CH ₂ CH ₂ —],
1,5-pentanediyl group: [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —],
Oxydiethylene group: [—CH ₂ CH ₂ OCH ₂ CH ₂ —],
Thiodiethylene group: [—CH ₂ CH ₂ SCH ₂ CH ₂ —],
3-oxothiodiethylene group: [—CH ₂ CH ₂ SOCH ₂ CH ₂ —],
3,3-dioxothiodiethylene group: [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —],
1,4-dimethyl-3-oxa-1,5-pentanediyl group: [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
3-oxopentanediyl group: [—CH ₂ CH ₂ COCH ₂ CH ₂ —],
1,5-dioxo-3-oxapentanediyl group: [—COCH ₂ OCH ₂ CO—],
4-oxa-1,7-heptanediyl group: [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —],
3,6-dioxa-1,8-octanediyl group: [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —],
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group: [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group: [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group: [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group: [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
4,7-dioxo-3,8-dioxa-1,10-decandiyl group: [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —],
3,8-dioxo-4,7-dioxa-1,10-decandiyl group: [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —],
1,3-cyclopentane-diyl _{group: [- 1,3-C 5 H} 8 -],
1,2-cyclohexanediyl group: [-1,2-C ₆ H _10- ],
1,3-cyclohexanediyl group: [-1,3-C ₆ H _10- ],
1,4-cyclohexanediyl group: [-1,4-C ₆ H _10- ],
2,5-tetrahydrofurandiyl group: [2,5-C ₄ H ₆ O—]
p- phenylene _{group: [- p-C 6 H} 4 -],
m- phenylene _{group: [- m-C 6 H} 4 -],
α, α'-o- xylylene _{group: [- o-CH 2 -C} 6 H 4 -CH 2 -],
α, α'-m- xylylene _{group: [- m-CH 2 -C} 6 H 4 -CH 2 -],
α, α'-p- xylylene _{group: [- p-CH 2 -C} 6 H 4 -CH 2 -],
Furan-2,5-diyl - bismethylene _{group: [2,5-CH 2 -C 4} H 2 O-CH 2 -]
Thiophene-2,5-diyl-bismethylene group: [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —]
Isopropylidenebis -p- phenylene _{group: [- p-C 6 H} 4 -C (CH 3) 2 -p-C 6 H 4 -]
Examples of the trivalent or higher valent linking group include a group formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO—. And a group formed by combining a plurality of groups and -CS- groups.

L ₀ , L ₁ , L ₂ , L ₃ and L ₄ may each have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), An alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) Etc. Preferred as a substituent is an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

L ₀ , L ₁ and L ₂ are preferably divalent linking groups having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, or L ₀ , L ₁ , L ₂ , L ₃ , L ₄ is more preferably a divalent linking group having 1 to 5 carbon atoms each having a main chain composed of only carbon.

  p1 and q1 each represents 0 or 1, and p1 + q1 is preferably 1 or more. p2 and q2 each represents 0 or 1, each preferably 1; p3 and p4 each represents 0 or 1.

  Specific examples of preferable alicyclic epoxy compounds are shown below, but the present invention is not limited thereto.

  In each of the above alicyclic epoxy compounds according to the present invention, a value obtained by dividing the molecular weight by the total number of epoxy groups in the molecule is preferably 160 to 300.

  The synthesis of the alicyclic epoxy compounds represented by the general formulas (A) and (I) to (VI) according to the present invention can be performed, for example, according to the methods described in the patent specifications listed below. it can.

A: US Pat. No. 2,745,847 B: US Pat. No. 2,750,395 C: US Pat. No. 2,853,498 D: US Pat. No. 2,853,499 E: US Pat. No. 2,863,881 In the following, synthesis examples of the above exemplary compounds are shown according to the methods described in the above patent specifications, but the present invention is not limited thereto.

(Synthesis Example 1)
Example Compound EP-9: Synthesis of Ethylglycol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Synthesis of Methyl- (4-methyl-3-cyclohexanecarboxylate)>
Methyl- (4-methyl-3-cyclohexanecarboxylate) was synthesized from isoprene and methyl acrylate as raw materials by a known Diels-Alder reaction. Reactions are described in the literature (J. Organomet. Chem., 285, 1985, 333-342, J. Phys. Chem., 95, 5, 1992, 2293-2297, Acta. Chem. Scand., 47, 6, 1993, 581-591) or reaction conditions according to the conditions described in US Pat. No. 1,944,731, etc., and the desired compound was obtained in high yield.

<Synthesis of Ethyleneglycol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of Methyl- (4-methyl-3-cyclohexanecarboxylate) and 62 g (1 mol) of ethylene glycol, and reacted at 80 to 90 ° C. for 8 hours. The reaction solution was washed with aqueous sodium bicarbonate and then distilled under reduced pressure to obtain the target compound. The yield was 92%.

<Synthesis of Exemplified Compound EP-9>
306 g (1 mol) of ethylglycol-bis- (4-methyl-3-cyclohexanecarbylate) is placed in a 2 L three-headed flask, and an acetone solution having a peracetic acid content of 25% by mass while maintaining the internal temperature at 35 to 40 ° C. 770 g (192 g (2.5 mol) peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared. The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-9. The yield was 78%.

  The structure of the obtained exemplary compound EP-9 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy root) ), 4.10 (s, 4H, —CH ₂ —O—)
(Synthesis Example 2)
Example Compound EP-12: Synthesis of Propane-1,2-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Propane-1,2-diol-bis- (4-methyl-3-cyclohexanecarbylate) )
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of Methyl- (4-methyl-3-cyclohexanecarboxylate) and 76 g (1 mol) of Propane-1,2-diol at 80 to 90 ° C. for 8 hours. Reacted. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-12>
Propane-1,2-diol-bis- (4-methyl-3-cyclohexenecarboxylate) 320 g (1 mol) was put into a 2 L three-headed flask, and the peracetic acid content was kept at 35-40 ° C. while maintaining the internal temperature at 35-40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-12. The yield was 75%.

