JP2005171122A - Active energy ray-curable composition containing specific oxetane compound, ink composition for inkjet using the same, and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition cured even by a light source having low illumination without being affected by environmental humidity; to provide an ink composition for inkjet, having excellent adhesiveness to a base material, and providing a high-quality image having high image quality without bleeding by using the curable composition; and to provide a method for forming the image by using the ink composition for the inkjet. <P>SOLUTION: The active energy ray-curable composition contains an oxetane compound represented by general formula (OT-I) [wherein, L<SP>T1</SP>is an oxygen atom, a sulfur atom or -CR<SP>T111</SP>(R<SP>T112</SP>)-; R<SP>T101</SP>to R<SP>T112</SP>are each a hydrogen atom or a substituent; p<SP>T1</SP>is 0 or 1; and q<SP>T1</SP>and r<SP>T1</SP>are each 0-3]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable composition containing a specific oxetane compound, an inkjet ink composition, and an image forming method. More specifically, a cationically polymerizable oxetane compound is used to produce a highly reactive and high-quality image. The present invention relates to a photocurable ink composition for inkjet and an image forming method.

  In recent years, the inkjet recording method can be easily and inexpensively produced images, 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 these, the UV inkjet method has been attracting attention in recent years because 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. 200204 and JP 2000-504778 A disclose an ultraviolet curable inkjet ink.

  As the UV ink, a radical polymerization type and a cationic polymerization type are mainly known.

  In the ultraviolet curable ink jet recording system, the image quality, that is, the impact dot diameter is the light irradiation timing after landing, light irradiation illuminance, energy, ink droplet size, ink sensitivity, surface energy, viscosity, substrate wettability, It is controlled by factors such as landing pattern and error diffusion pattern. In particular, factors that greatly influence image quality are ink sensitivity, viscosity, surface covering, substrate wettability, and exposure conditions. Among these, the ink sensitivity is greatly influenced by the ink film thickness and exposure illuminance in the case of the radical polymerization system because it is affected by the inhibition of polymerization by oxygen, and in the cationic polymerization system, it greatly depends on the temperature and humidity.

  In radical polymerization type UV curable ink, in order to improve polymerization inhibition by oxygen, there are a method of purging with an inert gas such as nitrogen, etc. Are known.

  In order to improve the influence of humidity on the cationic polymerization type ultraviolet curable ink, a method of heating the landed ink is known as disclosed in JP-A-2002-137375.

  As the cationic polymerizable monomer used in the cationic polymerization type ultraviolet curable ink, an epoxy compound having an oxirane ring, an oxetane compound, and a vinyl ether compound are known.

  In particular, it is known that the polymerization rate is remarkably increased by using both an epoxy compound and an oxetane compound. For example, it is described in Toagosei Research Annual Report TREND2 (1999), “Application of Oxetane Compound to Photocationic Curing System”, Japanese Patent Publication No. 2679586, and the like. In particular, since the oxetane compound has good heat resistance, adhesiveness, and chemical resistance, it is useful to use it together with an epoxy compound that increases the reactivity.

  As an application example of this technique, Japanese Patent Application Laid-Open No. 2001-220526 discloses use in an ultraviolet curable ink jet. In recent years, an ultraviolet curable ink jet recording system that cures ink by ultraviolet rays has attracted attention as a method for forming an image even on a substrate having poor ink absorbability.

  Generally, as the ultraviolet curable ink, a radical polymerization type ink is well known and put into practical use. On the other hand, the cationic polymerization type ink does not inhibit the polymerization caused by oxygen as seen in radical polymerization type inks, can use a light source with low illuminance, has no odor of acrylic monomer, and has low irritation. Although there are advantages such as being there, it has not yet been put into practical use.

  One reason for this is the property that the sensitivity decreases significantly under high humidity and the property that the sensitivity depends on the temperature. Environment-dependent inks have the essential problem that their image quality depends on the environment.

There has been disclosed a method of using a cationic polymerization-based ink to heat and irradiate the landed ink (for example, see Patent Document 1). However, the heating mechanism cannot be said to be preferable from the viewpoint of application of printer cost, a heat-sensitive substrate, and the like. Further, 2- (4-methoxyphenyl) -3,3-dimethyloxetane is disclosed as a compound that is used in combination with an oxetane compound to improve the reaction rate (see, for example, Patent Document 2). This compound is reactive enough to replace an alicyclic epoxy compound in the combined use of an oxetane compound such as di [1-ethyl (3-oxetanyl)] methyl ether and an alicyclic epoxy compound. However, in the case of using a low illuminance light source such as a fluorescent lamp, it cannot be said that the sensitivity level in a high humidity environment is still sufficient.
JP 2002-137375 A JP 2001-181386 A

  The present invention has been made in view of the above problems, and its purpose is to cure an active energy ray-curable composition containing a specific oxetane compound, which is cured without being affected by environmental humidity even with a low-illuminance light source, and To provide an ink-jet ink composition excellent in ink curability and substrate adhesion and capable of obtaining a high-quality image capable of obtaining a high-quality image without bleeding, and an image forming method using the ink-jet ink composition It is in.

The above object of the present invention can be achieved by the following constitution.
(Claim 1)
An active energy ray-curable composition comprising an oxetane compound represented by the following general formula (OT-I).

[In the above general formula (OT-I), L ^T1 represents an oxygen atom, a sulfur atom, —CR ^T111 (R ^T112 ) —, R ^{T101 to} R ^T112 represent a hydrogen atom or a substituent, and p ^T1 represents 0 or 1, q ^T1 and r ^T1 represent 0 to 3; ]
(Claim 2)
2. The active energy ray-curable composition according to claim 1, which has a substituent at at least one of R ^T101 , R ^T102 , R ^T105 , and R ^T106 .
(Claim 3)
The active energy ray-curable composition according to claim 2, wherein R ^T101 , R ^T102 , R ^T105 , and R ^T106 are substituted or unsubstituted alkyl groups.
(Claim 4)
The active energy ray-curable composition according to any one of claims 1 to 3, comprising a compound that generates an acid upon irradiation with an active energy ray.
(Claim 5)
5. The active energy ray-curable composition according to claim 4, wherein the compound that generates an acid upon irradiation with active energy rays is an onium salt compound.
(Claim 6)
6. The active energy ray-curable composition according to claim 5, wherein the compound that generates an acid upon irradiation with active energy rays is a sulfonium salt compound.
(Claim 7)
The active energy ray-curable composition according to claim 6, wherein the sulfonium salt compound is represented by the following general formula (I-1), (I-2) or (I-3).

[Wherein R ₁₁ , R ₁₂ and R ₁₃ represent substituents, and m, n and p each represents an integer of 0 to 5. X ₁₁ ⁻ represents a counter ion. ]

Wherein, R ₁₄ represents a substituent, q is an integer of 0 to 2. R ₁₅ and R _{16 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. X ₁₂ ⁻ represents a counter ion. ]

[Wherein, R ₁₇ represents a substituent, and r represents an integer of 0 to 3. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group. X ₁₃ ^- is a counter ion. ]
(Claim 8)
The active energy ray-curable composition according to claim 7, wherein the sulfonium salt compound represented by the general formula (I-1) is represented by the following general formula (T-1).

