JP4597735B2 - INK COMPOSITION, INKJET RECORDING METHOD, PRINTED MATERIAL, METHOD FOR PRODUCING A lithographic printing plate, and lithographic printing plate - Google Patents

Description

  The present invention relates to an ink composition suitably used for ink jet recording, an ink jet recording method, a printed material using the ink composition, a lithographic printing plate obtained using the ink composition, and a method for preparing the lithographic printing plate. It is. Specifically, an ink composition suitable for inkjet recording, which can be cured with high sensitivity to radiation irradiation, can form a high-quality image, and has good storage stability, an inkjet recording method, In addition, the present invention relates to a printed material using the same, a lithographic printing plate obtained by using the ink composition, and a method for producing the lithographic printing plate.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. In particular, the ink jet method can be implemented with an inexpensive apparatus, and the ink can be efficiently used because the ink is ejected only on the required image portion to form the image directly on the recording medium. Cost is low. Furthermore, there is little noise and it is excellent as an image recording method.

According to the inkjet system, printing is possible not only on plain paper but also on non-water-absorbing recording media such as plastic sheets and metal plates. However, high speed and high image quality are important issues for printing. The time required for drying and curing the droplets after printing has a property of greatly affecting the productivity of printed matter and the sharpness of the printed image.
As one of the ink jet methods, there is a recording method using an ink for ink jet recording that can be cured by irradiation of radiation. According to this method, the productivity of printing can be improved and a sharp image can be formed by irradiating the ink immediately after ink ejection or after a certain time and curing the ink droplets.
By achieving high sensitivity of ink for ink jet recording that can be cured by irradiation with radiation such as ultraviolet rays, high curability is imparted to radiation, improving productivity of ink jet recording, reducing power consumption, and applying to radiation generators. There are many benefits such as longer life by reducing the load and prevention of volatilization of low molecular weight materials due to insufficient curing. In addition, high sensitivity improves the strength of the image formed by the ink for ink jet recording in particular, and particularly when applied to the formation of a lithographic printing plate, the curing strength of the image area is increased, resulting in high printing durability. Will be obtained.

  Such a curable ink jet method using radiation, for example, ultraviolet rays has been attracting attention in recent years because it has a relatively low odor, and can be recorded on a recording medium having no quick drying and no ink absorption. An ultraviolet ray curable ink composition for inkjet that is used is disclosed (for example, see Patent Documents 1 to 5). Further, even for a support that is usually difficult to directly record with an ink jet recording method, it is possible to record an image with no blur, high sensitivity, high adhesion to a recording medium, and skin irritation or For the purpose of providing an inkjet recording ink with low sensitization and high safety, a composition containing a polymerizable compound consisting of a specific radical polymerization type acrylate compound group and a coloring material has been proposed ( For example, see Patent Documents 6 and 7.) Although these radical polymerization type inks are excellent in curing speed and can form images without bleeding, they have a problem that adhesion to a recording medium is reduced due to volume shrinkage during curing.

For this reason, for the purpose of improving the adhesion to the recording medium, a cationic polymerization type ink composition having a small shrinkage rate upon UV curing has been proposed (for example, see Patent Document 8). However, these cationic polymerization type inks are not sufficiently stable at the time of storage due to the reaction based on the acid generated with the passage of time, which has been a major obstacle to practical use. For this reason, as an attempt to improve the storage stability, a technique of adding a basic compound or a thermal base generator has been proposed (for example, see Patent Documents 9 to 11), but the basic compound was generated by exposure. It has been found that a new problem arises that the curing sensitivity of the ink is lowered due to the inhibition of the acid function. For this reason, both storage stability and high sensitivity are desired.
JP-A-63-235382 JP-A-3-216379 Japanese Patent Laid-Open No. 5-214280 Japanese Patent Publication No.6-212256 Japanese Patent Publication No. 6-62905 JP 2003-192943 A JP 2003-192944 A Japanese Patent Laid-Open No. 9-183928 JP 2003-312121 A JP 2003-341217 A JP 2004-91558 A

The object of the present invention made in consideration of the above problems is that it can be cured with high sensitivity to radiation irradiation, can form a high-quality image, has excellent adhesion on a recording medium, and An object of the present invention is to provide an ink composition having good storage stability and suitable for ink jet recording, and an ink jet recording method using the ink composition.
Another object of the present invention is to provide a printed matter, a lithographic printing plate, and a method for producing a lithographic printing plate, which are obtained using an ink composition that is excellent in storage stability and can be cured with high sensitivity by irradiation with radiation. It is to provide.

  As a result of intensive studies, the inventors have improved the storage stability while maintaining high sensitivity by using a polyfunctional amine compound having a basic nitrogen atom having a specific function as an additive. The inventors have found that an ink composition suitable for ink jet recording in which the ink composition has improved ejection properties, particle shape retention, and adhesion to a recording medium, and has completed the present invention.