  The structure of the obtained exemplary compound EP-12 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.23 (d, 3H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane) Ring), 3.15 (m, 2H, epoxy root), 4.03 (m, 1H, —O—CH ₂ —), 4.18 (m, 1H, —O—CH ₂ —), 5.15 (M, 1H,> CH-O-)
(Synthesis Example 3)
Synthesis of Exemplary Compound EP-17: 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <2,2-Dimethyl-propane-1,3- Synthesis of diol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of methyl- (4-methyl-3-cyclohexanecarboxylate) and 104 g (1 mol) of 2,2-dimethyl-propane-1,3-diol. It reacted at 80-90 degreeC for 12 hours. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 86%.

<Synthesis of Exemplified Compound EP-17>
348 g (1 mol) of 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3-cyclohexenecarboxylate) was placed in a 2 L three-headed flask, and the internal temperature was kept at 40 ° C. 770 g of an acetone solution having an acetic acid content of 25% by mass (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-17. The yield was 70%.

  The structure of exemplary compound EP-17 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 0.96 (s, 6H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane) Ring), 3.00 (m, 2H, epoxy root), 3.87 (s, 4H, —O—CH ₂ —)
(Synthesis Example 4)
Synthesis of Exemplified Compound EP-31: 1,3-Bis- (4-methyl-3,4-epoxy-cyclohexylmethyl) -2-propanol <Synthesis of 4-Methyl-3-cyclohexenylmethyl>
4-Methyl-3-cyclohexenyl aldehyde was synthesized from isoprene and acrolein by known Diels-Alder reactions. The reaction was performed under the reaction conditions according to the conditions described in the literature (J. Amer. Chem. Soc., 119, 15, 1997, 3507-3512, Tetrahedron Lett., 40, 32, 1999, 5817-5822). The target compound was obtained in high yield. Subsequently, 4-methyl-3-cyclohexenyl methanol was synthesized in a high yield by reducing this compound.

<Synthesis of 1,2-Bis- (4-methyl-3-cyclohexylmethyl) -2-propanol>
305 g (2.2 mol) of potassium carbonate was added to 1 L of acetone containing 284 g (2 mol) of 4-methyl-3-cyclohexenylethanol and 92 g (1 mol) of epichlorohydrin, and reacted at 50 ° C. for 8 hours. The precipitated salt was removed by filtration, the reaction solution was concentrated under reduced pressure, and the remaining crude product was distilled under reduced pressure to obtain the desired compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-31>
308 g (1 mol) of 1,2-Bis- (4-methyl-3-cyclomethylyloxy) -2-propanol was placed in a 2 L three-headed flask, and the peracetic acid content was maintained while maintaining the internal temperature at 35-40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-31. The yield was 83%.

  The structure of exemplary compound EP-31 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.4 to 2.0 (m, 14H, cyclohexane ring), 2.7 (s, 1H, —OH) ), 3.10 (m, 2H, epoxy base), 3.45 (d, 4H, -CH 2 -O -), 3.50 (m, 4H, -CH 2 -O -), 3.92 ( m, 1H,> CH-)
(Synthesis Example 5)
Exemplary Compound EP-35: Synthesis of Bis- (4-methyl-3,4-epoxy-cyclohexylmethyl) oxalate <Synthesis of Bis- (4-methyl-3-cyclomethylethyl) succinate>
To a 1 L toluene solution containing 284 g (2 mol) of 4-methyl-3-cyclohexenyl methanol and 100 g (1 mol) of succinic anhydride, 5 g of toluenesulfonic acid monohydrate was added, and water produced was separated with a water separator. The reaction was carried out at 110 to 120 ° C. for 8 hours while removing. The reaction solution was washed with an aqueous sodium bicarbonate solution, and toluene was distilled off by concentration under reduced pressure. The remaining crude product was distilled under reduced pressure to obtain the target compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-35>
335 g (1 mol) of Bis- (4-methyl-3-cyclohexylmethyl) succinate was put into a 2 L three-headed flask, and 770 g of an acetone solution having a peracetic acid content of 25% by mass while maintaining the internal temperature at 35 to 40 ° C. (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain Exemplified Compound EP-35. The yield was 75%.

  The structure of exemplary compound EP-35 was confirmed by NMR and MASS analysis.

1H NMR (CDCl3) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.4 to 2.0 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy base) 2.62 (s, 4H, —CH ₂ —CO—), 4.05 (d, 4H, —CH ₂ —O—)
Other alicyclic epoxide compounds according to the present invention listed above can also be synthesized in a high yield in the same manner as in the above method.

  In the present invention, from the viewpoint of safety such as AMES and sensitization, the epoxy compound having an oxirane group is particularly preferably at least one of an epoxidized fatty acid ester and an epoxidized fatty acid glyceride.

  The epoxidized fatty acid ester and the epoxidized fatty acid glyceride are not particularly limited as long as an epoxy group is introduced into the fatty acid ester or fatty acid glyceride.

  The epoxidized fatty acid ester is produced by epoxidizing an oleic acid ester, and examples thereof include methyl epoxy stearate, butyl epoxy stearate, octyl epoxy stearate and the like. Similarly, the epoxidized fatty acid glyceride is produced by epoxidizing soybean oil, linseed oil, castor oil and the like, and epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil and the like are used.

  Furthermore, in the present invention, a known vinyl ether compound can be used.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol. Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

  Among these vinyl ether compounds, in consideration of curability, adhesion, and surface hardness, di- or trivinyl ether compounds are preferable, and divinyl ether compounds are particularly preferable. In the present invention, one of the above vinyl ether compounds may be used alone, or two or more thereof may be used in appropriate combination.

  In the present invention, the photopolymerizable compound preferably contains 25 to 90% by mass of a compound having an oxetane ring, 10 to 70% by mass of a compound having an oxirane group, and 0 to 40% by mass of a vinyl ether compound. With this configuration, both curability and ejection stability are improved.

  In the present invention, it is particularly preferable to use a compound having an oxetane ring represented by the general formula (E) in order to further improve curability and ejection stability.

  Hereinafter, the compound containing the oxetane ring represented by the general formula (E) according to the present invention will be described.

In the general formula (E), R _{1 to} R ₆ each represent a hydrogen atom or a substituent, and at this time, R _{3 to} R ₆ do not simultaneously represent a hydrogen atom.

  Examples of the compound having one oxetane ring in the molecule include compounds represented by the following general formulas (2) to (5).

