JP2006045415A - Cationically polymerizable composition, ink composition for inkjet and image-formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cationically polymerizable composition excellent in curablity, to provide an ink composition for inkjet, excellent in ink curability and adhesion to substrate, obtaining blotless high quality images and excellent in preservability, and to provide an image-formation method using the ink composition for inkjet. <P>SOLUTION: The cationically polymerizable composition comprises at least one compound selected from compounds having one or more oxetane rings and at least one compound selected from compounds having at least one oxirane ring and substituted, with at least one aromatic group, at its carbon atom adjacent to an oxygen atom forming the oxirane ring. The ink composition for inkjet contains the cationically polymerizable composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cationically polymerizable composition containing an oxetane ring-containing compound, a specific oxirane ring-containing compound, a compound that generates an acid upon irradiation with active energy rays, and an ink-jet ink composition and an image forming method using the same. In detail, the oxetane ring-containing compound, the oxirane ring-containing compound having at least one aromatic group on the adjacent carbon atom of the oxygen atom constituting the oxirane ring, and a compound capable of generating an acid upon irradiation with active energy rays A photo-curable ink composition for ink-jet printing, which has high reactivity, good storage stability, and can provide a high-quality image, and a cationically polymerizable composition that uses the ink, and an ink-jet ink composition using the same. The present invention relates to 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, and ink that has improved color reproduction, durability, and emission suitability, ink absorption, coloring material coloring, surface gloss, etc. Using paper, it is also possible to obtain image quality comparable to silver halide photography. 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. It is disclosed (for example, see Patent Documents 1 and 2).

  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 the cationic polymerization type ultraviolet curable ink, in order to improve the influence of humidity, a method of heating the landed ink is known (for example, see Patent Document 3).

  Epoxy compounds having an oxirane ring, oxetane compounds, and vinyl ether compounds are known as monomers constituting the cationic polymerizable composition used in the cationic polymerization type UV curable ink which is one of the application fields of the cationic polymerization curing technology. .

  In particular, it is known that the polymerization rate is remarkably increased by using both an epoxy compound and an oxetane compound (see, for example, Non-Patent Document 1 and Patent Document 4). 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, use in an ultraviolet curable ink jet is disclosed (for example, see Patent Document 5). 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 type ink to heat and irradiate the landed ink (for example, refer to Patent Document 6). 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. An active energy ray curable composition in which an oxetane having a specific structure and an epoxy compound are used together is disclosed (for example, see Patent Document 7), and a curable composition in which a specific oxetane compound and an epoxy compound having an aromatic group are used in combination. In any case, a structure in which an aromatic group is substituted on the adjacent carbon atom of the oxirane ring of the epoxy compound is not disclosed. In addition, 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 9). 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-A-6-200204 (Example) JP 2000-504778 A (Examples 1 to 5) JP 2002-137375 A (Specifications, pages 3 to 5) Dongguan Synthetic Research Annual Report TREND 2 (1999), "Application of Oxetane Compounds to Photocationic Curing System" Japanese Patent No. 2679586 (Example) JP 2001-220526 A (Example) JP 2002-137375 A (Specifications, pages 3 to 5) JP-A-7-53711 (Example 1) JP 2001-40085 (Examples 1-8) JP 2001-181386 A (Example 1)

  The present invention has been made in view of the above problems, and its object is to provide a cationically polymerizable composition having excellent curability, and further excellent ink curability and substrate adhesion, and bleeding. It is an object of the present invention to provide an ink-jet ink composition which can obtain a high-quality image free of ink and has excellent storage stability, and an image forming method using the ink-jet ink composition.

  The above object of the present invention can be achieved by the following configuration.

(Claim 1)
At least one compound selected from compounds having one or more oxetane rings, and at least one aromatic group in an adjacent carbon atom of an oxygen atom having at least one oxirane ring and constituting the oxirane ring. And at least one compound selected from compounds in which is substituted.

(Claim 2)
At least one compound selected from compounds having at least one oxetane ring and having at least one aromatic group substituted on an adjacent carbon atom of an oxygen atom constituting the oxetane ring; and at least one or more compounds Cationic polymerizability characterized by containing at least one compound selected from compounds having an oxirane ring and having at least one aromatic group substituted on the adjacent carbon atom of the oxygen atom constituting the oxirane ring Composition.

(Claim 3)
The cationically polymerizable composition according to claim 1 or 2, comprising a compound that generates an acid upon irradiation with an active energy ray.

(Claim 4)
4. The cationic polymerizable composition according to claim 3, wherein the active energy ray is ultraviolet light.

(Claim 5)
The compound that generates an acid upon irradiation with active energy rays is at least one compound selected from sulfonium salt compounds represented by the following general formula (b). The cationically polymerizable composition described in 1.

(In the formula, R ^b1 to R ^b3 each represents a substituent, and X ^b- represents a counter ion.)
(Claim 6)
An ink-jet ink composition comprising the cationically polymerizable composition according to any one of claims 1 to 5.