That is, the present invention is as follows.
<1> (a) a cationically polymerizable compound, (b) a compound that generates an acid upon irradiation with radiation, (c) two bases in which atoms are bonded via a linking group having 2 or 3 carbon atoms at least have a sexual nitrogen atom, and wherein the polyfunctional amine compound and the basic nitrogen atom and hydrogen ions can coordinate, and (d) pKa containing organic acidic component showing a value of 2 to 6 An ink composition.

<2> The ink composition according to <1>, wherein the polyfunctional amine compound (c) is at least one compound selected from compounds (C-1) to (C-27) described later.

< 3 > (e) The ink composition according to <1 > or <2> , which contains a colorant.
< 4 > The ink composition according to < 3 >, wherein the colorant (d) is a pigment or an oil-soluble dye.
< 5 > The ink composition according to any one of <1> to < 4 >, which is for inkjet recording.

< 6 > A step of ejecting the ink composition according to any one of <1> to < 5 > onto a recording medium by an inkjet printer, and curing the ejected ink composition by irradiation with radiation. An ink jet recording method comprising a step.

< 7 > A printed matter obtained by ejecting the ink composition according to any one of <1> to < 5 > onto a recording medium using an inkjet printer, and then irradiating the ink composition to cure the ink composition. .

< 8 > After ejecting the ink composition according to any one of <1> to < 5 > onto a hydrophilic support, the ink composition is irradiated with radiation to cure the ink composition, thereby forming a hydrophobic region. A method for preparing a lithographic printing plate, characterized in that:
< 9 > formed by ejecting the ink composition according to any one of <1> to < 5 > on a hydrophilic support, and then irradiating the ink composition to cure the ink composition. A lithographic printing plate having a hydrophobic region.

The ink composition of the present invention can be used for normal printing to form an image with high image quality and excellent strength, and not only a high-quality printed matter can be obtained, but also suitable for the production of resists, color filters, and optical discs. It can be used and is also useful as an optical modeling material.
In addition, by applying an ink jet recording method, even when an ink composition is ejected onto a non-absorbable recording medium, it is cured with high sensitivity and a high-strength image area is directly formed based on digital data. sell. Therefore, the ink composition of the present invention is also suitably used for preparing a lithographic printing plate, particularly a lithographic printing plate having a large area of A2 or larger, and the lithographic printing plate obtained thereby has excellent printing durability. It will be a thing.

According to the present invention, it can be cured with high sensitivity to radiation irradiation, can form a high-quality image, has excellent adhesion to a recording medium, and has good storage stability. And an ink jet recording method using the ink composition can be provided.
Further, the printed matter obtained by using the ink composition of the present invention, which has excellent storage stability and can be cured with high sensitivity by irradiation with ultraviolet rays, has high image quality and excellent image portion strength. Further, by using the ink composition of the present invention, a lithographic printing plate having high printing durability and high image quality can be produced based on digital data.

[Ink composition]
The ink composition of the present invention can be cured by irradiation with radiation, (a) a cationically polymerizable compound , (b) a compound that generates an acid upon irradiation with radiation , (c) 2 atoms between atoms. or linked via the 3 linking group two basic nitrogen atoms and at least chromatic comprising a polyfunctional amine compound and the basic nitrogen atom and hydrogen ions can coordinate, and (d) pKa is 2 It is necessary to contain an organic acidic component having a value of ˜6, and ( e) a colorant is contained if desired.
The “radiation” as used in the present invention is not particularly limited as long as it can impart energy capable of generating a starting species in the ink composition by the irradiation, and widely includes α rays, γ rays, X Including rays, ultraviolet rays, visible rays, electron beams, and the like. Among these, from the viewpoints of curing sensitivity and device availability, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable. Therefore, the ink composition of the present invention is preferably an ink composition that can be cured by irradiating ultraviolet rays as radiation.
Hereinafter, each component used in the ink composition of the present invention will be described in order.

[(C) Atomic is at least have a two basic nitrogen atoms consisting coupled via a linking group having a carbon number of 2 or 3, multi and the basic nitrogen atom and hydrogen ions can coordinate Functional amine compound]
First, it is a characteristic component in the present invention component (c), between atoms at least have a two basic nitrogen atoms consisting coupled via a linking group having a carbon number of 2 or 3, wherein the base It is a polyfunctional amine compound (hereinafter referred to as “(c) a specific base component” as appropriate) capable of coordinating (so-called chelation) with a reactive nitrogen atom and a hydrogen ion.
Here, the “basic nitrogen atom” in the present invention refers to a nitrogen atom that is bonded only to a carbon atom, is in an unoxidized state, and has one lone electron pair.
According to the present invention, by utilizing such a phenomenon that two basic nitrogen atoms and hydrogen ions are coordinated, an acid that is an impurity present in the ink composition can be effectively captured, and the ink It has an excellent effect that the storage stability of the composition is greatly improved.