In the above general formulas (2) to (5), each Z is independently an oxygen or sulfur atom, or a divalent hydrocarbon group that may contain an oxygen or sulfur atom in the main chain, R _{1 to} R ₆ are An alkyl group having 1 to 6 carbon atoms such as a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group or a thienyl group; Groups R ₇ and R ₈ are alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group or butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group or 3-butenyl group, such as alkenyl group having 1 to 6 carbon atoms, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group Or an aryl group such as a phenoxyethyl group, an alkylcarbonyl group having 1 to 6 carbon atoms such as a propylcarbonyl group, a butylcarbonyl group or a pentylcarbonyl group, an carbonyl group such as an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group. Represents an alkoxycarbamoyl group having 1 to 6 carbon atoms such as ˜6 alkoxycarbonyl groups, ethoxycarbamoyl group, propylcarbamoyl group or butylpentylcarbamoyl group;

As the oxetane ring-containing compound used in the present invention, in the above general formulas (2) to (5), R ₁ is a lower alkyl group, particularly ethyl group, R ₇ and R ₈ are propyl group, butyl group, phenyl group or A benzyl group and those in which Z is a hydrocarbon group containing no oxygen or sulfur atom are preferred. Moreover, R < ₃ > -R < ₆ > does not represent a hydrogen atom simultaneously.

  Examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following general formulas (6), (7), and (13).

In the above general formulas (6) and (7), m is 2, 3 or 4, Z is independent, oxygen or sulfur atom, or a divalent hydrocarbon group which may contain oxygen or sulfur atom, R ₁ is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group or a butyl group, such as an alkyl group having 1 to 6 carbon atoms, a phenyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group Or a furyl group, R ₉ is, for example, a linear or branched alkylene group having 1 to 12 carbon atoms represented by the following general formula (8), a linear or branched poly (alkyleneoxy) group,

In the general formula (8), R ₁₀ represents a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.

  Or the polyvalent group selected from the group which consists of following General formula (9), (10) and (11) is represented.

In the general formula (9), n is 0 or an integer of 1 to 2000, R ₁₁ is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, and the following general formula (12) Represents a group selected from the group consisting of

In the general formula (12), j is 0 or an integer of 1 to 100, R ₁₃ is an alkyl having 1 to 10 carbon atoms, R ₁₂ is a carbon number such as a methyl group, an ethyl group, a propyl group, or a butyl group. 1-10 alkyl groups are represented.

In the general formula (10), R ₁₄ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or the like, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, A nitro group, a cyano group, a mercapto group, a lower alkyl carboxylate group or a carboxyl group is represented.

In the general formula (11), R ₁₅ represents an oxygen atom, a sulfur atom, NH, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ or C (CF ₃ ) ₂ .

As the compound having an oxetane ring used in the present invention, in the above general formulas (6) and (7), R ₁ is a lower alkyl group, particularly an ethyl group, R ₉ is represented by R ₁₄ in the general formula (10). A group that is a hydrogen atom, a hexamethylene group, in general formula (8), R ₁₀ is an ethyl group, in general formulas (9) and (12), R ₁₂ and R ₁₃ are methyl groups, and Z does not contain an oxygen or sulfur atom What is a hydrocarbon group is preferable. R _{3 to} R ₆ do not represent a hydrogen atom at the same time.

In the general formula (13), r is an integer of 25 to 200, R ₁₃ has the same meaning as R ₁₃ in the general formula (12), R ₁₆ represents an alkyl group or a trialkylsilyl group having 1 to 4 carbon atoms It is. R _{4 to} R ₆ do not represent a hydrogen atom at the same time.

  Although the specific example of a compound represented by general formula (E) below is shown, this invention is not limited only to these.

  These compounds can be easily synthesized by referring to the following documents, including the method described in the fourth lecture of "Catchball of Polymer Science and Organic Chemistry".

1) Hu Xianming, Richard M. et al. Kellogg, Synthesis, 533-538, May (1995)
2) A. O. Fitton, J .; Hill, D.C. Ejane, R.A. Miller, Synth. , 12, 1140 (1987)
3) Toshiro Imai and Shinya Nishida, Can. J. et al. Chem. Vol. 59, 2503-2509 (1981)
4) Nobujiro Shimizu, Shintaro Yamaoka, and Yuho Tsuno, Bull. Chem. Soc. Jpn. 56, 3853-3854 (1983)
5) Walter Fisher and Cyril A. Grob, Helv. Chim. Acta. , 61, 2336 (1978)
6) Chem. Ber. 101, 1850 (1968)
7) “Heterocyclic Compounds with Three-and Four-membered Rings”, Part Two, Chapter IX, Interscience Publishers, John Wiley & Sons, New York, 1964.
8) H.M. A. J. et al. Curless, “Synthetic Organic Photochemistry”, Plenum, New York (1984).
9) M.M. Braun, Nachr. Chem. Tech. Lab. 33, 213 (1985)
10) S.M. H. Schroeter, J.A. Org. Chem. , 34, 5, 1181 (1969)
11) D. R. Arnold, Adv. Photochem. 6,301 (1968)
12) “Heterocyclic Compounds with Three-and Four-membered Rings”, Part Two, Chapter IX, Interscience Publishers, John Wiley & Sons, New York, 1964.
Further, in the ink using the present invention, it is possible to use a monofunctional oxetane compound containing one oxetane ring and a polyfunctional oxetane compound containing two or more oxetane rings in combination for the film strength after curing and the recording material. It is further preferable in improving the adhesion of the resin. However, if a compound having 5 or more oxetane rings is used, the viscosity of the ink composition becomes high, which makes it difficult to handle, and the glass transition temperature of the ink composition becomes high. Sex is not enough. The compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.

  The actinic ray curable ink using the present invention contains various known dyes and / or pigments together with the actinic ray curable composition described above, but preferably contains a pigment.

  The pigments that can be preferably used in the present invention are listed below.