(Claim 7)
The inkjet ink composition according to claim 6 is ejected as ink droplets onto a recording material by a recording head having at least one nozzle capable of selectively controlling ejection of ink droplets. An image forming method comprising: jetting onto the recording material and landing the ink droplet, and then irradiating an active energy ray to cure the ink droplet.

  According to the present invention, it is possible to provide a cationic polymerizable composition having high reactivity and good storage stability, and maintaining excellent reactivity even when stored for a long period of time by using the cationic polymerizable composition of the present invention. Ink-jet ink composition that is superior in suppressing thickening and has excellent ink curability and substrate adhesion without being affected by environmental humidity even with a low illuminance light source, and provides high-quality and high-quality images without bleeding And an image forming method using the ink-jet ink composition.

  As a result of intensive studies in view of the above problems, the present inventor used a cationically polymerizable composition containing an oxetane ring-containing compound, a specific oxirane ring-containing compound, and a compound that generates an acid upon irradiation with active energy rays. The cation polymerizable curable composition having a stable curability without being affected by environmental humidity, and a specific oxetane ring-containing compound, a specific oxirane ring-containing compound, and an active energy ray. In the case of using a compound that generates an acid upon irradiation, it has been found that a cationically polymerizable composition having excellent curability can be obtained even with a light source having a low illuminance. As a result, the present invention has been found to have excellent properties, cured film properties and storage stability, and can obtain high-quality images. A.

  The present invention will be described in detail below. First, a compound having at least one oxetane ring in the present invention (in the present specification, also referred to as an oxetane ring-containing compound and an oxetane compound, both of which represent the same meaning) will be described. The oxetane ring represents a cyclic 4-membered ether structure, and the compound having at least one oxetane ring of the present invention may have at least one 4-membered ether structure in the molecule. The partial structure of is not particularly limited. The number of oxetane rings and other partial structures of the oxetane compound of the present invention are various performance evaluations necessary for exhibiting the performance desired by the user in actually using the cationic polymerizable composition of the present invention. You should decide after examination.

  Oxetane compounds represented by the following general formula (1) are more preferred in the present invention.

In General formula (1), R < ₁ > -R < ₆ > represents a hydrogen atom or a substituent respectively. However, all of R _{1 to} R ₆ do not represent hydrogen atoms at the same time.

In the general formula (1), examples of the substituent represented by R _{1 to} R ₆ include an alkyl group (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), alkenyl group (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, allyl group, etc.), Alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, propargyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group) , Octyloxy group, dodecyloxy group, cyclopentyloxy group, cyclohexylo Si group, etc.), acyl groups (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group) , Pyridylcarbonyl group etc.), acyloxy group (eg acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group etc.), alkoxycarbonyl group (eg methyl Oxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aromatic hydrocarbon group (for example, phenyl group) , Naphthyl group, anthracenyl group, etc.), heteroaromatic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzo Oxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1-isoquinyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothienyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, fluorine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, Trifluoromethyl group, pentafluoroethyl group, pen Fluorophenyl group), and the like. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ may be bonded to each other to form a divalent group and form a ring. Preferable substituents represented by R _{1 to} R ₆ are alkyl groups, alkoxy groups, acyloxy groups, alkoxycarbonyl groups, aromatic hydrocarbon groups, heteroaromatic groups, halogen atoms, and fluorinated hydrocarbon groups. is there.

These groups represented by R _{1 to} R ₆ may each further have a substituent.

Examples of groups that can be substituted for the substituents represented by R _{1 to} R ₆ include alkyl groups (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), alkenyl group (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, allyl group, etc.), alkynyl group ( For example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, propargyl group, etc.), aromatic hydrocarbon group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heteroaromatic group (for example, , Furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group, triazyl group, imida Ryl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1-isoquinylyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group) , Morpholyl group, oxazolidyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothienyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group) Group, propi Ruthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyl group) Oxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methyl) Aminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, Silylaminosulfonyl 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-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecyl) Carbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, Propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, Aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group Naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylurei group) Group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl) Group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, Cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, -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 groups, etc.), halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, etc.), fluorinated hydrocarbon groups (eg, fluoromethyl groups, trifluoromethyl groups, pentafluoroethyl groups, pentafluorophenyl groups, etc.), Examples include cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group), hydroxyl group, nitro group, carboxyl group, etc. Are each represented by R _{1 to} R ₆ described above. The substituent may be further substituted with a group having the same meaning as the substitutable group, and a plurality of these substituents may be bonded to each other to form a ring.

Preferred as a group that can be substituted for the substituent represented by each of R _{1 to} R ₆ is a halogen atom, alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group, aromatic hydrocarbon group, heteroaromatic group, hydroxyl group. , A fluorinated hydrocarbon group. Any of the arbitrary positions of the substituents represented by R _{1 to} R ₆ may have an oxetane ring having the same meaning as in the general formula (1) as a substituent, and may be a bifunctional or higher polyfunctional oxetane compound. .

  The oxetane compound of the present invention preferably has a substituent at the 2-position or 3-position of the oxetane ring.