The polyfunctional amine compound as the specific base component may have at least two basic nitrogen atoms that can coordinate with the hydrogen ion as described above in the molecule. Further, when the specific base component has 3 or more basic nitrogen atoms in the molecule, all of the basic nitrogen atoms may be capable of coordinating with hydrogen ions, Some of the basic nitrogen atoms may be capable of taking care of hydrogen ions.
In this way, the amount of hydrogen ions (acids) captured varies depending on the number of basic nitrogen atoms that can coordinate with hydrogen ions in the molecule, so depending on the structure of the polyfunctional amine compound that is a specific base component. , The amount added will be adjusted accordingly.

Further, the polyfunctional amine compound which is a specific base component, in the molecule, between the two basic nitrogen atoms are bonded through a linking group having 2 or 3 carbon atoms, whereby the two bases By coordinating a reactive nitrogen atom and a hydrogen ion, an intermediate state of a 5-membered or 6-membered ring including a hydrogen atom can be formed. This intermediate state is more preferable because the form in which hydrogen ions are coordinated is stabilized.

In the present invention, the “number of carbon atoms” in the linking group having 2 or 3 carbon atoms does not include the number of carbon atoms of the substituent, and is used only for linking two basic nitrogen atoms. Refers to the number of atoms. Thus, a single bond may be sufficient and the double bond may be sufficient between the carbon atom and basic nitrogen atom which comprise a coupling group.
Specific examples of the linking group having 2 or 3 carbon atoms include, in addition to an ethylene group and a propylene group, a monocyclic or polycyclic alicyclic structure, a monocyclic or polycyclic aromatic ring structure, and a monocyclic or Examples thereof include a carbon-containing atomic group that forms a part of a polycyclic heterocyclic structure.
These linking groups may further have a substituent, and for example, a basic nitrogen atom may be substituted via 2 or 3 carbon atoms.
These substituents may be bonded to other groups in the molecule to form a ring structure. The ring structure formed is an aliphatic ring, an aromatic ring, a heterocyclic ring containing a basic nitrogen atom, or the like.

  Specific examples of (c) specific base components [(c-1) to (c-27)] suitably used in the present invention are shown below, but the present invention is not limited thereto.

In the ink composition of the present invention, only one type of (c) specific base component may be added, or two or more types may be used in combination.
The content of the specific base component (c) in the ink composition is suitably 0.001 to 10% by mass, preferably 0.01 to 7% by mass, and more preferably based on the total solid content of the composition. It is 0.03-5 mass%.
The ratio of (c) the specific base component and (b) the compound that generates an acid upon irradiation with radiation is 0.001 to 0.5, preferably 0.005, in a molar ratio of (c) / (b). Used in the range of ~ 0.2.

[(A) Cationic polymerizable compound]
The (a) cationic polymerizable compound used in the present invention is not particularly limited as long as it is a compound that causes a polymerization reaction and cures by an acid generated from a photo acid generator (b) described later, and is a photo cationic polymerizable monomer. Various known cationically polymerizable monomers known as can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-220526. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like.

Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aromatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

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

  Examples of the aliphatic epoxide include dihydric polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Typical examples 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, di- or tri- or di- or tri-glycol or adducts thereof. Polyglycidyl ether of polyhydric alcohol such as glycidyl ether, diglycidyl ether of polyethylene glycol or alkylene oxide adduct thereof, diglycidyl ether of polyalkylene glycol represented by diglycidyl ether of polypropylene glycol or alkylene oxide adduct thereof, etc. Can be mentioned. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The epoxy compound may be monofunctional or polyfunctional.
Examples of monofunctional epoxy compounds that can be used in the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide etc. are mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy Hexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy- 6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8 -Diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  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.

The vinyl ether compound may be monofunctional or polyfunctional.
Specifically, examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether , Methoxypolyethyleneglycol Vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Examples include chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

  Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound in the present invention refers to a compound having an oxetane ring, and a known oxetane compound can be arbitrarily selected and used as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. .
The compound having an oxetane ring that can be used in the ink composition of the present invention is preferably a compound having 1 to 4 oxetane rings in the structure. By using such a compound, it becomes easy to maintain the viscosity of the ink composition within a good handling range, and obtain high adhesion between the cured ink composition and the recording medium. Can do.

  Examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following general formulas (1) to (3).

In the general formulas (1) to (3), R ^a1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. Represents. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.

In the general formula (1), R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, or an alkylcarbonyl having 2 to 6 carbon atoms. Group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group. It is done. Examples of the group having an aromatic ring include a phenyl group, a benzyl group, a fluorobenzyl group, a methoxybenzyl group, and a phenoxyethyl group. Examples of the alkylcarbonyl group include an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
Examples of the N-alkylcarbamoyl group include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group.