C. I Pigment Yellow-1, 3, 12, 13, 14, 17, 42, 81, 83, 87, 95, 109,
C. I Pigment Orange-16, 36, 38,
C. I Pigment Red-5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 101, 144, 146, 185,
C. I Pigment Violet-19, 23,
C. I Pigment Blue-15: 1, 15: 3, 15: 4, 18, 27, 29, 60,
C. I Pigment Green-7, 36,
C. I Pigment White-6, 18, 21,
C. I Pigment Black-7,
In the present invention, it is preferable to use white ink in order to improve the color concealment property on a transparent substrate such as a plastic film. In particular, in soft packaging printing and label printing, it is preferable to use white ink, but since the discharge amount increases, the use amount is naturally from the viewpoint of the above-described discharge stability and the occurrence of curling and wrinkling of the recording material. There is a limit.

  For the dispersion of the pigment, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used. Further, a dispersing agent can be added when dispersing the pigment. As the dispersant, a polymer dispersant is preferably used. Examples of the polymer dispersant include Avecia's Solsperse series and Ajinomoto Fine-Techno's PB series. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The dispersion medium is used using a solvent or a polymerizable compound. However, the radiation curable ink of the present invention is preferably solvent-free because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  The pigment is preferably dispersed so that the average particle diameter of the pigment particles is 0.08 to 0.5 μm, and the maximum particle diameter is 0.3 to 10 μm, preferably 0.3 to 3 μm. The selection of the dispersion medium, the dispersion conditions, and the filtration conditions are appropriately set. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained. In the ink of the present invention, the color material concentration is preferably 1% by mass to 10% by mass of the whole ink.

  Various additives other than those described above can be used in the actinic ray curable ink using the present invention. For example, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added. In addition, for the purpose of improving storage stability, any known basic compound can be used, but representative examples include basic organic compounds such as basic alkali metal compounds, basic alkaline earth metal compounds, and amines. Compounds and the like. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

  In the ink of the present invention, it is preferable that the viscosity at 25 ° C. is 7 to 50 mPa · s in order to obtain stable discharge and good curability regardless of the curing environment (temperature / humidity).

  As a recording material in which the present invention can be used, various non-absorbable plastics and films used for so-called soft packaging can be used in addition to ordinary uncoated paper, coated paper, etc. For example, polyethylene terephthalate (PET) film, stretched polystyrene (OPS) film, stretched polypropylene (OPP) film, stretched nylon (ONy) film, polyvinyl chloride (PVC) film, polyethylene (PE) film, triacetyl cellulose (TAC) ) A film etc. can be mentioned. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, polyvinyl alcohol (PVA), rubbers and the like can be used. Moreover, it is applicable also to metals and glass. Among these recording materials, the structure of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, or a PVC film that can be shrunk by heat. These substrates are not only susceptible to curling and deformation of the film due to ink curing shrinkage and heat generation during the curing reaction, but also the ink film is difficult to follow the substrate shrinkage.

  The surface energies of these various plastic films differ greatly, and it has been a problem in the past that the dot diameter after ink landing varies depending on the recording material. With the configuration of the present invention, a good high-definition image can be formed on a wide range of recording materials having a surface energy of 35 to 60 mN / m, including OPP films having a low surface energy, OPS films, and PET having a relatively large surface energy. .

  As the recording material using the present invention, a long (web) recording material is used in terms of the cost of the recording material such as packaging cost and production cost, the production efficiency of the print, and the ability to cope with prints of various sizes. It is more advantageous to do so.

  Next, an image forming method will be described.

  As an image forming method using the present invention, a method is preferred in which the ink is ejected and drawn on a recording material by an ink jet recording method, and then the ink is cured by irradiation with an actinic ray such as ultraviolet rays.

  In this case, the total ink film thickness after the ink has landed on the recording material and cured by irradiation with actinic rays is preferably 2 to 20 μm. In the actinic ray curable inkjet recording in the screen printing field, the total ink film thickness currently exceeds 20 μm, but in the flexible packaging printing field where the recording material is often a thin plastic material, the recording material described above is used. In addition to the problem of curling and wrinkles, there is a problem in that the entire printed material is changed in its strain and texture.

  Here, “total ink film thickness” means the maximum value of the film thickness of the ink drawn on the recording material, and even for a single color, other two colors are superimposed (secondary color), three colors are superimposed, four colors are used. Even when recording is performed by the overlapping (white ink base) inkjet recording method, the meaning of the total ink film thickness is the same.

  As the ink discharge conditions, it is preferable from the viewpoint of discharge stability that the ink jet recording head and the ink are heated to 35 to 100 ° C. and discharged. Actinic radiation curable ink has a large viscosity fluctuation range due to temperature fluctuations, and the viscosity fluctuations directly affect the droplet size and droplet ejection speed, causing image quality degradation. It is necessary to keep. The control range of the ink temperature is set temperature ± 5 ° C., preferably set temperature ± 2 ° C., more preferably set temperature ± 1 ° C.

  Moreover, it is preferable that the amount of droplets discharged from each nozzle is 2 to 15 pl. Originally, in order to form a high-definition image, it is necessary for the amount of droplets to be within this range, but when discharging with this amount of droplets, the above-described discharge stability becomes particularly severe. Even if ejection is performed with a small droplet amount such as an ink droplet amount of 2 to 15 pl, the ejection stability is improved, and a high-definition image can be stably formed.

  In the above image forming method, it is preferable that the actinic ray is irradiated for 0.001 second to 2.0 seconds after landing of the ink, more preferably 0.001 second to 1. 0 seconds. In order to form a high-definition image, it is particularly important that the irradiation timing is as early as possible.

  As a method for irradiating actinic rays, the basic method is disclosed in JP-A-60-132767. According to this, the light source is provided on both sides of the head unit, and the head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of applying a collimated light source to a mirror surface provided on the side of the head unit and irradiating the recording unit with UV light is disclosed. Yes. Any of these irradiation methods can be used in the image forming method using the present invention.

  In addition, irradiation with actinic rays is divided into two stages. First, actinic rays are irradiated by the above-described method within 0.001 to 2.0 seconds after ink landing, and further, actinic rays are irradiated after all printing is completed. The method is also a preferred embodiment. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

  Conventionally, in the UV ink jet system, a light source with high illuminance in which the total power consumption of the light source exceeds 1 kW · hr is usually used in order to suppress dot spreading and bleeding after ink landing. However, when these light sources are used, particularly in printing on a shrink label or the like, the shrinkage of the recording material is so large that it cannot be used practically.