(In the formula, 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, and 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 a counter anion.)
(Claim 9)
An inkjet ink composition for forming an image on a recording medium by an inkjet method, comprising the active energy ray-curable composition according to any one of claims 1 to 8.
(Claim 10)
The inkjet ink composition according to claim 9, comprising an oxetane compound having no substituent at the 2-position.
(Claim 11)
The ink composition for inkjet according to claim 9 or 10, comprising an epoxy compound or a vinyl ether compound.
(Claim 12)
50 parts by mass to 80 parts by mass of an oxetane compound having no substituent at the 2-position, 0 parts by mass to 50 parts by mass of an epoxy compound, and at least one oxetane compound represented by the general formula (OT-I) is 1 The ink composition for inkjet according to any one of claims 9 to 11, wherein the ink composition is contained in an amount of 20 to 20 parts by mass.
(Claim 13)
The ink composition for inkjet according to claim 11 or 12, wherein the epoxy compound is selected from at least one of alicyclic epoxide compounds represented by the following general formulas (VI) to (VIII): Stuff.

[Wherein, R ₆₀₁ represents an aliphatic group, and m6 represents 0 to 2. X ₁ represents — (CH ₂ ) _n6 — or — (O) _n6 —, and n6 represents 0 or 1. p1 and q1 each represents 0 or 1. r1 represents 1-3. L ₃ 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 ₇₀₁ represents an aliphatic group, and m7 represents 0 to 2. X ₂ represents — (CH ₂ ) _n7 — or — (O) _n7 —, and n7 represents 0 or 1. p2 and q2 each represents 0 or 1. r2 represents 1-3. L ₄ represents a C 1-15 r 2 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₈₀₁ represents an aliphatic group, and m8 represents 0-2. X ₃ represents — (CH ₂ ) _n8 — or — (O) _n8 —, and n8 represents 0 or 1. R ₈₀₂ and R ₈₀₃ each represent a substituent, and p3 represents 0 or 1. ]
(Claim 14)
An ink droplet is ejected onto a recording medium using a recording head having at least one nozzle capable of selectively controlling the ejection of an ink droplet, using the inkjet ink composition according to any one of claims 9 to 13. Then, after the ink has landed, the ink is cured by irradiating with active energy rays.

  As a result of intensive studies in view of the above problems, the present inventor has found that an oxanthrene ring, a xanthene ring, a phenoxathiin ring, or a dibenzofuran via a carbon atom in which two oxetane rings are bonded to adjacent positions of oxygen atoms in the oxetane ring. An active energy ray-curable composition containing at least one oxetane compound bonded to a specific position of the ring (hereinafter referred to as “the bifunctional oxetane compound of the present invention”) is a low-illuminance light source. It was possible to cure without being affected by the environmental humidity, and furthermore, when the active energy ray-curable composition of the present invention was used for an ink jet ink composition, it was found that a high-quality image was obtained, and the present invention was achieved. It depends on you.

  Furthermore, in the inkjet ink composition containing the active energy ray-curable composition of the present invention, even when a small amount of the bifunctional oxetane compound of the present invention is added to other polymerizable compounds constituting the ink composition, the environmental humidity It has become clear that it exerts a sufficient improvement effect on the inhibition of the curing reaction by.

  An active energy ray cationic curable composition containing 2- (4-methoxy-phenyl) -3,3-dimethyl-oxetane is described in Japanese Patent Application Laid-Open No. 2001-181386. There is no specific mention regarding compositions containing functional oxetanes.

  It is also shown in the above patent that the ink composition obtained by mixing 2- (4-methoxy-phenyl) -3,3-dimethyl-oxetane with other oxetane compounds has excellent curability. As a composition, an ink in which 20 to 40 parts by mass of 2- (4-methoxy-phenyl) -3,3-dimethyl-oxetane is mixed with 60 to 80 parts by mass of another oxetane compound is excellent in curing. However, it has not been suggested whether an ink obtained by adding a small amount of oxetane to another polymerizable compound exhibits sufficient curability.

  In the inkjet ink composition containing the active energy ray-curable composition of the present invention, the bifunctional oxetane compound of the present invention is 1% by mass to 20% by mass with respect to another polymerizable compound constituting the inkjet ink composition. Even when it is added at an addition ratio, it exhibits an improvement effect on the inhibition of the curing reaction due to environmental humidity. It was completely unexpected that an effect could be obtained even with such a small amount of addition.

  In the active energy ray-curable composition of the present invention, the active energy ray-curable composition of the present invention is used as an inkjet ink composition by giving a substituent to the 3-position of the oxetane ring of the bifunctional oxetane compound of the present invention. In some cases, compatibility with other polymerizable compounds can be improved, and safety, hydrophobicity, viscosity, surface tension, and other physical properties can be appropriately designed.

  Moreover, in the inkjet ink composition of the present invention, by using together with the active energy ray-curable composition containing the oxetane compound of the present invention together with an oxetane compound having no substituent at the 2-position, an inkjet ink composition is obtained. It was possible to obtain a preferable low viscosity, to improve the reactivity and to strengthen the cured film strength. Epoxy compounds or vinyl ether compounds are other cationic polymerizable monomers that can be used in combination, and by using these in combination, film properties, adhesion to a substrate, and ink properties can be appropriately adjusted.

  According to the present invention, an active energy ray-curable composition containing a specific oxetane compound that cures without being affected by environmental humidity even with a light source of low illuminance, and has excellent ink curability and substrate adhesion, and has no bleeding. It was possible to provide an ink-jet ink composition capable of obtaining a high-quality image capable of obtaining a quality image and an image forming method using the ink-jet ink composition.

  Details of the present invention will be described below.

In the general formula (OT-I), L ^T1 represents an oxygen atom, a sulfur atom, —CR ^T111 (R ^T112 ) —, preferably an oxygen atom or —CR ^T111 (R ^T112 ) —, more preferably an oxygen atom. is there.

Examples of the substituent represented by R ^{T101 to} R ^T112 in the general formula (OT-I) include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), cycloalkyl group having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), carbon 1 to 6 alkenyl groups (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkenyl groups having 1 to 6 carbon atoms (for example, acetylenyl group, 1 -Propynyl group, 2-propynyl group, 2-butynyl group, etc.), alkoxy groups having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butyl group) Xy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl Group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryloxycarbonyl group, and the like.

Two substituents on the same carbon, such as R ^T101 and R ^T102 and R ^T103 and R ^T104 , may be bonded to each other at the terminal to form a divalent group to form a ring.

  These groups may further have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, 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 (eg, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxy Examples include carbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group, and the like. As the substituent, a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group are preferable.

  The bifunctional oxetane compound of the present invention preferably has at least one substituent at the 3-position of either oxetane ring, and one or more at each 3-position of the two oxetane rings. It is more preferable that it has two substituents at the 3-positions of the two oxetane rings. Preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.), and a cycloalkyl group having 3 to 6 carbon atoms (for example, a cyclo group). Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert- Butoxy group, etc.), acyl group (eg, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group) Ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) It is. These may be further substituted, and preferred as a substituent are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group.

  As the oxetane of the present invention, a substituted or unsubstituted alkyl group is preferably substituted at the 3-position, and it is more preferable that the 3-position of the oxetane becomes a tertiary carbon by substitution with two alkyl groups. preferable. Preferred as a substituent for the alkyl group are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group.

The bifunctional oxetane compound of the present invention can be made more reactive by substituting an electron-withdrawing group at the 4-position. The electron withdrawing group is a substituent having a positive Hammett substituent constant σp. Specific examples of the electron withdrawing group include —NO ₂ , —CN, —SO ₂ —Alkyl, —SO ₂ -Aryl, -CO-Alkyl, -CO-Aryl, -CO-O-Alkyl, -CO-O-Aryl, and halogen atoms (fluorine atom, chlorine atom, bromine atom). In the oxetane compound of the present invention, a preferable electron-withdrawing group as a substituent at the 4-position is an alkyl group in which the electron-withdrawing group is substituted on a carbon atom at the α to γ positions, and particularly an alkyl group substituted with a fluorine atom. Is preferred.