  The substituent that can be substituted at the 2-position of the oxetane ring is not particularly limited, but is preferably an aromatic group, and the aromatic group of the present invention is the aromatic hydrocarbon group (for example, phenyl group) described above. , Naphthyl group, anthracenyl group, etc.), heteroaromatic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzo An oxazolyl group, a quinazolyl group, a phthalazyl group, a pyrrolyl group, a 2-quinolyl group, a 1-isoquinyl group, and the like. These aromatic groups may further have a substituent, and examples of the substituent are the same groups as the above-described halogen atom, alkyl group, alkoxy group, acyloxy group, and alkoxycarbonyl group. When the substituent at the 2-position is an aromatic group, it may further have a substituent at the 3-position, and examples of preferred substituents are the same groups as the alkyl group and alkoxy group described above.

  The oxetane compound of the present invention having a substituent at the 2-position is more preferably an oxetane compound represented by the following general formula (A) or the following general formula (B).

In general formula (A), Q _A represents a (mA + nA) valent aromatic group, R _A1 to R _A4 each represents a hydrogen atom or a substituent, R _A5 represents a substituent, and mA represents a positive number of 1 to 3. NA represents an integer of 0 to 5. The aromatic group represented by Q _A represents a group having the same meaning as the aromatic group having the (mA + nA) valence described above. The substituents represented by R _A1 to R _A4 represent the same groups as the substituents represented by R ₁ to R ₆ described above, and each of R _A1 to R _A4 is preferably a hydrogen atom, an alkyl group, or an alkoxy group. It is. The substituent represented by R _A5 represents the same group as the substituent represented by R ₁ to R ₆ described above, and the plurality of R _A5 may be the same or different, and may be bonded to each other to form a divalent group. And may form a ring. R _A5 is preferably an alkyl group or an alkoxy group, and at least one of the plurality of R _A5 is more preferably an alkoxy group. mA is preferably an integer from 1 to 2, nA is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, and mA + nA is preferably an integer from 1 to 6, more preferably Is an integer from 1 to 3.

Formula (B) medium Q _B represents (nB + 2) valent aromatic group, the R _B1 R _B4 each represents a hydrogen atom or a substituent, R _B5 represents a substituent, L _B is connected in mB value Represents a group, mB represents an integer of 2 to 4, and nB represents an integer of 0 to 4.
The aromatic group represented by Q _B represents a group having the same meaning as the above-described aromatic group having an (nB + 2) valence. The substituents represented by R _B1 to R _B4 represent the same groups as the substituents represented by R ₁ to R ₆ described above, and each of R _B1 to R _B4 is preferably a hydrogen atom, an alkyl group, or an alkoxy group. It is. The substituent represented by R _B5 represents the same group as the substituent represented by R ₁ to R ₆ described above, and the plurality of R _B5 may be the same or different, and may be bonded to each other to form a divalent group. And may form a ring. R _B5 is more preferably an alkyl group or an alkoxy group. mB is preferably an integer of 2 or 3, and nB is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

L _B is primarily preferably contain an oxygen atom or a sulfur atom is also mB-valent linking group or a single bond good 0-15 carbon atoms in the chain, the main chain may contain an oxygen atom or a sulfur atom divalent Examples of the linking group include the following groups and groups formed by combining these groups with a plurality of —O— groups, —S— groups, —CO— groups, and —CS— groups.
Methylene group [—CH ₂ —], ethylidene group [> CHCH ₃ ], isopropylidene group [> C (CH ₃ ) ₂ ], 1,2-ethylene group [—CH ₂ CH ₂ —], 1,2-propylene Group [—CH (CH ₃ ) CH ₂ —], 1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —], 2,2-dimethyl-1,3-propanediyl group [—CH ₂ C ( _{CH 3) 2 CH 2 -]} , 2,2- dimethoxy-1,3-propanediyl group _{[-CH 2 C (OCH 3)} 2 CH 2 -], 2,2- dimethoxy-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 H ₂ CH ₂ -], oxydiethylene group _{[-CH 2 CH 2 OCH 2 CH} 2 -], thiodiethylene group _{[-CH 2 CH 2 SCH 2 CH} 2 -], 3- oxo thiodiethylene group [-CH ₂ CH ₂ SOCH ₂ CH ₂ —], 3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —], 1,4-dimethyl-3-oxa-1,5-pentanediyl group [— CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —], 3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —], 1,5-dioxo-3-oxapentanediyl group [— COCH ₂ OCH ₂ CO—], 4-oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —], 3,6-dioxa-1,8-octanediyl group [— _{CH 2 CH 2 OCH 2 CH 2} OC ₂ CH ₂ -], 1,4,7- trimethyl-3,6-dioxa-1,8-diyl group _{[-CH (CH 3) CH 2} OCH (CH 3) CH 2 OCH (CH 3) CH 2 -], 5,5-dimethyl-3,7-dioxa-1,9 Nonanjiiru 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-Nonanjiiru 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- cyclohexane-diyl group _{[-1,2-C 6 H 10 -} ], 1,3- cyclohexane-diyl group _{[-1,3-C 6 H 10 -} ], 1, 4-cyclohexanediyl group [-1,4-C ₆ H _10- ], 2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O-], p-phenylene group [-p-C ₆ H ₄ -], m-phenylene group _{[-m-C 6 H 4 -} ], α, α'-o- xylylene group _{[-o-CH 2 -C 6 H} 4 -CH 2 -], α, α'-m - xylylene group _{[-m-CH 2 -C 6 H} 4 -CH 2 -], α, α'-p- xylylene group _{[-p-CH 2 -C 6 H} 4 -CH 2 -] Furan-2,5-diyl - bismethylene group _{[2,5-CH 2 -C 4 H} 2 O-CH 2 -], thiophene-2,5-diyl - bismethylene group [2,5-CH ₂ -C ₄ H ₂ S—CH ₂ —], an isopropylidenebis-p-phenylene group [—pC ₆ H ₄ —C (CH ₃ ) ₂ —pC ₆ H ₄ —].