In the general formula (2), R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or a carbonyl group. An alkylene group containing a group, an alkylene group containing a carboxyl group, an alkylene group containing a carbamoyl group, or a group shown below is represented. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

In the polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, Represents a carboxyl group or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2000.
R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure.

In the above monovalent, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  Examples of the compound having 3 to 4 oxetane rings include compounds represented by the following general formula (4).

In the general formula (4), R ^a1 is synonymous with R ^a1 in the formula (1). R ^a9 is a polyvalent linking group, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by A to C below, or a branched poly (alkylene group such as a group represented by D below. (Oxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group, or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following general formula (5) having an oxetane ring in the side chain.

In the general formula (5), R ^a1 has the same meaning as R ^a1 in Formula (1). Also, R ^a8 has the same meaning as R ^a8 in the general formula (4). R ^a11 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.

The compound having such an oxetane ring is described in detail in the above-mentioned JP-A No. 2003-341217, paragraph numbers [0021] to [0084], and the compounds described herein can be suitably used in the present invention.
Among the oxetane compounds used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and tackiness of the ink composition.

In the ink composition of the present invention, these cationic polymerizable compounds may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during ink curing. Is preferably a combination of at least one compound selected from an oxetane compound and an epoxy compound and a vinyl ether compound.
The content of the (a) cationic polymerizable compound in the ink composition is suitably 10 to 95% by mass, preferably 30 to 90% by mass, and more preferably 50 to 85%, based on the total solid content of the composition. It is the range of mass%.

[(B) Compound generating acid upon irradiation]
The ink composition of the present invention contains a compound that generates an acid upon irradiation with radiation (hereinafter, appropriately referred to as a “photoacid generator”).
Examples of the photoacid generator that can be used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and light used for microresists. (400-200 nm ultraviolet rays, far ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam, ion beam, etc. A compound capable of generating can be appropriately selected and used.

  Examples of such a photoacid generator include an onium salt such as a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, a sulfonium salt, a selenonium salt, an arsonium salt, or the like, which decomposes upon irradiation with radiation to generate an acid. Halogen compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl type protecting groups, compounds that generate sulfonic acids upon photolysis, such as iminosulfonates, disulfone compounds, diazoketosulfones And diazodisulfone compounds.

  Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal etal, Polymer, 21, 423 (1980), U.S. Pat. Nos. 4,069,055, 4,069,056, Re27,992, JP-A-3-140,140 Ammonium salts described in the above, and the like. C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, and the like; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-296514 and the like,

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

  J. et al. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 1047 (1979), etc., selenonium salts, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat. -32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243 Organic halogen compounds described in JP-A No. 63-298339, etc .; Meier et al, J.A. Rad. Curing, 13 (4), 26 (1986), T.A. P. Gill et al, Inorg. Chem. , 19, 3007 (1980), D.M. Astruc, Acc. Chem. Res. , 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-161445, etc.

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

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

  In addition, a group in which an acid is generated by light or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, M.P. E. Woodhouse et al., J. MoI. Am. Chem. Soc. 104, 5586 (1982), S .; P. Pappas et al. Imaging Sci. , 30 (5), 218 (1986), S .; Kondo et al, Makromol. Chem. , Rapid Commun. , 9, 625 (1988), Y. et al. Yamada et al, Makromol. Chem. 152, 153, 163 (1972), J. Am. V. Crivello et al, J.A. PolymerSci. , Polymer Chem. Ed. 17, 3845 (1979), U.S. Pat. No. 3,849,137, German Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, The compounds described in JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A 63-146029, and the like can be used.

  Further, V.V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al, J.A. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent No. 126,712, and the like.

  Preferred examples of the photoacid generator that can be used in the present invention include compounds represented by the following general formulas (b1), (b2), and (b3).

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

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

Rc ¹ represents an organic group.
Examples of the organic group represented by Rc ¹ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these is a single bond, —O—, —CO _2. -, - S -, - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as. Rd ¹ represents a hydrogen atom or an alkyl group.

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

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

In general formula (b1), the carbon number of the organic group represented by R ²⁰¹ , R ²⁰² or R ²⁰³ is generally 1 to 30, preferably 1 to 20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ²⁰¹ to R ^203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

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

The photoacid generator may be a compound having a plurality of structures represented by the general formula (b1). For example, at least one of R ²⁰¹ to R ²⁰³ of the compound represented by the general formula (b1) is, directly and at least one R ²⁰¹ to R ²⁰³ of another compound represented by formula (b1), or, It may be a compound having a structure bonded through a linking group.

  More preferable examples of the compound represented by the general formula (b1) include compounds (b1-1), (b1-2), and (b1-3) described below.