In the general formula (OT-I), pT1 represents 0 or 1, preferably 1. qT1 and rT1 represent 0 to 3. When qT1 and rT1 are 2 or more, a plurality of R ^T109 or R ^T110 may be the same or different, and when substituted at adjacent positions, they are bonded to each other to form a divalent group. A ring may be formed.

  In general formula (OT-I), it is preferable that an oxygen atom is bonded to the ortho-position or para-position of the benzene ring to which the oxetane ring is bonded. That is, when the oxetane ring is bonded to the oxanthrene ring, the bonding position of the oxetane ring may be any position of the oxanthrene ring, and at least one of the benzene rings bonded to the oxetane ring has an oxygen atom bonded to the para position. More preferably, the benzene ring to which the oxetane ring is bonded most preferably has an oxygen atom bonded to the para position. When the oxetane ring is bonded to the xanthene ring, the two oxetane rings are preferably bonded to the 2-position and 5-position, 2-position and 7-position, 4-position and 5-position, 4-position and 7-position, More preferably, it is bonded to the 7-position. When the oxetane ring is bonded to the phenoxathiin ring or dibenzofuran ring, it is preferably bonded to the 2nd and 6th positions, the 2nd and 8th positions, the 4th and 6th positions, the 4th and 8th positions, More preferably, it is bonded to the 8-position.

  Specific examples of the oxetane compound of the present invention are shown below, but the present invention is not limited thereto.

  The synthesis of the oxetane compound of the present invention can be carried out according to the methods described in the literature below.

A: Hu Xianming, Richard M. et al. Kellogg, Synthesis, 533-538, May (1995)
B: A. O. Fitton, J .; Hill, D.C. Ejan, R.A. Miller, Synth. , 12, 1140 (1987)
C: Toshiro Imai and Shinya Nishida, Can. J. et al. Chem. Vol. 59, 2503-2509 (1981)
D: Nobujiro Shimizu, Shintaro Yamaoka and Yuho Tsuno, Bull. Chem. Soc. Jpn. 56, 3853-3854 (1983)
E: Walter Fisher and Cyril A.E. Grob, Helv. Chim. Acta. , 61, 2336 (1978)
F: Chem. Ber. 101, 1850 (1968)
G: “Heterocyclic Compounds with Three- and Four-membered Rings”, Part Two, Chapter IX, Interscience Publishers, John Wiley & Son, N
H: Bull. Chem. Soc. Jpn. 61, 1653 (1988)
I: Pure Appl. Chem. , A29 (10), 915 (1992)
J: Pure Appl. Chem. , A30 (2 &amp; 3), 189 (1993)
K: Japanese Patent Laid-Open No. 6-16804 L: German Patent 1,021,858 According to the above literature, examples of synthesis of exemplary compounds are shown below, but the present invention is not limited thereto.

[Synthesis Example 1]
Synthesis of exemplary compound OT-1

Isobutyl aldehyde 4.2 equivalent and compound (1) 1.0 equivalent were melt | dissolved in methanol, and the methanol solution of 2.1 equivalent of potassium hydroxide was dripped at room temperature. Subsequently, after reacting at 60 degreeC for 4 hours, the reaction liquid was concentrate | evaporated under reduced pressure. The concentrated mixture was dissolved by heating with 10 times the amount of water, allowed to cool, and then the precipitated crystals were filtered, washed with water, and dried under reduced pressure with a dehydrating agent for 2 days. Compound (2) was obtained as white crystals. Yields were 80-85%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

  This compound (2) was sulfonated in methylene chloride using 2.1 moles of methanesulfonyl chloride and 2.2 moles of triethylamine. The reaction solution was washed with water until the pH of the aqueous layer reached 7, then 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added, and the mixture was stirred at 30 ± 5 ° C for 6 minutes. Reacted for hours. The reaction solution was washed with water, dehydrated over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain the desired OT-1 crude crystals. The crude yield was 90-95%.

This crude product was recrystallized from ethyl acetate-hexane to obtain an oxetane compound of Exemplified Compound OT-1. Yields were 70-75%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 2]
Synthesis of Exemplary Compound OT-14

Isobutyl aldehyde 4.2 equivalent and compound (3) 1.0 equivalent were melt | dissolved in methanol, and the methanol solution of 2.1 equivalent of potassium hydroxide was dripped at room temperature. Subsequently, after reacting at 60 degreeC for 4 hours, the reaction liquid was concentrate | evaporated under reduced pressure. The concentrated mixture was dissolved by heating with 10 times the amount of water, allowed to cool, and then the precipitated crystals were filtered, washed with water, and dried under reduced pressure with a dehydrating agent for 2 days. Compound (4) was obtained as white crystals. Yields were 80-90%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

  This compound (4) was sulfonated in methylene chloride using 2.1 moles of methanesulfonyl chloride and 2.2 moles of triethylamine. The reaction solution was washed with water until the pH of the aqueous layer reached 7, then 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added, and the mixture was stirred at 30 ± 5 ° C for 6 minutes. Reacted for hours. The reaction solution was washed with water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired crude OT-14 product. The crude yield was almost quantitative.

This crude product was recrystallized from acetonitrile to obtain an oxetane compound of Exemplified Compound OT-14. The yield was 55-70%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 3]
Synthesis of exemplary compound OT-31

The Friedel-Crafts reaction was carried out using 2.2 equivalents of 3-chloro-2,2-dimethyl-propionyl chloride and 1 equivalent of compound (5) using aluminum chloride as a catalyst (2 equivalents) to give compound (6), compound (7 ) Was obtained. The crude yield was 90-95%. Compound (6) and compound (7) were isolated and purified by silica gel column chromatography. The yield of compound (6) was 65 to 70%, and the yield of compound (7) was 20 to 25%. Each was confirmed as the target product by ¹ H NMR (CDCl ₃ ) and mass spectrum.
Subsequently, this compound (6) was reduced in alcohol using 2.4 equivalents of sodium borohydride to obtain a compound (8). The yield was over 90%. ^It was confirmed as the target product by ¹ H NMR (CDCl ₃ ) and IR (KBr method).

  This compound (8) was dissolved in methylene chloride, 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added and reacted at 30 ± 5 ° C for 12 hours. After the reaction solution was washed with water, the organic phase was washed with water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired crude OT-31. The crude yield was 85-90%.

This crude product was recrystallized from acetonitrile to obtain an oxetane compound of Exemplified Compound OT-31. The yield was 75-80%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 4]
Synthesis of exemplary compound OT-33

Lithium enolate was prepared by reacting 2.1 equivalents of diisopropyl ketone with lithium diisopropylpyramide (2.1 equivalents, hexane solution) in THF at −40 ° C. In this solution, 1 equivalent of THF solution of Compound (9) was added dropwise at −10 ° C. for 30 minutes to 1 hour. Subsequently, after reacting at room temperature for 6 hours, the reaction solution was concentrated under reduced pressure. Extraction was performed from the concentrated mixture with methylene chloride to obtain a compound (10). The yield was 70-80%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

Subsequently, this compound was reduced using 2.4 equivalents of sodium borohydride to obtain a compound (11). The yield was over 90%. ^It was confirmed as the target product by ¹ H NMR (CDCl ₃ ) and IR (KBr method).