  Examples of the trivalent or higher valent linking group include a group formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO—. And a group formed by combining a plurality of groups and -CS- groups.

  The manufacturing method of the oxetane compound described above is not particularly limited, and may be a conventionally known method, and can be synthesized according to the method described in the following literature.

A: Hu Xianming, Richard M. et al. Kellogg, Synthesis, 533-538, May (1995)
B: A. O. Fitton, J .; Hill, D.C. Ejane, 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: JP-A-6-16804 L: German Patent 1,021,858 Specification Examples of oxetane compounds represented by the following general formula (1), general formula (A), and general formula (B) The present invention is not limited to these examples.

  The substituent that can be substituted at the 3-position of the oxetane ring is not particularly limited, but preferably the above-described alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group, aromatic hydrocarbon group, heteroaromatic group, halogen atom, A group having the same meaning as the fluorinated hydrocarbon group can be raised.

  As the oxetane compound having a substituent at the 3-position, an oxetane compound not substituted at the 2-position is more preferable. 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 a methyl group, an ethyl group, a propyl group, butyl alkyl group having 1 to 6 carbon atoms such as, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl group, 2-methyl-2 -Alkenyl groups having 2 to 6 carbon atoms such as propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group, aromatic groups such as phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group and phenoxyethyl group A group having a ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group and a butylcarbonyl group, an alkoxy having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group Carbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl group Number 2-6 carbons of an N- alkylcarbamoyl group. 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 formula (102), R ¹ is the same as the group in 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 the general formula (103), R ⁴ is 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, or a carbon such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. A C 1-4 alkoxy group, 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 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. 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. Examples of R ^{7 also} 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 the above A, 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, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Examples of these specific compounds include the following compounds.

  Next, a compound having at least one oxirane ring and having at least one aromatic group substituted on the adjacent carbon atom of the oxygen atom constituting the oxirane ring (hereinafter referred to as the oxirane compound of the present invention or the present invention) It is also referred to as an epoxy compound, and each represents a synonymous compound). The oxirane ring of the present invention refers to a 3-membered cyclic ether structure, and an example of a compound having an oxirane ring is a compound usually known as an epoxy compound. The oxirane compound of the present invention is not particularly limited as long as it has at least one 3-membered cyclic ether structure in the molecule and has an aromatic group at the 2-position of the oxirane ring. The number of oxirane rings and other partial structures of the oxirane compound of the present invention are various performance evaluations necessary for exhibiting the performance desired by the user in actually using the cationic polymerizable composition of the present invention. You should decide after examination.

The aromatic group of the present invention refers to the above-described aromatic hydrocarbon group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heteroaromatic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, Pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1-isoquinyl group, etc.) Represents a group. These aromatic groups may further have a substituent. Examples of the substituent are groups having the same meanings as the groups represented by R ₁ to R ₆ in the general formula (1) described above. A halogen atom, an alkyl group, an alkoxy group, an acyl group, and an acyloxy group are preferable.

  The oxirane compound of the present invention is more preferably a compound represented by the following general formula (C) or the following general formula (D).

In formula (C), Q _C represents an (mC + nC) -valent aromatic group, R _C1 and R _C2 each represent a hydrogen atom or a substituent, R _C3 represents a substituent, and mC is an integer of 1 to 3 MC represents an integer of 0 to 5. Aromatic group represented by Q _C represents (mC + mC) value of the above aromatic groups as defined for groups. The substituents represented by R _C1 and R _C2 represent the same groups as the substituents represented by R ₁ to R ₆ described above, and each of R _C1 and R _C2 is preferably a hydrogen atom, an alkyl group, or an alkoxy group. R _C1 and R _C2 are preferably not hydrogen atoms at the same time. The substituent represented by R _C3 represents the same group as the substituent represented by R ₁ to R ₆ described above, and the plurality of R _C3 may be the same or different, and may be bonded to each other to form a divalent group. And may form a ring. R _C3 is preferably an alkyl group or an alkoxy group, and at least one of the plurality of R _C3 is more preferably an alkoxy group. mC is preferably an integer of 1 to 2, mC is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and mC + mC is preferably an integer of 1 to 6, more preferably Is an integer from 1 to 3.