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

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

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

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

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

The aryl group represented by R ²⁰¹ to R ²⁰³ include an alkyl group, cycloalkyl group, an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., You may have a C6-C14), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferred. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Substituents, of the three R ²⁰¹ to R ^203, may be substituted on any one, or may be substituted on all of three. When R ^{201 to} R ²⁰³ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

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

The cycloalkyl group represented by R ^{201 to} R ²⁰³ is preferably a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group), and more preferably a cyclic 2-oxoalkyl group. .

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

Next, the compound (b1-3) will be described.
The compound (b1-3) is a compound represented by the following general formula (b1-3), and is a compound having a phenacylsulfonium salt structure.

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

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

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

The alkoxy group represented by R ^{1c to} R ^5c may be linear, branched or cyclic, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, preferably a linear chain having 1 to 5 carbon atoms and Branched alkoxy group (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy group having 3 to 8 carbon atoms (for example, cyclopentyloxy group, Cyclohexyloxy group).

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

Preferably, any one of R ^{1c to} R ^5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of carbon numbers from R ^1c to R ^5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

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

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

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

The aryl group represented by R ²⁰⁴ to R ^207, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group represented by R ²⁰⁴ to R ²⁰⁷ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group Propyl group, butyl group, pentyl group). Cycloalkyl groups represented by R ²⁰⁴ to R ²⁰⁷ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
Examples of the substituent that R ^{204 to} R ²⁰⁷ may have include, for example, an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), and an aryl group (eg, carbon (Chemical formula 6-15), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group etc. can be mentioned.

  In the present invention, compounds that generate an acid upon irradiation with actinic rays or radiation that may be used (photoacid generator) are further represented by the following general formulas (b4), (b5), and (b6). A compound can be mentioned.

In general formulas (b4) to (b6), Ar ³ and Ar ⁴ each independently represents an aryl group.
In general formulas (b5) and (b6), R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
In general formula (b5), A represents an alkylene group, an alkenylene group or an arylene group.

  Preferable examples of the photoacid generator include compounds represented by general formulas (b1) to (b3).

  Preferred examples of the (b) photoacid generator [(b-1) to (b-96)] that can be used in the present invention are listed below, but the present invention is not limited thereto.

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

(B) A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the (b) photoacid generator in the ink composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably in terms of the total solid content of the ink composition. Is 1-7 mass%.

  In the ink composition of the present invention, various additives can be used in combination with the essential components according to the purpose. These optional components will be described.

[(D) Organic acidic component having a pKa value of 2 to 6]
In the ink composition of the invention, (d) pKa organic acidic component showing a value of from 2 to 6 (hereinafter, simply referred to as "organic acidic component".) Added. The organic acidic component (d) having a pKa value of 2 to 6 used in the present invention corresponds to a qualitatively weakly acidic organic compound. When the pKa of the organic acidic component is larger than 6, the sensitivity is lowered when it is added to the ink composition of the present invention. When the pKa is smaller than 2, the stability of the ink composition with time is deteriorated. In the present invention, it is preferable to apply an organic acidic component having a pKa value of 2 to 6.

  Specific examples of the organic acidic component having a pKa value of 2 to 6 include carboxylic acids. Examples of carboxylic acids include acetic acid, phenylacetic acid, phenoxyacetic acid, methoxypropionic acid, lactic acid, hexanoic acid, heptanoic acid, octanoic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, cyclopropylcarboxylic acid, cyclobutanecarboxylic acid. Acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 1-adamantanecarboxylic acid, 1,3-adamantanedicarboxylic acid, norbornene-2,3-dicarboxylic acid, abietic acid, trans-retinoic acid, cyclohexylacetic acid, dicyclohexylacetic acid, Adamantane acetic acid, malonic acid, malonic acid monomethyl ester, fumaric acid, maleic acid, maleic acid monomethyl ester, itaconic acid, crotonic acid, succinic acid, adipic acid, sebacic acid, glycolic acid, diglycolic acid, mandelin , Tartaric acid, malic acid, arginic acid, cinnamic acid, methoxycinnamic acid, 3,5-dimethoxycinnamic acid, benzoic acid, salicylic acid, 4-hydroxybenzoic acid, gallic acid, 3-nitrobenzoic acid, 3-chloro Benzoic acid, 4-vinylbenzoic acid, t-butylbenzoic acid, 1-naphthoic acid, 1-hydroxy-2-naphthoic acid, fluorenone-2-carboxylic acid, 9-anthracenecarboxylic acid, 2-anthraquinonecarboxylic acid, phthalic acid , Phthalic acid monomethyl ester, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid monomethyl ester, and other aliphatic or aromatic monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids having 1 to 20 carbon atoms. However, it is not limited to this.