  In the image forming method using the present invention, it is preferable to use an actinic ray having a maximum illuminance in a wavelength region of 254 nm, and a high-definition image can be formed even when a light source having a total power consumption of 1 kW · hr or more is used. In addition, the shrinkage of the recording material is within a practically acceptable level.

  In the image forming method using the present invention, it is preferable that the total power consumption of the light source for irradiating active light is less than 1 kW · hr. Examples of the light source having a total power consumption of less than 1 kW · hr include, but are not limited to, a fluorescent tube, a cold cathode tube, and an LED.

  Next, an ink jet recording apparatus (hereinafter simply referred to as a recording apparatus) using the present invention will be described.

  Hereinafter, the recording apparatus will be described with reference to the drawings as appropriate. Note that the recording apparatus of the drawings is merely one aspect of the recording apparatus of the present invention, and the recording apparatus of the present invention is not limited to this drawing.

  FIG. 1 is a front view illustrating a configuration of a main part of the recording apparatus. The recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like. In the recording apparatus 1, the platen unit 5 is installed under the recording material P. The platen unit 5 has a function of absorbing ultraviolet rays, and absorbs excess ultraviolet rays that have passed through the recording material P. As a result, a high-definition image can be reproduced very stably.

  The recording material P is guided by the guide member 6 and moves from the near side to the far side in FIG. 1 by the operation of the conveying means (not shown). A head scanning unit (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.

  The head carriage 2 is installed on the upper side of the recording material P, and stores a plurality of recording heads 3 to be described later according to the number of colors used for image printing on the recording material P, with the discharge ports arranged on the lower side. The head carriage 2 is installed with respect to the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.

  In FIG. 1, the head carriage 2 is white (W), yellow (Y), magenta (M), cyan (C), black (K), light yellow (Ly), light magenta (Lm), and light cyan (Lc). Although the drawing is carried out assuming that the recording heads 3 of light black (Lk) and white (W) are accommodated, the number of colors of the recording heads 3 accommodated in the head carriage 2 is determined as appropriate. Is.

  The recording head 3 has a discharge port by operating a discharge means (not shown) provided with a plurality of actinic ray curable inks (for example, UV curable ink) supplied by an ink supply means (not shown). To the recording material P. The UV ink ejected by the recording head 3 is composed of a coloring material, a polymerizable monomer, an initiator, and the like, and the monomer crosslinks when the initiator acts as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by a polymerization reaction.

  During the scanning in which the recording head 3 moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. 1 by driving the head scanning means, a certain area (landing possible area) in the recording material P On the other hand, UV ink is ejected as ink droplets, and ink droplets are landed on the landable area.

  The above scanning is performed as many times as necessary, and after UV ink is ejected toward one landable area, the recording material P is appropriately moved from the front to the back in FIG. 1, the recording head 3 discharges UV ink to the next landable area adjacent in the depth direction in FIG.

  By repeating the above operation and ejecting the UV ink from the recording head 3 in conjunction with the head scanning means and the conveying means, an image composed of an aggregate of UV ink droplets is formed on the recording material P.

  The irradiation unit 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength. Here, as the ultraviolet lamp, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a hot cathode tube, a cold cathode tube, a black light, an LED (light emitting diode) and the like can be applied. Cathode tubes, mercury lamps or black lights are preferred. In particular, a low-pressure mercury lamp, a hot cathode tube, a cold cathode tube, and a germicidal lamp that emit ultraviolet rays having a wavelength of 254 nm are preferable in terms of efficient bleeding prevention and dot diameter control. By using a hot cathode tube as the radiation source of the irradiation means 4, the irradiation means 4 for curing the UV ink can be produced at low cost.

  The irradiating means 4 has substantially the same shape as the maximum one that can be set by the recording apparatus (UV inkjet printer) 1 among the landable areas in which the recording head 3 ejects UV ink by one scan driven by the head scanning means. , Having a shape larger than the landable area.

  The irradiation means 4 is fixed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.

  As described above, as a means for adjusting the illuminance of the ink discharge portion, not only the entire recording head 3 is shielded, but in addition, the ink discharge of the recording head 3 is determined from the distance h1 between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the portion 31 and the recording material P (h1 <h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). Further, it is more preferable to provide a bellows structure 7 between the recording head 3 and the irradiation means 4.

  Here, the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be changed as appropriate by replacing the ultraviolet lamp or filter provided in the irradiation means 4.

  The ink using the present invention has very excellent ejection stability, and is particularly effective when an image is formed using a line head type recording apparatus.

  FIG. 2 is a top view illustrating another example of the configuration of the main part of the ink jet recording apparatus.

  The ink jet recording apparatus shown in FIG. 2 is called a line head system, and a plurality of ink jet recording heads 3 of each color are fixedly arranged on the head carriage 2 so as to cover the entire width of the recording material P. ing.

  On the other hand, on the downstream side of the head carriage 2, there is provided irradiation means 4 arranged so as to cover the entire width of the recording material P and cover the entire area of the ink printing surface. As the ultraviolet lamp used in the illuminating means 4, the same one as described in FIG. 1 can be used.

  In this line head system, the head carriage 2 and the irradiating means 4 are fixed, and only the recording material P is conveyed, and ink ejection and curing are performed to form an image.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<Preparation of ink composition set>
According to the following method, ink composition sets 1 to 8 having the compositions shown in Tables 1 to 8 were prepared.

  3 parts by mass of a dispersing agent (PB822 manufactured by Ajinomoto Fine Techno Co., Ltd.) and each photopolymerizable compound shown in Tables 1 to 8 were placed in a stainless beaker and stirred for 1 hour while heating on a 65 ° C hot plate. Mix and dissolve. Next, after adding the coloring materials described in Tables 1 to 6 to this solution, the solution was placed in a plastic bottle together with 200 g of zirconia beads having a diameter of 1 mm and sealed, and subjected to dispersion treatment for 2 hours using a paint shaker. Next, the zirconia beads are removed, and various additives such as photoacid generators, acid proliferators, and surfactants are added in combinations shown in Tables 1 to 8, and this is added to a 0.8 μm membrane to prevent printer clogging. Ink composition sets 1 to 8 were prepared by filtering with a filter.