  This compound (11) was sulfonated in methylene chloride using 2.2 moles of methanesulfonyl chloride and 2.4 moles of triethylamine. The reaction solution was washed with water until the pH of the aqueous layer reached 7, then 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added, and the mixture was added at 30 ± 5 ° C. Reacted for hours. The reaction solution was washed with water, the organic phase was washed with water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired crude oxetane. The crude yield was 75-85%.

This crude product was recrystallized from acetonitrile to obtain an oxetane compound of OT-33. Yields were 70-75%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 5]
Synthesis of Exemplary Compound OT-36 OT-36 was synthesized in the same manner as in [Synthesis Example 3] using Compound (7) synthesized in [Synthesis Example 3]. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 6]
Synthesis of exemplary compound OT-43

Isobutyl aldehyde 4.2 equivalent and compound (12) 1.0 equivalent were melt | dissolved in methanol, and the methanol solution of 2.1 equivalent of potassium hydroxide was dripped at room temperature. Subsequently, after reacting at 60 degreeC for 4 hours, the reaction liquid was concentrate | evaporated under reduced pressure. The concentrated mixture was dissolved by heating with 10 times the amount of water, allowed to cool, and then the precipitated crystals were filtered, washed with water, and dried under reduced pressure with a dehydrating agent for 2 days. Compound (13) was obtained as white crystals. The yield was over 95%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

  This compound (13) was sulfonated in methylene chloride using 2.1 moles of methanesulfonyl chloride and 2.2 moles of triethylamine. The reaction solution was washed with water until the pH of the aqueous layer reached 7, then 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added, and the mixture was stirred at 30 ± 5 ° C for 6 minutes. Reacted for hours. The reaction solution was washed with water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired crude OT-43. The crude yield was almost quantitative.

This crude product was recrystallized from acetonitrile to obtain an oxetane compound of Exemplified Compound OT-14. The yield was 70-80%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

[Synthesis Example 7]
Synthesis of exemplary compound OT-53

Friedel-Crafts reaction was carried out using 2.2 equivalents of 4,4,4-trifluoro-2,2-dimethyl-3-oxo-butanoic acid chloride and 1 equivalent of dibenzofuran as the catalyst (2 equivalents) using aluminum chloride as a catalyst. A reaction mixture of (14) and compound (15) was obtained. The crude yield was 90-95%. Compound (14) and compound (15) were isolated and purified by silica gel column chromatography. The yield of compound (14) was 60 to 70%, and the yield of compound (7) was 25 to 30%. Each was confirmed as the target product by ¹ H NMR (CDCl ₃ ) and mass spectrum.

Subsequently, this compound (14) was reduced in alcohol using 4.6 moles of sodium borohydride to obtain a compound (16). The yield was over 95%. ^It was confirmed as the target product by ¹ H NMR (CDCl ₃ ) and IR (KBr method).

  This compound (16) was sulfonated in methylene chloride using 2.2 moles of methanesulfonyl chloride and 2.4 moles of triethylamine. The reaction solution was washed with water until the pH of the aqueous layer reached 7, then 1 mol% tetra-n-butylammonium hydrogensulfate and 50% sodium hydroxide solution (10 equivalents) were added, and the mixture was added at 30 ± 5 ° C. Reacted for hours. After the reaction solution was washed with water, the organic phase was washed with water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the desired crude OT-53. The crude yield was 85-90%.

This crude product was recrystallized from acetonitrile to obtain an oxetane compound of Exemplified Compound OT-53. Yields were 70-75%. ¹ H NMR (CDCl ₃ ) and mass spectrum confirmed the target product.

  Other oxetane compounds of the present invention represented by the general formula (OT-I) can also be synthesized in a similar manner by a similar method.

  In the ink-jet ink of the present invention, it is preferable to use the oxetane compound of the present invention together with an oxetane compound not substituted at the 2-position to obtain an effect of improving the sensitivity or improving the properties of the cured film.

  Hereinafter, the oxetane compound in which the 2-position is not substituted will be described.

  As an example of the oxetane compound in which the 2-position is not substituted, a compound represented by the following general formula (101) can be given.

In General Formula (101), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as 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 or an aryl group. , Furyl group or thienyl group. R ² is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl- C2-C6 alkenyl group such as 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc. A group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group; Alkoxycarbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl Is N- alkylcarbamoyl group having a carbon number of 2-6 and the like. As the oxetane compound used in the present invention, it is particularly preferable to use a compound having one oxetane ring because the resulting composition has excellent tackiness, low viscosity and excellent workability.

  An example of a compound having two oxetane rings includes a compound represented by the following general formula (102).

In General Formula (102), R ¹ is the same group as that in General Formula (101). R ³ is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, alkylene containing carbamoyl group Group.

Moreover, as R < ³ >, the polyvalent group selected from the group shown by the following general formula (103), (104) and (105) can also be mentioned.

In General Formula (103), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (104), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

In General Formula (105), R ⁶ represents an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. n is an integer of 0-2000. R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. R ⁷ may further include a group selected from the group represented by the following general formula (106).

In General Formula (106), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. m is an integer of 0-100.

  Specific examples of the compound having two oxetane rings include the following compounds.

Exemplary compound 11 is a compound in which R ¹ is an ethyl group and R ³ is a carboxyl group in the general formula (102). The exemplified compound 12 is a compound in which R ¹ is an ethyl group, R ³ is the general formula (105), R ⁶ and R ⁷ are methyl groups, and n is 1 in the general formula (102).

In the compound having two oxetane rings, a preferred example other than the above compound is a compound represented by the following general formula (107). In formula (107), R ¹ has the same meaning as R ¹ in the general formula (101).

  Moreover, as an example of a compound having 3 to 4 oxetane rings, a compound represented by the following general formula (108) can be given.

In formula (108), R ¹ has the same meaning as R ¹ in the general formula (101). As R ⁹ , for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polysiloxy groups such as those shown. j is 3 or 4.

In A above, R ¹⁰ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Illustrative compound 13 is an example of a compound having 3 to 4 oxetane rings.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (109).

In formula (109), R ⁸ has the same meaning as R ⁸ in the general formula (106). R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

  Preferable specific examples of the oxetane compound used in the present invention include the following compounds.

  The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method, for example, Pattisson (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Examples of these specific compounds include the following compounds.

  Moreover, in the inkjet ink of this invention, it is preferable to contain an epoxy compound or a vinyl ether compound with the oxetane compound of this invention.

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

  The alicyclic epoxide can be 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. Cyclohexene oxide or cyclopentene oxide-containing compounds are preferred.

  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 Of polyalkylene glycols such as diglycidyl ether, polypropylene glycol or diglycidyl ether of its alkylene oxide adduct Glycidyl ether, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Among these epoxides, in view of rapid 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.

  Particularly preferred as the alicyclic epoxide is a compound represented by the following general formula (VI), (VII) or (VIII).

In the formula, R ₆₀₁ represents an aliphatic group, and m6 represents 0-2. X ₁ represents — (CH ₂ ) _n6 — or — (O) _n6 —, and n6 represents 0 or 1. p1 and q1 each represents 0 or 1. r1 represents 1-3. L ₃ 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.

In the formula, R ₇₀₁ represents an aliphatic group, and m7 represents 0 to 2. X ₂ represents — (CH ₂ ) _n7 — or — (O) _n7 —, and n7 represents 0 or 1. p2 and q2 each represents 0 or 1. r2 represents 1-3. L ₄ represents a C 1-15 r 2 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the formula, R ₈₀₁ represents an aliphatic group, and m8 represents 0 to 2. X ₃ represents — (CH ₂ ) _n8 — or — (O) _n8 —, and n8 represents 0 or 1. R ₈₀₂ and R ₈₀₃ each represent a substituent, and p3 represents 0 or 1.