[(E) Colorant]
The ink composition of the present invention can form a visible image by adding a colorant. For example, when forming an image area of a lithographic printing plate, it is not always necessary to add it, but it is also preferable to use a colorant from the viewpoint of plate inspection of the obtained lithographic printing plate.
There is no restriction | limiting in particular in the coloring agent which can be used here, According to a use, well-known various color materials and (pigment, dye) can be selected suitably, and can be used. For example, when forming an image excellent in weather resistance, a pigment is preferable. As the dye, both water-soluble dyes and oil-soluble dyes can be used, but oil-soluble dyes are preferred.

[Pigment]
The pigment preferably used in the present invention will be described.
The pigment is not particularly limited, and all commercially available organic and inorganic pigments or pigments dispersed in an insoluble resin or the like as a dispersion medium, or the resin is grafted onto the pigment surface Can be used. Moreover, what dye | stained the resin particle with dye can be used.
Examples of these pigments include, for example, “Pigment Dictionary” (2000), edited by Seijiro Ito. Herbst, K.M. Hunger “Industrial Organic Pigments”, JP 2002-12607 A, JP 2002-188025 A, JP 2003-26978 A, and JP 2003-342503 A3.

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

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

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

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

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

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

For dispersing the pigment, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used. be able to.
It is also possible to add a dispersant when dispersing the pigment. Examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a high molecular weight unsaturated acid ester, a high molecular weight copolymer, a modified polyacrylate, an aliphatic Examples thereof include polyvalent carboxylic acids, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate esters, and pigment derivatives. It is also preferable to use a commercially available polymer dispersant such as the Solsperse series from Zeneca.
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.

  In the ink composition, as a dispersion medium for various components such as pigments, a solvent may be added, or the solvent-free low molecular weight component (a) cationic polymerizable compound may be used as a dispersion medium. However, the ink composition of the present invention is a radiation curable ink, and is preferably solventless in order to cure the ink after it is applied to a recording medium. This is because if the solvent remains in the cured ink image, the solvent resistance is deteriorated or a VOC (Volatile Organic Compound) problem of the remaining solvent occurs. From such a viewpoint, as the dispersion medium, (a) a cationically polymerizable compound is used, and among them, it is preferable to select a cationically polymerizable monomer having the lowest viscosity in terms of dispersion suitability and handling properties of the ink composition. .

The average particle diameter of the pigment is preferably 0.02 to 0.4 μm, more preferably 0.02 to 0.1 μm, and more preferably 0.02 to 0.07 μm.
The selection of pigment, dispersant, dispersion medium, dispersion conditions, and filtration conditions are set so that the average particle diameter of the pigment particles is within the above-mentioned preferable range. 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.

〔dye〕
The dye used in the present invention is preferably oil-soluble. Specifically, it means that the solubility in water at 25 ° C. (the mass of the dye dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, a so-called water-insoluble oil-soluble dye is preferably used.

The dye used in the present invention preferably has an oil-solubilizing group introduced into the above-described dye mother core in order to dissolve the necessary amount in the ink composition.
As the oil-solubilizing group, long chain, branched alkyl group, long chain, branched alkoxy group, long chain, branched alkylthio group, long chain, branched alkylsulfonyl group, long chain, branched acyloxy group, long chain, branched alkoxycarbonyl group, Long chain, branched acyl group, long chain, branched acylamino group long chain, branched alkylsulfonylamino group, long chain, branched alkylaminosulfonyl group and these long chains, aryl groups containing branched substituents, aryloxy groups, aryloxycarbonyl Group, arylcarbonyloxy group, arylaminocarbonyl group, arylaminosulfonyl group, arylsulfonylamino group and the like.
In addition, for water-soluble dyes having carboxylic acid and sulfonic acid, long chain, branched alcohol, amine, phenol, aniline derivatives are used as oil-solubilizing alkoxycarbonyl groups, aryloxycarbonyl groups, alkylaminosulfonyl groups, A dye may be obtained by conversion to an arylaminosulfonyl group.

The oil-soluble dye preferably has a melting point of 200 ° C. or lower, more preferably has a melting point of 150 ° C. or lower, and still more preferably has a melting point of 100 ° C. or lower. By using an oil-soluble dye having a low melting point, the precipitation of dye crystals in the ink composition is suppressed, and the storage stability of the ink composition is improved.
Further, it is desirable that the oxidation potential is noble (high) in order to improve fading, particularly resistance to oxidizing substances such as ozone and curing characteristics. For this reason, as the oil-soluble dye used in the present invention, those having an oxidation potential of 1.0 V (vs SCE) or more are preferably used. The oxidation potential is preferably higher, the oxidation potential is more preferably 1.1 V (vs SCE) or more, and particularly preferably 1.15 V (vs SCE) or more.