  In addition, each color ink viscosity (measurement temperature: 25 ° C.) of each prepared ink composition set is as follows. The viscosity is indicated by the viscosity range at the maximum and minimum viscosity of each color ink.

Ink composition set 1: 28 to 33 mPa · s
Ink composition set 2: 31-34 mPa · s
Ink composition set 3: 24-27 mPa · s
Ink composition set 4: 22 to 26 mPa · s
Ink composition set 5: 28 to 33 mPa · s
Ink composition set 6: 24 to 27 mPa · s
Ink composition set 7: 25 to 28 mPa · s
Ink composition set 8: 27 to 31 mPa · s

  Details of each ink, each compound, and display described in Tables 1 to 8 are as follows.

K: dark black ink C: dark cyan ink M: dark magenta ink Y: dark yellow ink W: white ink Lk: light black ink Lc: light cyan ink Lm: light magenta ink Ly: light yellow ink Color material 1: C.I. I. pigment Black 7
Color material 2: C.I. I. pigment Blue 15: 3
Color material 3: C.I. I. pigment Red 57: 1
Color material 4: C.I. I. pigment Yellow 13
Coloring material 5: Titanium oxide (anatase type average particle size 0.20 μm)
[Photopolymerizable compound]
* E1: Alicyclic epoxy compound Celoxide 2021P: Daicel Chemical Industries, Ltd. Celoxide 3000: Daicel Chemical Industries, Ltd. LDO: ATOFINA Corporation * E2: Epoxylated fatty acid isobutyl D-55: Adeka Sizer D-55 (Asahi Denka Kogyo Co., Ltd.) Manufactured epoxidized fatty acid butyl epoxy compound)
E-4030: Sansosizer E-4030 (Epoxylated fatty acid butyl produced by Shin Nippon Chemical Co., Ltd.)
* E3: Epoxidized soybean oil Vikoflex 7010: manufactured by ATOFINA Vikoflex 9010: manufactured by ATOFINA * O: oxetane compound OXT-211: 3-ethyl-3- (phenoxymethyl) oxetane (manufactured by Toagosei Co., Ltd.)
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
RSOX: Toagosei Co., Ltd. [Acid Proliferator]
ACPRESS 11M: Nippon Chemix Co., Ltd. [Photoacid generator]
UVI6992: Triphenylsulfonium salt (Syracure UVI6992 manufactured by Union Carbide) Propylene carbonate 50% solution [Surfactant]
F178k: Megafax F178k Perfluoroalkyl group-containing acrylic oligomer (Dainippon Ink Chemical Co., Ltd.)
OP-85R: Nonionic OP-85R (Sorbitan ester type nonionic surfactant) Sorbitan trioleate HLB = 1.8 (manufactured by NOF Corporation)
F1405: Megafax F1405 Perfluoroalkyl group-containing ethylene oxide adduct (manufactured by Dainippon Ink & Chemicals, Inc.)
F470: Megafax F470 Perfluoroalkyl group-containing acrylic oligomer (Dainippon Ink and Chemicals)
TF907: Megafax EXP TF907 Perfluoroalkyl group-containing ethylene oxide adduct (Dainippon Ink Chemical Co., Ltd.)
[Dispersant]
PB822: Ajinomoto Fine Techno Co., Ltd. [Others]
* 1: γ-caprolactone (reagent manufactured by Kanto Chemical Co., Inc.)
* 2: N-ethyldiethanolamine (basic compound)
* 3: Propylene carbonate (reagent, manufactured by Kanto Chemical Co., Inc.)
* 4: Tributylamine (basic compound)
* 5: γ-butyrolactone (reagent manufactured by Kanto Chemical Co., Inc.)
<< Inkjet image forming method >>
Each ink composition set 1 to 3 and 7 prepared above is loaded into an ink jet recording apparatus having the structure shown in FIG. 1 having a piezo ink jet nozzle, and each surface energy shown in Tables 9 and 10 is obtained. The following image recording was continuously performed on each long recording material having a width of 600 mm and a length of 500 m. The ink supply system was composed of an ink tank, a supply pipe, a front chamber ink tank immediately before the head, a pipe with a filter, and a piezo head. The ink was insulated from the front chamber tank to the head portion and heated at 50 ° C. The piezo head was driven so that 2 to 15 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi, and each ink was ejected continuously. After each ink landed, the ink was cured by irradiating ultraviolet rays from a hot cathode tube as the irradiation light source A shown in Tables 9 and 10 instantly (less than 2 seconds after landing) by the lamp units on both sides of the carriage. When the total ink film thickness was measured after image recording, it was in the range of 2.3 to 13 μm. In the present invention, dpi represents the number of dots per 2.54 cm.

  Next, with the line head type ink jet recording apparatus shown in FIG. 2, the ink composition sets 4 to 6 and 8 are used to irradiate ultraviolet rays from two low-pressure mercury lamps (line light sources) as the irradiation light source B. It hardened | cured and each image was formed similarly.

  Printing was performed by the above two methods under three conditions: an environment of 10 ° C. and 20% RH, an environment of 25 ° C. and 50% RH, and an environment of 30 ° C. and 80% RH.

  In addition, the detail of each irradiation light source of Table 9 and Table 10 is as follows.

Irradiation light source A: Hot cathode tube (U-tube manufactured by Nippon Po, Inc. Light source power consumption less than 1 kW · hr)
Irradiation light source B: Low-pressure mercury lamp (custom-made by Iwasaki Electric Co., Ltd.)
Moreover, the illumination intensity of each irradiation light source of Table 9 and Table 10 measured and displayed the integrated illumination intensity of 220-420 nm by URS40 made from Ushio Electric.

  Moreover, the detail of the irradiation position of Table 9 and Table 10 is as follows.

* 1: Both ends of the recording head (Fig. 1 method)
* 2: Downstream position in the recording material conveyance direction (Fig. 2 method)
Details of the abbreviations of the recording materials shown in Tables 9 and 10 are as follows.

OPP: oriented polypropylene
PET: Polyethylene terephthalate
PVC: polyvinyl chloride

<Evaluation of inkjet recording image>
Each image recorded by the above image forming method was subjected to the following evaluations.

[Evaluation of character quality]
Using each color ink of Y, M, C, and K, a 6-point MS Mincho character was printed at a target density, and the character roughness was enlarged and evaluated with a loupe, and character quality was evaluated according to the following criteria.