  Furthermore, the alicyclic epoxide represented by the general formula (VI), (VII) or (VIII) will be described.

In the above formula, R ₆₀₁ , R ₇₀₁ and R ₈₀₁ each represents an aliphatic group, and the aliphatic group is an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group) Group, etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1 -Propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl groups having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.) ). Preferably, it is a C1-C3 alkyl group, and a methyl group and an ethyl group are more preferable. m6, m7 and m8 represent 0 to 2, and preferably 1 or more.

X ₁ represents — (CH ₂ ) _n6 — or — (O) _n6 —, X ₂ represents — (CH ₂ ) _n7 — or — (O) _n7 —, and X ₃ represents — (CH ₂ ) _n8 — or — (O) represents _n8- . n6, n7, and n8 represent 0 or 1, and when n6, n7, and n8 are 0, it represents that X ₁ , X ₂ , and X ₃ do not exist.

  m6 + n6, m7 + n7 or m8 + n8 is preferably 1 or more.

L ₃ is an r 1 + 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, and L ₄ is a 1 to 1 carbon atom which may contain an oxygen atom or a sulfur atom in the main chain. 15 represents an r2 + 1-valent linking group or a single bond.

Examples of the divalent linking group having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain include the following groups, and these groups and —O— group, —S— group, —CO— group, Examples include groups formed by combining a plurality of —CS— groups.
Methylene group [—CH ₂ —]
An ethylidene group [> CHCH ₃ ],
Isopropylidene [> 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 —],
An oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —],
A 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 O CH (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 O CH (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-cyclopentanediyl 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 _{[-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 linking group include groups formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO— group, Examples include groups formed by combining a plurality of —CS— groups.

L ₃ and L ₄ may 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 (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) ), And the like. As the substituent, a halogen atom, an alkyl group, and an alkoxy group are preferable.

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

L ₃ and L ₄ are preferably those having a branch due to secondary or higher carbon in the main chain, and more preferably those having a branch due to tertiary 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, and 1 is preferable for each. r1 and r2 each represent 1 to 3, and preferably 1 or 2, respectively.

R ₈₀₂ and R ₈₀₃ represent 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 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, Etc.), an alkoxy group having 1 to 8 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 (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) ), And the like. Preferred as a substituent are a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group. These substituents may be further substituted. Examples of the substituent include the same as those mentioned above.

R ₈₀₂ and R ₈₀₃ may be bonded at the end to form a ring, or R ₈₀₂ and R ₈₀₃ may be substituted on the same carbon.

  p3 represents 0 or 1, and 1 is preferable.

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

  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, Di- or trivinyl ether compounds such as methylolpropane 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-propyl Pills 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.

  The inkjet ink of the present invention is characterized by containing a photoacid generator together with the oxetane compound of the present invention.

  As the photoacid generator used in the cationic polymerization type ink, for example, a chemically amplified photoresist or a compound used for photocationic polymerization is used (edited by Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing). (1993), pages 187-192). Examples of compounds suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium. SO ₃ ^- salt, CF ₃ SO ₃ ^- and sulfonic acid salts such as salts.

Thigh and PF ₆ with borate compound as counter anion ^- salt acid generating ability is higher preferred. Specific examples of the onium compound are shown below.

  Secondly, sulfonated products that generate sulfonic acid can be mentioned. Specific compounds are exemplified below.

  Thirdly, a halide that generates hydrogen halide can also be used. Specific compounds are exemplified below.

  Fourthly, an iron allene complex can be mentioned.

Examples of the photocationic polymerization initiator used in the present invention include arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Cyracure UVI-6974 manufactured by Union Carbide, Adekaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., and Adeka). Optomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172), allyl iodonium salt derivative (for example, RP-2074 manufactured by Rhodia), allene-ion complex derivative (for example, Irgacure manufactured by Ciba Geigy) 261), acid generators such as diazonium salt derivatives, triazine-based initiators and other halides. It is preferable to contain a cationic polymerization initiator in the ratio of 0.2-20 mass parts with respect to 100 mass parts of compounds which have cationic polymerizability. When the content of the polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product. These cationic photopolymerization initiators can be used alone or in combination of two or more.
Preferred photoacid generators used in the present invention are onium salts such as sulfonium salts, iodonium salts, ammonium salts, phosphonium salts, etc. Among them, sulfonium salt compounds are preferred. More preferable sulfonium salt compounds include sulfonium salts represented by the following general formulas (I-1), (I-2) and (I-3).

_{Wherein, R 11, R 12, R} 13 represents a substituent, m, n, p is an integer of 0-5. X ₁₁ ⁻ represents a counter ion.

Wherein, R ₁₄ represents a substituent, q is an integer of 0 to 2. R ₁₅ and R _{16 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. X ₁₂ ⁻ represents a counter ion.

In the formula, R ¹⁷ represents a substituent, and r represents an integer of 0 to 3. R ¹⁸ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ each represents a substituted substituent, an unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or It represents a substituted or unsubstituted aryl group. X ₁₃ ^- is a counter ion.

  Furthermore, the sulfonium salt represented by general formula (I-1), (I-2), (I-3) is demonstrated.

In the general formula (I-1), R ₁₁ , R ₁₂ and R ₁₃ each represent a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl 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.), carbon number -6 alkylthio groups (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl groups having 6 to 14 carbon atoms (for example, phenyl group) , Naphthyl group, anthracenyl group, etc.), aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, naphthoxy group, etc.), arylthio group having 6 to 10 carbon atoms (for example, phenylthio group, naphthylthio group, etc.), acyl Group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl) Group, ethoxycarbonyl group, tert-butyl group Alkoxycarbonyl group, etc.), heteroatom-containing aromatic Hajime Tamaki (such as furyl group having 4 to 8 carbon atoms, a thienyl group, etc.), a nitro group, a cyano group, and the like. Preferred examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylthio group, and an acyl group.

  Of these substituents, possible ones may be further substituted.

  m, n and p each represents an integer of 0 to 5, and each is preferably 1 or more.

X ₁₁ ⁻ represents a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ and CF _3. SO ₃ ^- may be mentioned sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

In the general formula (I-2), R ₁₄ represents a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl 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.), carbon number -6 alkylthio groups (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl groups having 6 to 14 carbon atoms (for example, phenyl group) , Naphthyl group, anthracenyl group, etc.), aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, naphthoxy group, etc.), arylthio group having 6 to 10 carbon atoms (for example, phenylthio group, naphthylthio group, etc.), acyl Group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl) Group, ethoxycarbonyl group, tert-butyl group Alkoxycarbonyl group, etc.), heteroatom-containing aromatic Hajime Tamaki (such as furyl group having 4 to 8 carbon atoms, a thienyl group, etc.), a nitro group, a cyano group, and the like. Preferably, they are a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Of these substituents, possible ones may be further substituted.

q represents an integer of 0 to 2, preferably 1 or more, and more preferably 2. R ₁₅ and R _{16 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group.

  Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl 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.), carbon number -6 alkylthio groups (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl groups having 6 to 14 carbon atoms (for example, phenyl group) , Naphthyl group, anthracenyl group, etc.), aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, naphthoxy group, etc.), arylthio group having 6 to 10 carbon atoms (for example, phenylthio group, naphthylthio group, etc.), acyl Group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl) Group, ethoxycarbonyl group, tert-butyl group Alkoxycarbonyl group, etc.), heteroatom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (such as furyl group, a thienyl group, etc.), a nitro group, a cyano group, a hydroxyl group, and the like.