In formula (D), Q _D represents an (nD + 2) -valent aromatic group, R _D1 and R _D2 each represent a hydrogen atom or a substituent, R _D3 represents a substituent, and L _D represents an mD-valent linkage. Represents a group, mD represents an integer of 2 to 4, and nD represents an integer of 0 to 4.

The aromatic group represented by Q _D represents a group having the same meaning as the above-described aromatic group having an (nD + 2) valence. The substituent represented by R _D1 and R _D2 represents the same group as the substituent represented by R ₁ to R ₆ described above, and each of R _D1 and R _D2 is preferably a hydrogen atom, an alkyl group, or an alkoxy group. R _D1 and R _D2 are preferably not hydrogen atoms at the same time. The substituent represented by R _D3 represents a group having the same meaning as the substituent represented by R ₁ to R ₆ described above, and the plurality of R _D3 may be the same or different, and are bonded to each other to form a divalent group. And may form a ring. R _D3 is more preferably an alkyl group or an alkoxy group. mD is preferably an integer of 2 or 3, and nD is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

L _D is preferably an mD-valent linking group having 0 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, or a divalent group which may contain an oxygen atom or a sulfur atom in the main chain. examples of linking groups may be mentioned L _B and a linking group having the same meaning in general formula (B). Even 3 or more valences linking group can include L _B and a linking group having the same meaning in general formula (B).

  The method for producing the oxirane compound of the present invention described above is not particularly limited, and may be a conventionally known method, which can be synthesized according to the methods described in the following documents.

A: E.E. Borredon, F.M. Clavellanas, M .; Delmas, A.M. Gasset, J .; V. Sinisterra, J. et al. Org. Chem. 55, 501-504 (1990).
B: Elisabeth Borredon, Michel Delmas, Antonio Gasset, Tetrahedron Letters, 23 (50), 5283-5286 (1982).
C: E.I. J. et al. Corey, Michael Chaykovsky, J .; Amer. Chem. Soc. , 87, 1353-1364 (1965).
D: A. Guy, J .; Doussot, C.I. Ferroud, R.A. Garreau, A.M. Godefrey-Falguieres, SYNTHESIS, 821-822, September (1992).
E: Luis Bohe, Majed Kammun, Tetrahedron Letters, 43803-805 (2002).
F: Pausacker Lynch, J.A. Chem. Soc. , 1525 (1955).
Although the example of the compound represented by the oxirane compound of this invention, general formula (C), and general formula (D) below is given, this invention is not limited to these.

  The cationically polymerizable composition of the present invention may further contain a compound that generates an acid upon irradiation with active energy rays (also referred to as a photoacid generator, a photocationic polymerization initiator, or a cationic polymerization initiator).

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

First, BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p-CH of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium. ₃ C ₆ H ₄ SO ₃ ^- salt, CF ₃ SO ₃ ^- and sulfonic acid salts such as salts. Those having a borate compound as a counter anion and PF ₆ ^- salts acid generation capability 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 derivatives (for example, RP-2074 manufactured by Rhodia), allene-ion complex derivatives (for example, Irgacure manufactured by Ciba Geigy) 261), acid generators such as diazonium salt derivatives, triazine-based initiators and other halides.

  A compound that generates an acid upon irradiation with active energy rays is preferably a sulfonium salt compound represented by the general formula (b).

In the general formula (b), R ^b1 to R ^b3 each represents a substituent, and each may be the same or different, and the substituent is not particularly limited, but examples thereof include an alkyl group (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), alkenyl group (for example, vinyl group, Allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (eg, phenyl group, naphthyl group, etc.), heteroaromatic group (eg, furyl group, thienyl group, pyridyl group, Pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzo Table with imidazolyl group, a benzoxazolyl group, a quinazolyl group, phthalazyl group), a Hajime Tamaki (e.g., a pyrrolidyl group, imidazolidyl group, morpholyl group, and oxazolidyl group) or the like, R ^b3 these R ^b1 The substituents that may be substituted may further have substituents. Examples of groups that can be substituted for the substituents represented by R ^b1 to R ^b3 include the alkyl groups, alkenyl groups, alkynyl groups, and aromatic groups described above. In addition to hydrocarbon groups, heteroaromatic groups, and heterocyclic groups, alkoxy groups (eg, methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cyclo Alkoxy groups (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy groups (eg, phenoxy group, naphthyloxy group) ), 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 (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyl) Oxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl 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) Group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group) Ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), Group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group) Group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylamino) Carbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl Bonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2- Pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Etc.), alkylsulfonyl groups (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 atom etc.), fluorinated hydrocarbon group (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 ), A hydroxyl group, a nitro group, a carboxyl group, and the like. These substituents may be further substituted with the above-described substituents, and a plurality of these substituents are bonded to each other to form a ring. It may be. R ^B1 to R ^B3 may be optionally bonded to each other to form a ring. R ^b1 to R ^b3 are preferably an alkyl group or an aromatic hydrocarbon group, which may further have a substituent, and examples of the substituent include the substituents represented by R ^b1 to R ^b3 described above. Examples of groups that can be substituted for the group can be given.