As the yellow dye, a compound having a structure represented by the general formula (Y-I) described in JP-A No. 2004-250483 is preferable.
Particularly preferred dyes are dyes represented by general formulas (Y-II) to (Y-IV) described in paragraph [0034] of JP-A No. 2004-250483. And the compounds described in paragraph numbers [0060] to [0071] of JP-A-250483. The oil-soluble dye of the general formula (Y-I) described in the publication may be used not only for yellow but also for inks of any color such as black ink and red ink.

The magenta dye is preferably a compound having a structure represented by the general formulas (3) and (4) described in JP-A No. 2002-114930. Specific examples include paragraphs of JP-A No. 2002-114930. Examples include the compounds described in [0054] to [0073].
Particularly preferred dyes are azo dyes represented by the general formulas (M-1) to (M-2) described in paragraph numbers [0084] to [0122] of JP-A No. 2002-121414, and specific examples Examples thereof include compounds described in paragraph numbers [0123] to [0132] of JP-A No. 2002-121414. The oil-soluble dyes represented by the general formulas (3), (4) and (M-1) to (M-2) described in the publication are used not only for magenta but also for any color ink such as black ink and red ink. May be.

Examples of the cyan dye include dyes represented by formulas (I) to (IV) described in JP-A No. 2001-181547, and paragraphs [0063] to [0078] of JP-A No. 2002-121414. The dyes represented by the general formulas (IV-1) to (IV-4) described above are preferred, and specific examples include paragraph numbers [0052] to [0066] of JP-A No. 2001-181547. Examples thereof include the compounds described in paragraph Nos. [0079] to [0081] of Kai 2002-121414.
Particularly preferred dyes are phthalocyanine dyes represented by general formulas (CI) and (C-II) described in paragraphs [0133] to [0196] of JP-A No. 2002-121414, A phthalocyanine dye represented by formula (C-II) is preferred. Specific examples thereof include the compounds described in JP-A No. 2002-121414, paragraph numbers [0198] to [0201]. The oil-soluble dyes of the formulas (I) to (IV), (IV-1) to (IV-4), (CI) and (C-II) are not only cyan but also black ink or green ink. The ink may be used for any color ink.

-Oxidation potential-
The oxidation potential value (Eox) of the dye in the present invention can be easily measured by those skilled in the art. For this method, see, for example, Delahay, “New Instrumental Methods in Electrochemistry” (1954, published by Interscience Publishers); J. et al. "Electrochemical Methods" by Bard et al. (1980, published by John Wiley & Sons) and Akira Fujishima et al., "Electrochemical Measurement Methods" (1984, published by Gihodo Publishing Co., Ltd.).
Specifically, the oxidation potential is 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / min in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Approximate the oxidization wave in a straight line by dissolving 1 liter and sweeping to the oxidation side (noble side) using carbon (GC) as the working electrode and rotating platinum electrode as the counter electrode by cyclic voltammetry and DC polarography equipment Then, the intermediate potential of the line segment formed by the intersection of this straight line and the residual current / potential line and the intersection of the straight line and the saturation current line (or the intersection of the straight line parallel to the vertical axis passing through the peak potential value) Values are measured as values for SCE (saturated calomel electrode). This value may deviate by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, but the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone). . The supporting electrolyte and solvent to be used can be selected appropriately depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Akira Fujishima et al., “Electrochemical measurement method” (1984, published by Gihodo Publishing Co., Ltd.), pages 101 to 118.

  Specific examples of the dye that can be used in the present invention are shown below, but the dye used in the present invention is not limited to the following specific examples.

  These colorants are preferably added in an amount of 1 to 20% by mass in terms of solid content in the ink composition, and more preferably 2 to 10% by mass.

[Other ingredients]
The various additives used as necessary are described below.
[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but is generally about 0.5 to 15% by mass in terms of solid content.

[Sensitizer]
A sensitizer may be added to the ink composition of the present invention as necessary for the purpose of improving the acid generation efficiency of the photoacid generator and increasing the photosensitive wavelength. Any sensitizer may be used as long as the photoacid generator is sensitized by an electron transfer mechanism or an energy transfer mechanism. Preferably, aromatic polycondensed compounds such as anthracene, 9,10-dialkoxyanthracene, pyrene and perylene, aromatic ketone compounds such as acetophenone, benzophenone, thioxanthone and Michlerketone, heterocyclic compounds such as phenothiazine and N-aryloxazolidinone Is mentioned. The addition amount is appropriately selected according to the purpose, but is generally 0.01 to 1 mol%, preferably 0.1 to 0.5 mol%, based on the photoacid generator.

〔Antioxidant〕
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
The addition amount is appropriately selected according to the purpose, but is generally about 0.1 to 8% by mass in terms of solid content.