  Preferred are a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, and an acyl group.

R ₁₅ and R ₁₆ are preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, An acyl group and a hydroxyl group.

X ₁₂ ⁻ represents a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ and CF _3. SO ₃ ^- may be mentioned sulfonate ion such. As the counter anion, borate ion and PF ₆ -are preferable because of their high acid generating ability.

In the general formula (I-3), R ₁₇ represents a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl 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.), carbon number To 14 aryl groups (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl groups (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy groups (for example, acetoxy group, propionyloxy) Group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group) , Anthracenyl group, etc.), a C4-C8 heteroatom-containing aromatic ring group (eg, furyl group, thienyl group, etc.), nitro group, cyano group, and the like.

  Preferably, they are a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group.

r represents an integer of 0 to 3, preferably 1 or more, and more preferably 2. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group.

  Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl 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.), carbon number To 14 aryl groups (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl groups (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy groups (for example, acetoxy group, propionyloxy) Group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group) , Anthracenyl group, etc.), a C4-C8 heteroatom-containing aromatic ring group (eg, furyl group, thienyl group, etc.), nitro group, cyano group, and the like.

  Preferably, they are a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group.

R ₁₈ is preferably a hydrogen atom or an unsubstituted lower alkyl group (methyl group, ethyl group, propyl group), and R ₁₉ and R ₂₀ are preferably a substituted, unsubstituted alkyl group, or substituted, unsubstituted. The substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an acyl group.

X ₁₃ ^- is a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ and CF _3. SO ₃ ^- may be mentioned sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

  Specific examples of the sulfonium salt represented by the general formulas (I-1), (I-2) and (I-3) are shown below, but the present invention is not limited thereto.

  More preferred examples of the sulfonium salt represented by the general formula (I-1) include a sulfonium salt represented by the following general formula (T-1).

In the formula, 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, An alkylthio group and an arylthio group are represented, mt1 represents an integer of 0 to 4, nt1 and pt1 each represents an integer of 1 to 5, and XT1 represents a counter anion.

  Furthermore, the sulfonium salt represented by the general formula (T-1) will be described.

In the general formula (T-1), R ^T11 and R ^T12 each represents an alkyl group or an aromatic group, and 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, etc. The aromatic group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may have a condensed ring. Examples thereof include 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) Group, benzimidazolyl group, benzoxazolyl group, a quinazolyl group, phthalazyl 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, benzo Oxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolyl group) Group), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy) Group), 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 (For example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl) Bonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylamino) Sulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylca Rubonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, Phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl) Carbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl Group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthyl Aminocarbonyl 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, cyclohexylsulfini) Group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl 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 atom (for example, fluorine atom, chlorine atom, bromine) Atoms), fluorinated hydrocarbon groups (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, Trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), and these substituents may be further substituted with the above substituents, and these substituents are A plurality of them 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 alkyl group substituted with a halogen atom or an aromatic group substituted with an alkoxy group, more preferably an unsubstituted alkyl group or an aromatic group, or an alkyl group substituted with a fluorine atom, Alternatively, examples of the alkyl group substituted with an alkoxy group and substituted with a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

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, and the alkyl group and the aromatic group represent the same groups as R ^T11 and R ^T12 described above. , 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, and examples include an alkoxy group (for example, methoxy group, ethoxy group, propyl group). Oxy 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 etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), etc. Among these, the alkylthio group, the arylthio group, a R ^T11 described above to a sulfur atom, R ^T12 synonymous groups attached thereto one location group, examples, alkylthio group (e.g., 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.), etc. It is done. 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. And may have a condensed ring, and examples of the substituent include the same groups as the examples of the substituent of R ^T11 described above. These substituents may be substituted, or a plurality of 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. Preferably, it is an unsubstituted alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an alkyl group substituted with a halogen atom or an aromatic group substituted with an alkoxy group, More preferably, it is an unsubstituted alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, an alkyl group substituted with a fluorine atom, or an aromatic group substituted with an alkoxy group. Examples of alkyl groups substituted by fluorine atoms include fluoromethyl group, trifluoromethyl group, pentafluoroethyl Group, and pentafluorophenyl group.

mt1 represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and nt1 and pt1 each represents an integer of 1 to 5, each preferably 1 to 3, more preferably Each is 1 to 2. A plurality of R ^T12, R ^T13, R ^T14, each may be the same or different, may be R ^T11 and R ^T12 or plural R ^T12 are bonded to each other to form a ring, R ^T12 and R may ^T13 or a plurality of R ^T13 each other combine to form a ring, may be R ^T12 and R ^T14 or plural R ^T14 are bonded to each other to form a ring, R ^T12 and R ^T14 are 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 at the ortho-position or para-position, more preferably at the para-position, with respect to the benzene ring to which the sulfonium ion is bonded. X ^T1 represents a counter anion. Examples of the counter anion include halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF. Examples thereof include complex ions such as ₆ ⁻ , and sulfonate ions such as p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ F ₅ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , and CF ₃ SO ₃ ^— . As the counter anion, BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are preferable because of their high acid generating ability.

  Specific examples of the sulfonium salt represented by the general formula (T-1) are shown below, but the present invention is not limited thereto.

  Examples of the photopolymerization accelerator include anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), and phenothiazine derivatives (for example, 10-methylphenothiazine, 10-ethylphenothiazine). 10-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylphenothiazine-5,5-dioxide, etc.). These photopolymerization accelerators can be used alone or in combination.

  In addition to the components described above, various additives can be used in the inkjet ink of the present invention.

  As the color material used in the inkjet ink of the present invention, a color material that can be dissolved or dispersed in the main component of the polymerizable compound can be used, but a pigment is preferable from the viewpoint of weather resistance.

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

C. I. Pigment Yellow-1, 3, 12, 13, 14, 17, 81, 83, 87, 95, 109, 42,
C. I. Pigment 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, 144, 146, 185, 101,
C. I. Pigment Violet-19, 23,
C. I. Pigment Blue-15: 1, 15: 3, 15: 4, 18, 60, 27, 29,
C. I. Pigment Green-7, 36,
C. I. Pigment White-6, 18, 21,
C. I. Pigment Black-7,
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. It is also possible to add a dispersant when dispersing the pigment. As the dispersant, a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Avecia. 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, but the actinic ray curable ink used in the present invention is preferably solventless 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 inkjet ink of the present invention, the color material concentration is preferably 1% by mass to 10% by mass with respect to the entire ink.

  In the present invention, a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.

  Examples of the thermal base generator include compounds that release amines by decomposition by reactions such as organic acid and base salts that are decomposed by decarboxylation by heating, intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Those which cause some kind of reaction by heating and release a base are preferably used. Specifically, the salt of trichloroacetic acid described in British Patent No. 998,949, the salt of alpha-sulfonylacetic acid described in US Pat. No. 4,060,420, and the propionic acids described in JP-A-59-157737 Salts, 2-carboxycarboxamide derivatives, salts with a base component described in JP-A-59-168440 and a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base, JP-A-59-180537 Hydroxam carbamates utilizing the Lossen rearrangement described in No. 5, and aldoxime carbamates described in JP-A No. 59-195237 that generate nitriles by heating. In addition, British Patent No. 998,945, US Pat. No. 3,220,846, British Patent No. 279,480, Japanese Patent Laid-Open Nos. 50-22625, 61-32844, 61-51139, 61 The thermal base generators described in Nos. -52638, 61-51140, 61-53634 to 61-53640, 61-55644, 61-55645 and the like are useful. More specifically, guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, guanidine p-chlorophenylsulfonylacetate, guanidine p-methanesulfonylphenylsulfonylacetate, potassium phenylpropiolate, phenylpropiool Examples include acid guanidine, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate, and tetramethylammonium phenylpropiolate. The thermal base generator can be used in a wide range.