X ^b− represents a counter ion, and examples of the counter anion include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , Complex ions such as SbF ₆ ⁻ and GaF ₆ ⁻ , benzene sulfonate ions (for example, p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ ), alkyl sulfonate ions (for example, CH ₃ SO _{^{3 -, C 2 H 5 SO}} 3 -), fluorinated alkyl sulfonate ion (e.g. _{^{CF 3 SO 3 -, C 2}} F 5 SO 3 -, C 9 F 19 SO 3 -), fluorinated alkyl benzene sulfonate ion ( For example, p-CF ₃ —C ₆ H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzenesulfonate ions (for example, p-F—C ₆ H ₄ SO ₃ ⁻ , C ₆ Examples thereof include sulfonate ions such as F ₅ SO ₃ ⁻ ). Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

  The compound represented by the general formula (b) is preferably any of the sulfonium salts represented by the following general formulas (I-1), (I-2), and (I-3).

In the general formula _{(I-1), R 11} , R 12, R 13 represents a substituent, m, n, p is an integer of 0 to 2. X ₁₁ ⁻ represents a counter ion.

In the general formula (I-2), R ₁₄ represents a substituent, and q represents 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 general formula (I-3), 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.

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, 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.) ), 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.), C1-C6 alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-6 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, Anthracenyl group etc.), C6-C10 aryloxy groups (e.g. phenoxy group, naphthoxy group etc.), C6-C10 arylthio groups (e.g. phenylthio group, naphthylthio group etc.), acyl groups (e.g. acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxy Carbonyl group and the like), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, 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 2, 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 ^- can be given 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, chlorine atom, bromine atom, fluorine atom, etc.) and an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, 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 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.), 1 to 6 carbon atoms An alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), Kirthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, Anthracenyl group etc.), C6-C10 aryloxy groups (e.g. phenoxy group, naphthoxy group etc.), C6-C10 arylthio groups (e.g. phenylthio group, naphthylthio group etc.), acyl groups (e.g. acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxyca Boniru group), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, etc. thienyl group), 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, 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.) ), 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.), C1-C6 alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-6 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, Anthracenyl group etc.), C6-C10 aryloxy groups (e.g. phenoxy group, naphthoxy group etc.), C6-C10 arylthio groups (e.g. phenylthio group, naphthylthio group etc.), acyl groups (e.g. acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxy Carbonyl group and the like), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, a thienyl group, etc.), a nitro group, a cyano group, and a hydroxyl group. 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 ^- can be given 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-3), R ₁₇ represents 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.) ), A cycloalkyl group having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (eg, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-6 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, tri Fluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group, anthracenyl group) Group), a C4-C8 hetero atom-containing aromatic ring group (for example, furyl group, thienyl group, etc.), nitro group, cyano group, and the like. A halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group are preferable. 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, unsubstituted alkyl group, a substituted, unsubstituted alkenyl group, a substituted, unsubstituted alkynyl group, or a substituted, unsubstituted Represents a substituted aryl group. 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.) ), A cycloalkyl group having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (eg, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-6 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, tri Fluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group, anthracenyl group) Group), a C4-C8 hetero atom-containing aromatic ring group (for example, furyl group, thienyl group, etc.), nitro group, cyano group, and the like. A halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group are preferable.

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 ^- can be given 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.

  Furthermore, the general formula (I-1) is more preferably 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 X _T1 ⁻ 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, and the like. The group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may have a condensed ring. Examples include an aromatic hydrocarbon group (for example, phenyl group, naphthyl group, etc.), aromatic heterocycle. Ring group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group) Benzimidazolyl group, benzoxazolyl group, a quinazolyl group and a 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, oxazolid group) Group), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) Etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), alkylthio groups (eg 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 (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarb) Nyl 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-ethylhexylcal A bonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group, etc.), an acyloxy group (for example, an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an octylcarbonyloxy group, a 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 , Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylamino Carbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2- Pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group) 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2 -Ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group, dimethylamino group, butyl) Amino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom) , Bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxyl group, mercapto group, silyl group ( For example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a phenyldiethylsilyl group, and the like.

These substituents may be further substituted with the above substituents, and a plurality of these substituents may be bonded to each other to form a ring. The alkyl group or aromatic group represented by R ^T11 and 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, or an alkoxy group. Examples of the substituted aromatic group and the alkyl group 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 groups (eg, phenoxy group, naphthyloxy group, etc.) Gerare, the alkylthio group, the arylthio group, a R ^T11 described above to a sulfur atom, R ^T12 synonymous groups attached thereto one location group, an alkylthio group (e.g., examples include a 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.) and the like.