◎: No roughness ○: Slightly gritty △: Slightly visible, but can be recognized as text, but can be used as barely as possible.
Print at 720 dpi so that 1 dot of each color of Y, M, C, K is adjacent to each other, enlarge each adjacent color dot with a loupe, visually observe the color mixture due to bleeding, and evaluate the color mixture according to the following criteria It was.

◎: Adjacent dot shape maintains a perfect circle and no bleeding occurs. ○: Adjacent dot shape maintains an almost perfect circle and almost no bleeding. Δ: Adjacent dot is slightly blurred and dot shape is slightly. Table 11 shows the evaluation results obtained as described above. Levels that are broken but can be used at the last minute ×: Levels where adjacent dots are blurred and mixed and cannot be used.

  As is apparent from Table 11, the image forming method having the configuration according to the present invention is superior to the comparative example in character quality and color mixing (bleeding) with respect to all recording materials even under various printing environments. It can be seen that a high-definition image can be recorded without the occurrence of the above.

Example 2
<< Preparation of actinic ray curable inkjet ink composition >>
An actinic ray curable inkjet ink composition 101 having the following composition was prepared.

Triarylsulfonium salt compound: TAS-1 5 parts by mass Epoxy compound: EP-17 95 parts by mass The above-described triarylsulfonium salt compound and epoxy compound are changed to the compounds shown in Table 12, and the actinic ray curable inkjet ink composition 102- 126 was prepared.

  Details of the compounds described in Table 12 are shown below.

UVI 6990: Triphenylsulfonium salt (manufactured by Cyracure UVI 6990 Union Carbide)
Celoxide 3000: Alicyclic epoxy (manufactured by Daicel UCB)
Celoxide 2021P: Alicyclic epoxy (Daicel UCB)
1 ml of the obtained actinic radiation curable inkjet ink composition was applied to a 157 cm ² PET film, placed in a 6.1 L transparent sealed container and heated to 30 ° C., and irradiated with a high pressure mercury lamp at an irradiation energy of 10 mJ / cm. Irradiation was performed at ^{2 for} 20 seconds. Next, the gas in the sealed container was collected, and benzene was quantified by gas chromatography. Benzene was identified by GC-MS, and benzene was quantified using a calibration curve prepared by analyzing a certain amount of benzene by gas chromatography. The detected amount of benzene was shown as the generated mass (μg) per 1 m ² of the closed container volume. The results are shown in Table 12.

  Moreover, the change of the viscosity of the obtained hardening composition is also shown collectively. The change in viscosity was judged from the tactile sensation of the experimenter by touching the light unirradiated coating film and the coating film after the light irradiation with a metal spatula. “Gelification” means that a gel-like coating film was formed, and “Thickening” means that there is a clear difference in viscosity between the light unirradiated film and the film after light irradiation. `` Slightly thickened '' means that there is a slight difference in viscosity between the light-unirradiated film and the film after light irradiation. This shows that no significant difference in tactile sensation was found in the membrane.

  As is apparent from Table 12, when an actinic ray curable inkjet ink composition comprising the triarylsulfonium salt and the epoxy compound according to the present invention is irradiated with ultraviolet rays, gelation occurs without causing benzene generation, and polymerization proceeds. It shows that you are doing.

Example 3
<Preparation of inkjet ink>
(Preparation of ink 201)
Ink 201 having the following composition was prepared. Ink 201 was prepared by dispersing each composition excluding the photoacid generator for 4 hours using a sand grinder, adding a photoacid generator, and filtering through a 0.8 μm membrane filter. It was prepared by dehydration under reduced pressure while heating.

C. I. Pigment Red 184 3 parts by weight UVI-6990 5 parts by weight Aron Oxetane OXT-221 70 parts by weight Celoxide 3000 30 parts by weight Solsperse 24000 (manufactured by Avecia) 1 part by weight (preparation of inks 202 to 238)
Inks 202 to 230 and 235 to 238 of the present invention were obtained in the same manner as the ink 201 except that the pigment, photoacid generator, epoxy compound, and oxetane compound were changed to the compositions shown in Table 13 below.

  Details of the compounds described in Table 13 are shown below.

<Pigment>
P0: C.I. I. Pigment Red 184
P1: 250 parts of crude copper phthalocyanine (“Copper phthalocyanine” manufactured by Toyo Ink Manufacturing Co., Ltd.), 2500 parts of sodium chloride and 160 parts of polyethylene glycol (“Polyethylene glycol 300” manufactured by Tokyo Chemical Industry Co., Ltd.) 1 gallon) kneader (manufactured by Inoue Seisakusho) was kneaded for 3 hours. Next, this mixture is poured into 2.5 liters of warm water, heated to about 80 ° C. and stirred for about 1 hour with a high speed mixer to form a slurry, followed by filtration and water washing 5 times to repeat sodium chloride and solvent And then dried by spray drying to obtain Pigment P1.

  P2: 250 parts of quinacridone red pigment (“Cincacia Magenta RT-355-D” manufactured by Ciba Geigy), 2500 parts of sodium chloride and 160 parts of “polyethylene glycol 300” were added to 4.55 L (1 gallon) of styrene. ) The mixture was charged into a kneader, and pigment P2 was obtained in the same manner as P1.

<Epoxy compound>
Celoxide 3000: Alicyclic epoxy (manufactured by Daicel UCB)
Celoxide 2021P: Alicyclic epoxy (Daicel UCB)
<Photoacid generator>
UVI 6990: Triphenylsulfonium salt (manufactured by Cyracure UVI 6990 Union Carbide)
PI-1: Triphenylsulfonium salt (compound described in German Patent No. 2061280, page 2)
PI-2: Triphenylsulfonium salt (compound described in U.S. Pat. No. 4,407,759 Table III)
<Oxetane compound>
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
<< Inkjet image recording and evaluation >>
Using the inks prepared above, image recording and evaluation of the obtained images were performed according to the following methods.