  The ink of the present invention contains an acid proliferating agent that newly generates an acid by an acid generated by irradiation with actinic rays, which is already known, including JP-A-8-248561 and JP-A-9-34106. Is also possible.

  The ink-jet ink of the present invention is produced by well dispersing the pigment together with an active energy ray-curable compound and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with an active energy ray-curable compound. Sufficient dispersion is possible even with dispersion by a normal disperser, so it does not take excessive dispersion energy and does not require a great amount of dispersion time. Ink excellent in the quality is prepared. The ink is preferably filtered through a filter having a pore diameter of 3 μm or less, more preferably 1 μm or less.

  The ink-jet ink of the present invention is preferably adjusted to have a high viscosity at 25 ° C. of 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics even from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz. When the viscosity is less than 5 mPa · s, a decrease in the followability of the discharge is recognized in the high-frequency head, and when it exceeds 50 mPa · s, the discharge characteristic itself even if a mechanism for reducing the viscosity by heating is incorporated in the head. Drop, the stability of the discharge becomes poor, and it becomes impossible to discharge at all.

  The ink-jet ink of the present invention preferably has a conductivity of 10 μS / cm or less in a piezo head and does not cause electrical corrosion inside the head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In the present invention, the surface tension of the ink at 25 ° C. is preferably in the range of 25 to 40 mN / m. If the surface tension of the ink at 25 ° C. is less than 25 mN / m, stable emission is difficult to obtain, and if it exceeds 40 mN / m, a desired dot diameter cannot be obtained. Outside the range of 25 to 40 mN / m, it is difficult to obtain uniform dot diameters for various supports even when the light is emitted and irradiated with light while controlling the viscosity and moisture content of the ink as in the present invention. It becomes.

  In order to adjust the surface tension, a surfactant may be contained as necessary. Examples of the surfactant preferably used in the ink according to the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl. Nonionic surfactants such as allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and surfactants having a polymerizable group Compound etc. are mentioned. Of these, particularly preferred are surface active compounds having a polymerizable group such as an unsaturated bond, oxirane, or oxetane ring, such as silicone-modified acrylate, fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, and fluorine-modified oxetane. .

  Various additives other than those described above can be used in the ink of 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 order to improve the adhesion with the recording medium, it is also effective to add a trace amount of organic solvent. In this case, it is effective to add in the range where the solvent resistance and VOC problems do not occur, and the amount used is in the range of 0.1 to 5%, preferably 0.1 to 3%. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

  In the image forming method of the present invention, the ink composition is ejected and drawn on a recording material by an ink jet recording method, and then the ink is cured by irradiation with an actinic ray such as ultraviolet rays.

  In the image forming method of the present invention, it is preferable that the ink is heated together with the ink jet nozzles during ink ejection so that the ink liquid has a low viscosity. As heating temperature, it is 30-80 degreeC, Preferably it is 35-60 degreeC.

  In the present invention, the total ink film thickness after the ink has landed 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. Not only because of curling and wrinkling problems, but also because it has the problem of changing the texture and texture of the entire printed matter. Moreover, in this invention, it is preferable that the amount of droplets discharged from each nozzle is 2 to 15 pl.

  In the present invention, in order to form a high-definition image, it is preferable that the irradiation timing is as early as possible. However, in the present invention, the light irradiation is started at a timing at which the viscosity or water content of the ink is in a preferable state. Is preferred.

  Specifically, as the irradiation condition of the generated light, actinic light irradiation is preferably started within 0.001 to 2.0 seconds after ink landing, and more preferably 0.001 to 0.4 seconds. Also, it is preferable to terminate the light irradiation after 0.1 to 3 seconds, preferably within 0.2 to 1 second, until the ink fluidity is lost. By setting it as the above condition, enlargement of the dot diameter and bleeding between the dots can be prevented.

  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 recording head unit, and the recording head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. 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 surface of a recording head unit and irradiating the recording unit with UV light is disclosed. ing. Any of these irradiation methods can be used in the image forming method of 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.

Examples of light sources used for actinic ray irradiation include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps, high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, and UV lasers. , Xenon flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, LEDs, and the like, but are not limited to these. Among these, fluorescent tubes are preferred because of their low energy and low cost. A light source having a light emission wavelength peak at 250 to 370 nm, preferably 270 to 320 nm is preferable in terms of sensitivity. The illuminance is 1 to 3000 mW / cm ² , preferably 1 to 200 mW / cm ² . In addition, in the case of curing with an electron beam, the curing is usually performed with an electron beam having an energy of 300 eV or less, but it is also possible to cure instantaneously with an irradiation amount of 1 to 5 Mrad.

  The inkjet ink of the present invention is used to print an image on a recording medium (also referred to as a base material). As the recording medium, all of a wide range of conventional synthetic resins used in various applications are used. Specific examples include polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like. The thickness and shape of the synthetic resin base material are not limited at all.

  As a base material that can be used in the present invention, a non-absorbent support can be used in addition to normal uncoated paper, coated paper, etc. Among them, a non-absorbent support is used as the base material. It is preferable.

  In the present invention, various non-absorbing plastics and films thereof can be used as the non-absorbing support. Examples of the various plastic films include PET film, OPS film, OPP film, ONy film, and PVC film. , PE film, and TAC film. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, 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. The constitution of the present invention includes an OPP film having a low surface energy, an OPS film, and a PET having a relatively large surface energy, but the substrate preferably has a wetting index of 40 to 60 mN / m.

  In the present invention, it is more advantageous to use a long (web) recording material 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 printing of various sizes. is there.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

Example 1
<< Preparation of Active Energy Ray Curing Composition >>
An active energy ray-curable composition 101 having the following composition was prepared.

<Oxetane compound 1>
Exemplified Compound OT-1 15 parts by mass <Oxetane Compound 2>
Oxetane A 80 parts by mass <Photoacid generator>
Example Compound Example TAS-1 5 parts by mass The active energy ray-curable composition 102 to the active energy ray-curable composition 101 is changed to the compounds shown in Table 1 by changing the oxetane compound 1, the oxetane compound 2 and the photoacid generator of the active energy ray-curable composition 101 to 127 was prepared.

  The detail of each compound described in Table 1 is shown below.

<Photoinitiator>
SP-152: Triphenylsulfonium salt (Adekaoptomer SP-152 manufactured by Asahi Denka Co., Ltd.)
UVI-6990: Triphenylsulfonium salt (manufactured by Cyracure UVI6990 Union Carbide)
<Oxetane ring-containing compound>
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
Oxetane A: 2- (4-methoxy-phenyl) -3,3-dimethyl-oxetane (oxetane described in JP-A No. 2001-181386)
1 g of the obtained active energy ray-curable composition was applied onto a PET film, and a fluorescent tube having a main peak at 308 nm was used as a light source. Irradiation was 10 mW / cm ² under a light source for 120 seconds. The change in viscosity of the cured composition was sensory evaluated.

  Exposure was performed in a low humidity environment (25 ° C., 20% RH) and a high humidity environment (25 ° C., 80% RH).