The aromatic group, aryloxy group, and arylthio group described above may have a condensed ring. The alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, and arylthio group described above may further have a substituent, and a plurality of these substituents are bonded to each other to form a ring. 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, and 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, and fluorine Examples of alkyl groups substituted with atoms include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, It can be exemplified 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} , may be the same or different and each, R ^T11 and R ^T12, or a plurality of R ^T12 each other may bond together to form a ring, R ^T12 and R ^T13 or a plurality of R ^T13 each other may bond together 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 coupled To form a ring. At least one of R ^T13 is preferably bonded to the ortho-position or para-position relative to the benzene ring to which the sulfonium ion is bonded, and more preferably bonded to the para-position. At least one of R ^T14 for benzene ring sulfonium ion is bonded, it is preferable to bind the ortho- or para-position, and more preferably bonded at the para position.

X _T1 ⁻ represents a counter anion, which includes halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF _6. ^-, GaF ₆ ^- complex ions such as, benzene sulfonic acid ion _{(e.g., p-CH 3 C 6 H} 4 SO 3 -, C 6 H 5 SO 3 -), alkylsulfonate ion (e.g., CH ₃ SO ₃ ^- , C ₂ H ₅ SO ₃ ⁻ ), fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (for example, P-CF ₃ —C ₆ H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzenesulfonate ions (for example, p-F—C ₆ H ₄ SO ₃ ⁻ , C _And sulfonate ions such as ₆ F ₅ SO ₃ ⁻ ). Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

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

  The cationic polymerization initiator is preferably contained at a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass of the compound having cationic polymerizability. If the content of the polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, there is no further effect of improving curability. One or more of these cationic polymerization initiators can be selected and used.

  Further, the cationic polymerizable composition of the present invention may further contain another epoxy compound.

  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 are compounds represented by the following general formulas (A), (I), (II), (III), (IV), (V) and (VI).

Wherein, R ₁₀₀ represents a substituent, m0 represents an integer of 0 to 2, r0 represents an integer of 1-3. L ₀ represents a C 1-15 r 0 + 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 ₁₀₁ represents a substituent, m1 represents an integer of 0 to 2, p1 and q1 each represents 0 or 1, and r1 represents an integer of 1 to 3. L ₁ represents a C 1-15 r 1 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

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

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

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

In the formula, R ₁₀₅ represents a substituent, and m5 represents 1 or 2.

In the formula, R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2.

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

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

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

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

A 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 OCH (CH ₃ ) CH ₂ —],
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —],
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—],
4-oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —],
3,6-dioxa-1,8-octanediyl group [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —],
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —],
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —],
1,3-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 valent linking group include a group formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO—. And a group formed by combining a plurality of groups and -CS- groups.

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

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

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

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

  The cationically polymerizable composition of the present invention may further contain a vinyl ether compound. 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.

  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 preferable 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, light irradiation is started at a timing at which the viscosity or moisture 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, 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 cationically polymerizable composition >>
A cationically polymerizable composition 101 having the following composition was prepared.

Oxetane compound: Compound example 1 75 parts by mass Oxirane compound: Compound example AP-21 20 parts by mass Photoacid generator: Compound example TAS-13 5 parts by mass The oxetane compound and oxirane compound of the above active energy ray-curable composition are shown in Table 1. Modifications were made to prepare cationically polymerizable compositions 102-135.

1 ml of the resulting cationic polymerizable composition was applied to a 157 cm ² PET film, heated to 30 ° C., and maintained at a humidity of 80%, using a high pressure mercury lamp at an irradiation energy of 10 mJ / cm ² . Irradiation was performed for 2 seconds. Table 1 shows changes in the viscosity of the obtained cured composition. Further, 10 ml of the cationic polymerization composition was sealed in a sample bottle, and the change in viscosity of the cationic polymerization curable composition after being stored for 3 days in a constant temperature bath at 70 ° C. and 80% humidity was evaluated. These results are also shown in Table 1. Further, among the cationic polymerization compositions after storage for 3 days, UV irradiation experiments were again performed under the same conditions as before storage for those having little viscosity change. The results are shown in Table 1.

  The change in viscosity was judged from the tactile sensation of the experimenter by touching the light unirradiated coating film and the coating film after the light irradiation with a metal spatula. “Curing” indicates that a completely cured and robust coating was formed, “Gelification” indicates that a gel-like coating was formed, and “Thickened” indicates that the coating was not irradiated with light. Clearly there is a difference in viscosity between the film and the film after light irradiation. “Slightly thickened” means that there is a slight difference in viscosity between the light unirradiated film and the film after light irradiation. “No thickening” means that no significant difference was found in the tactile sensation between the light-unirradiated coating film and the light-irradiated coating film. As is apparent from the table, when the cationic polymerizable composition comprising the oxetane compound and the oxirane compound of the present invention is irradiated with ultraviolet rays, the coating film is cured and the polymerization proceeds. Furthermore, even if it preserve | saves at 70 degreeC for 3 days, the cationically polymerizable composition has shown that there is almost no viscosity raise, maintaining favorable polymerizability.