[Image Evaluation A]
(Image recording)
Piezo-type ink jet nozzles (nozzle pitch 360 dpi, dpi in the present invention represents the number of dots per 2.54 cm) that can produce a droplet size of 7 pl for each ink obtained, and the nozzle portion heated to 50 ° C. Controlled and corona-treated polyethylene terephthalate film was used as a base material and emitted, and a magenta solid image and a 6-point MS Mincho font were printed. The light source is a fluorescent tube having a main peak at 308 nm. Under the condition that the illuminance of the substrate surface is 10 mW / cm ² directly under the light source, the exposure is started 0.3 seconds after landing and the exposure is performed after 0.8 seconds. Ended. The exposure energy was 5 mJ / cm ² . This image printing was performed in a low humidity environment (25 ° C., 20% RH) and a high humidity environment (25 ° C., 80% RH).

(Image evaluation)
The following evaluation was performed on each image obtained as described above.

<Evaluation of ink curability>
For the printed images formed under each environment, the ink curability was evaluated according to the following criteria.

○: The image has no tackiness even when touched immediately after the exposure is finished. Δ: The image has a slight tackiness when touched immediately after the exposure is finished, but the tackiness disappears after one minute. X: The tackiness remains even after one minute after the exposure. Evaluation of material adhesion>
A solid tape of 25 mm in width is affixed to the solid image formed in each environment and pressed firmly, then quickly peeled off at a 90 ° peel angle, and the state of the image after isolation is visually observed. The base material adhesion was evaluated according to the above criteria.

○: The image is not peeled even when the tape is peeled △: The image is peeled off partly by the tape peeling ×: The whole image is peeled off by the tape peeling <Evaluation of image bleeding resistance>
The 6-point MS Mincho characters formed under each environment were observed with a loupe, the state of adjacent dots was observed, and image blur resistance was evaluated according to the following criteria.

◯: Almost no bleeding between 2 dots Δ: Slight bleeding between 2 dots is observed X: The dots are greatly blurred Tables 14 and 15 show the results obtained as described above.

[Image Evaluation B]
In the image evaluation A, image recording and evaluation were performed in the same manner except that the exposure irradiation start time after printing the ink was changed to 0.4 seconds and the exposure irradiation end time was changed after 0.9 seconds. . The exposure time and exposure energy were 5 mJ / cm ² for 0.5 seconds, respectively, as in image evaluation A. The obtained results are shown in Tables 16 and 17.

  As is apparent from Tables 14 to 17, the ink containing the actinic ray curable inkjet ink composition of the present invention has excellent ink curability and substrate in a high humidity environment and various exposure environments as compared with the comparative example. It can be seen that a high-quality image with excellent adhesion and no bleeding can be obtained.

It is a front view which shows an example of a structure of the principal part of the inkjet recording device of this invention. It is a top view which shows another example of a structure of the principal part of the inkjet recording device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inkjet recording device 2 Head carriage (light-shielding)
DESCRIPTION OF SYMBOLS 3 Inkjet recording head 31 Ink discharge port 4 Irradiation means 5 Platen part 6 Guide member 7 Bellows structure P Recording material

Claims (9)

A triarylsulfonium salt compound, which is a compound represented by the following general formula (T-1).

[Wherein R ^T11 and R ^T12 represent an alkyl group or an aromatic group, Z ^T1 represents an oxygen atom or a sulfur atom, and R ^T13 and R ^T14 represent an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, respectively. , An alkylthio group and an arylthio group, mt1 represents an integer of 0 to 4, nt1 and pt1 each represents an integer of 1 to 5, and X ^T1 represents PF ₆ . ] The triarylsulfonium salt compound according to claim 1, wherein the compound represented by the general formula (T-1) is a compound represented by the following general formula (T-2).

[Wherein R ^T21 , R ^T22 , R ^T23 and R ^T24 each represents an alkyl group or an aromatic group, Z ^T2 represents an oxygen atom or a sulfur atom, and R ^T25 and R ^T26 each represent an alkyl group or a fluorocarbon. hydrogen group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, mt2, nt 2 and pt2 each represents an integer of 0 to 4, X ^T2 represents PF _6. ] The triarylsulfonium salt compound according to claim 2, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-3).

[Wherein, R ^T31 represents an alkyl group having 1 to 10 carbon atoms, R ^T32 and R ^T33 each represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and X ^T3 represents PF ₆ Represents. ] The triarylsulfonium salt compound according to claim 2, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-4).

[Wherein, R ^T41 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^T42 represents a substituent, mt4 represents an integer of 0 to 4, and R ^T43 and R ^T44 each represent 1 to C carbon atoms. Represents 10 alkyl groups, and X ^T4 represents PF ₆ . ] The triarylsulfonium salt compound according to claim 2, wherein the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-5).

[Wherein, R ^T51 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^T52 represents a substituent, mt5 represents an integer of 0 to 4, and R ^T53 and R ^T54 each represents 1 to C carbon atoms. Represents 10 alkyl groups, and X ^T5 represents PF ₆ . ] An active energy ray-curable composition comprising the triarylsulfonium salt compound according to any one of claims 1 to 5 and an epoxy compound. The active energy ray-curable composition according to claim 6, wherein the epoxy compound is an alicyclic epoxy compound represented by the following general formula (A).

Wherein, R ₁₀₀ represents a substituent, m0 represents an integer of 0 to 2. r0 represents an integer of 1 to 3. L ₀ represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ] The active energy ray-curable composition according to claim 6, wherein the epoxy compound is at least one selected from alicyclic epoxy compounds represented by the following general formulas (I) to (VI).

Wherein, R ₁₀₁ represents a substituent, m1 represents an integer of 0 to 2. p1 and q1 each represents 0 or 1. r1 represents an integer of 1 to 3. L ₁ represents a C 1-15 r 1 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

Wherein, R ₁₀₂ represents a substituent, m2 represents an integer of 0 to 2. p2 and q2 each represents 0 or 1. r2 represents an integer of 1 to 3. L ₂ represents an r2 + 1-valent linking group or a single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₃ represents a substituent, and m3 represents an integer of 0 to 2. p3 represents 0 or 1. L ₃ represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₄ represents a substituent, and m4 represents an integer of 0 to 2. p4 represents 0 or 1. L ₄ represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₁₀₅ represents a substituent, and m5 represents 1 or 2. ]

[Wherein, R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2. ] An actinic ray curable inkjet ink composition comprising the active energy ray curable composition according to any one of claims 6 to 8.

Images