  The change in viscosity was judged from the tactile sensation of the experimenter by touching the non-light-irradiated coating film and the coating film after the light irradiation with a metal spatula. "Solidification" indicates that a solid coating was formed, and "Thickened" indicates that there is a clear difference in viscosity between the unirradiated coating and the coating after irradiation. “Slightly thickened” means that there is a slight difference in viscosity between the light-unirradiated film and the film after light-irradiation. This indicates that no significant difference was found in the tactile sensation of the coating film. The results are shown in Table 1. As is apparent from the table, it can be seen that the active energy ray-curable composition of the present invention undergoes polymerization regardless of the environmental humidity fluctuation.

Example 2
<Preparation of inkjet ink>
(Preparation of magenta ink 1)
Magenta ink 1 having the following composition was prepared. The magenta ink 1 was prepared by dispersing each composition excluding the photoacid generator for 4 hours using a sand grinder, adding the photoacid generator, and filtering through a 0.8 μm membrane filter, and then at 50 ° C. The solution was prepared by dehydration under reduced pressure while heating.

C. I. Pigment Red 184 3 parts by mass Oxetane A 20 parts by mass OXT-221 80 parts by mass Solsperse 24000 (manufactured by Avecia) 1 part by mass UVI-6990 5 parts by mass (preparation of inks 2 to 20)
The active energy ray-curable inkjet ink of the present invention was prepared in the same manner as ink 1 except that the pigment, epoxy compound, oxetane-containing compound, and photoinitiator were changed to the configuration shown in Table 2 below. Some inks 2-20 were obtained.

  The detail of each compound described in Table 2 is 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 4.55 L (1 gallon) made of stainless steel. ) 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) = EP-27
Celoxide 2021P: Alicyclic epoxy (manufactured by Daicel UCB) = EP-1
<Photoinitiator>
<< Inkjet image recording and evaluation >>
Using the magenta inks prepared as described above, image recording and evaluation of the obtained images were performed according to the following methods.

[Image Evaluation A]
(Image recording)
Piezo-type inkjet nozzles (nozzle pitch 360 dpi, dpi as used in the present invention represents the number of dots per 2.54 cm) for each magenta ink obtained to obtain a droplet size of 7 pl, and the nozzle portion at 50 ° C. Heat-controlled, 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 starts 0.2 seconds after landing and the exposure is 0.7 seconds later. 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 1 minute. ×: The tackiness remains even after 1 minute after the exposure. Evaluation of material adhesion>
A solid tape (R) with a width of 25 mm was applied to the solid image formed in each environment and strongly pressed, and then quickly peeled off at a peeling angle of 90 degrees, and the state of the image after peeling was visually observed, The substrate adhesion was evaluated according to the standard.

○: 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.

◯: There is almost no bleeding between two dots. Δ: Slight bleeding between two dots is observed. X: The dots are greatly blurred Table 3 shows 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 0.6 seconds and the exposure irradiation end time was changed after 1.1 seconds. . The exposure time and exposure energy were 5 mJ / cm ² for 0.5 seconds, respectively, as in image evaluation A. Table 4 shows the obtained results.

  As is clear from Tables 1 to 4, the active energy ray-curable composition containing the bifunctional oxetane compound of the present invention is cured without being affected by the environmental humidity compared to the comparative example, and this active energy ray curing is performed. It can be seen that the ink-jet ink composition using the composition is excellent in ink curability and substrate adhesion even in a high humidity environment and in various exposure environments, and can obtain a high-quality image without bleeding.

Claims (14)

An active energy ray-curable composition comprising an oxetane compound represented by the following general formula (OT-I).

[In the above general formula (OT-I), L ^T1 represents an oxygen atom, a sulfur atom, —CR ^T111 (R ^T112 ) —, R ^{T101 to} R ^T112 represent a hydrogen atom or a substituent, and p ^T1 represents 0 or 1, q ^T1 and r ^T1 represent 0 to 3; ] 2. The active energy ray-curable composition according to claim 1, which has a substituent at at least one of R ^T101 , R ^T102 , R ^T105 , and R ^T106 . The active energy ray-curable composition according to claim 2, wherein R ^T101 , R ^T102 , R ^T105 , and R ^T106 are substituted or unsubstituted alkyl groups. The active energy ray-curable composition according to any one of claims 1 to 3, comprising a compound that generates an acid upon irradiation with an active energy ray. 5. The active energy ray-curable composition according to claim 4, wherein the compound that generates an acid upon irradiation with active energy rays is an onium salt compound. 6. The active energy ray-curable composition according to claim 5, wherein the compound that generates an acid upon irradiation with active energy rays is a sulfonium salt compound. The active energy ray-curable composition according to claim 6, wherein the sulfonium salt compound is represented by the following general formula (I-1), (I-2) or (I-3).

[Wherein R ₁₁ , R ₁₂ and R ₁₃ represent substituents, and m, n and p each represents an integer of 0 to 5. X ₁₁ ⁻ represents a counter ion. ]

Wherein, R ₁₄ represents a substituent, q is an integer of 0 to 2. R ₁₅ and R _{16 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. X ₁₂ ⁻ represents a counter ion. ]

[Wherein, R ₁₇ represents a substituent, and r represents an integer of 0 to 3. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group. X ₁₃ ^- is a counter ion. ] The active energy ray-curable composition according to claim 7, wherein the sulfonium salt compound represented by the general formula (I-1) is represented by the following general formula (T-1).

(In the formula, 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, and 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 a counter anion.) An inkjet ink composition for forming an image on a recording medium by an inkjet method, comprising the active energy ray-curable composition according to any one of claims 1 to 8. The inkjet ink composition according to claim 9, comprising an oxetane compound having no substituent at the 2-position. The ink composition for inkjet according to claim 9 or 10, comprising an epoxy compound or a vinyl ether compound. 50 parts by mass to 80 parts by mass of an oxetane compound having no substituent at the 2-position, 0 parts by mass to 50 parts by mass of an epoxy compound, and at least one oxetane compound represented by the general formula (OT-I) is 1 The ink composition for inkjet according to any one of claims 9 to 11, wherein the ink composition is contained in an amount of 20 to 20 parts by mass. The ink composition for inkjet according to claim 11 or 12, wherein the epoxy compound is selected from at least one of alicyclic epoxide compounds represented by the following general formulas (VI) to (VIII): Stuff.

[Wherein, R ₆₀₁ represents an aliphatic group, and m6 represents 0 to 2. X ₁ represents — (CH ₂ ) _n6 — or — (O) _n6 —, and n6 represents 0 or 1. p1 and q1 each represents 0 or 1. r1 represents 1-3. L ₃ 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 ₇₀₁ represents an aliphatic group, and m7 represents 0 to 2. X ₂ represents — (CH ₂ ) _n7 — or — (O) _n7 —, and n7 represents 0 or 1. p2 and q2 each represents 0 or 1. r2 represents 1-3. L ₄ represents a C 1-15 r 2 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[Wherein, R ₈₀₁ represents an aliphatic group, and m8 represents 0-2. X ₃ represents — (CH ₂ ) _n8 — or — (O) _n8 —, and n8 represents 0 or 1. R ₈₀₂ and R ₈₀₃ each represent a substituent, and p3 represents 0 or 1. ] An ink droplet is ejected onto a recording medium using a recording head having at least one nozzle capable of selectively controlling the ejection of an ink droplet, using the inkjet ink composition according to any one of claims 9 to 13. Then, after the ink has landed, the ink is cured by irradiating with active energy rays.