<Photo acid generator>
ESACURE1187: Triphenylsulfonium salt (manufactured by ESACURE 1187 lambertie)
UVI 6990: Triphenylsulfonium salt (Syracure UVI 6990 manufactured by Union Carbide)
RODOSIL 2074: Iodonium salt (RODOSIL 2074 manufactured by RODIA)
CGI552: Iodonium salt (CGI552 manufactured by Ciba Geigy)
CI2855: Aryl dialkylsulfonium salt (CI2855 manufactured by Nippon Soda Co., Ltd.)
<Oxirane compounds>
Celoxide 3000: Alicyclic epoxy (manufactured by Daicel UCB)
Celoxide 2021P: Alicyclic epoxy (Daicel UCB)
<Oxetane compound>
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
OXT-212: 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane Example 2
<Preparation of inkjet ink>
(Preparation of magenta ink 201)
Magenta ink 1 having the following composition was prepared. The magenta ink 201 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. The solution was prepared by dehydration under reduced pressure while heating.

Pigment: C.I. I. Pigment Red 184 3 parts by weight Dispersant: Solsperse 24000 (Avecia) 1 part by weight Oxetane compound: OXT221 75 parts by weight Oxirane compound: Celoxide 3000 20 parts by weight Photoacid generator: UVI 6990 5 parts by weight (Preparation of inks 202 to 249) )
Inks 201 to 249, which are ink jet inks of the present invention, were prepared in the same manner as ink 201 except that the oxetane compound, oxirane compound, photoacid generator, and pigment were changed to the configuration shown in Table 2 below. 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 added to 4.55 L (1 gallon) of styrene. ) The mixture was charged into a kneader, and pigment P2 was obtained in the same manner as P1.

<Photo acid generator>
ESACURE1187: Triphenylsulfonium salt (manufactured by ESACURE 1187 lambertie)
UVI 6990: Triphenylsulfonium salt (Syracure UVI 6990 manufactured by Union Carbide)
<Oxirane compounds>
Celoxide 3000: Alicyclic epoxy (manufactured by Daicel UCB)
Celoxide 2021P: Alicyclic epoxy (Daicel UCB)
<Oxetane compound>
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
OXT-212: 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane << Inkjet image recording and evaluation >>
Using the inks prepared above, image recording and evaluation of the obtained images were performed according to the following methods. Each ink was sealed in a glass sample bottle and stored in a thermostat at 70 ° C. and 80% RH for 3 days, and then the same image recording and image evaluation were performed.

[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 (amount with ink solution 10 g / m ² ) and 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 1 mW / cm ² directly under the light source, the exposure starts 0.3 seconds after landing and the exposure is 0.5 seconds later. Ended.

The exposure energy was 0.5 mJ / cm ² . This image printing was performed in an environment of 30 ° C., 20% RH and 85% RH.

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

<Evaluation of ink curability>
The printed images were evaluated for ink curability 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>
Paste a 25 mm wide cello tape (registered trademark) on the solid image and press it firmly, then quickly peel it off at a 90 degree peel angle, visually observe the image after separation, and follow the criteria below. Adhesion was evaluated.

○: 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 font was observed with a loupe, the state of adjacent dots was observed, and image bleeding resistance was evaluated according to the following criteria.

○: Almost no bleeding between 2 dots Δ: Slight bleeding between 2 dots is observed ×: The dots are greatly blurred Tables 3 and 4 show the results obtained as described above.

  As is clear from Tables 3 and 4, it can be seen that the ink composition for inkjet according to the present invention is excellent in ink curability and substrate adhesion, and can obtain a high-quality image without bleeding. In addition, it can be seen that the ink composition for ink-jet recording of the present invention maintains remarkably excellent ink curability even after ink storage.

Claims (7)

At least one compound selected from compounds having one or more oxetane rings, and at least one aromatic group in an adjacent carbon atom of an oxygen atom having at least one oxirane ring and constituting the oxirane ring. And at least one compound selected from compounds in which is substituted. At least one compound selected from compounds having at least one oxetane ring and having at least one aromatic group substituted on an adjacent carbon atom of an oxygen atom constituting the oxetane ring; and at least one or more compounds Cationic polymerizability characterized by containing at least one compound selected from compounds having an oxirane ring and having at least one aromatic group substituted on the adjacent carbon atom of the oxygen atom constituting the oxirane ring Composition. The cationically polymerizable composition according to claim 1 or 2, comprising a compound that generates an acid upon irradiation with an active energy ray. 4. The cationic polymerizable composition according to claim 3, wherein the active energy ray is ultraviolet light. The compound that generates an acid upon irradiation with active energy rays is at least one compound selected from sulfonium salt compounds represented by the following general formula (b). The cationically polymerizable composition described in 1.

(In the formula, R ^b1 to R ^b3 each represents a substituent, and X ^b- represents a counter ion.) An ink-jet ink composition comprising the cationically polymerizable composition according to any one of claims 1 to 5. The inkjet ink composition according to claim 6 is ejected as ink droplets onto a recording material by a recording head having at least one nozzle capable of selectively controlling ejection of ink droplets. An image forming method comprising: jetting onto the recording material and landing the ink droplet, and then irradiating an active energy ray to cure the ink droplet.