[Anti-fading agent]
In the ink composition of the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, VII, I to J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
The addition amount is appropriately selected according to the purpose, but is generally about 0.1 to 8% by mass in terms of solid content.

[Conductive salts]
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition of the present invention for the purpose of controlling ejection properties.

〔solvent〕
In order to improve the adhesion to the recording medium, it is also effective to add a very small amount of an organic solvent to the ink composition of the present invention.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC, and the amount is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass with respect to the whole ink composition. % Range.

[Polymer compound]
Various polymer compounds can be added to the ink composition of the present invention in order to adjust film physical properties. High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

[Surfactant]
A surfactant may be added to the ink composition of the present invention.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

[Preferred physical properties of ink composition]
The ink composition of the present invention preferably has an ink viscosity of 7 to 30 mPa · s, more preferably 7 to 20 mPa · s at the temperature at the time of ejection in consideration of ejection properties, and is in the above range. It is preferable to adjust the composition ratio appropriately. The ink viscosity at 25 to 30 ° C. is 35 to 500 mPa · s, preferably 35 to 200 mPa · s. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be prevented, uncured monomer can be reduced, and odor can be reduced. Dot bleeding at the time of landing can be suppressed, and as a result, the image quality is improved. If the ink viscosity at 25 to 30 ° C. is less than 35 mPa · s, the effect of preventing bleeding is small, and conversely if it is greater than 500 mPa · s, there is a problem in the delivery of the ink liquid.

  The surface tension of the ink composition of the present invention is preferably 20 to 30 mN / m, more preferably 23 to 28 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

The ink composition of the present invention thus adjusted is suitably used as an ink for inkjet recording. When used as an ink for ink jet recording, the ink composition is ejected onto a recording medium by an ink jet printer, and then the ejected ink composition is irradiated with radiation and cured to perform recording.
In the printed matter obtained with this ink, the image portion is cured by irradiation with radiation such as ultraviolet rays, and the strength of the image portion is excellent. Part), and can be used for various purposes.

[Inkjet recording method and inkjet recording apparatus]
Next, an ink jet recording method and an ink jet recording apparatus that can be suitably employed in the present invention will be described below.
The inkjet recording method of the present invention includes a step of ejecting the above-described ink composition of the present invention onto a recording medium by an inkjet printer, and a step of curing the ejected ink composition by irradiation with radiation. Features.

  In the ink jet recording method, it is preferable that the ink composition is heated to 40 to 80 ° C. to lower the viscosity of the ink composition to 7 to 30 mPa · s and then ejected. Stability can be achieved. In general, radiation curable ink compositions generally have a higher viscosity than aqueous inks, and thus have a large viscosity fluctuation range due to temperature fluctuations during ink ejection. This viscosity variation of the ink composition directly affects the droplet size and the droplet ejection speed, which causes image quality degradation. Therefore, it is necessary to keep the ink composition temperature as constant as possible when ejecting the ink. It is. The control range of the ink composition temperature is preferably set temperature ± 5 ° C., more preferably set temperature ± 2 ° C., and further preferably set temperature ± 1 ° C.

  One feature of the ink jet recording apparatus is that it includes a means for stabilizing the temperature of the ink composition, and the portion to be kept at a constant temperature is a piping system from an ink tank (an intermediate tank if there is an intermediate tank) to the nozzle ejection surface. All of the members are targeted.

  The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the ink composition flow rate and the environmental temperature. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

  Next, radiation irradiation conditions will be described. A basic irradiation method is disclosed in JP-A-60-132767. Specifically, a light source is provided on both sides of the head unit, and the head and the light source are scanned by a 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 WO99 / 54415, as an irradiation method, a method using an optical fiber or a method in which a collimated light source is applied to a mirror surface provided on the side surface of the head unit to irradiate the recording unit with UV light is disclosed. In the present invention, these irradiation methods can be used.

  In the present invention, the ink composition is heated to a constant temperature, and the time from landing to irradiation is desirably 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, and more preferably Preferably, radiation is applied after 0.01 to 0.15 seconds. Thus, by controlling the time from landing to irradiation to an extremely short time, it is possible to prevent the landing ink from bleeding before being cured. Also, since the ink composition can be exposed to a porous recording medium before it penetrates deeper than the light source reaches, unreacted monomer remains, and as a result, odor can be reduced. Can do. By using the inkjet recording method described above and the ink composition of the present invention in combination, a great synergistic effect is brought about. In particular, when an ink composition having an ink viscosity of 35 to 500 MP · s at 25 ° C. is used, a great effect can be obtained. By adopting such a recording method, the dot diameter of the landed ink can be kept constant even on various recording media having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. When inks with low lightness are stacked, it is difficult for the irradiation line to reach the lower ink, and the curing sensitivity is hindered, the residual monomer is increased, odor is generated, and the adhesion is liable to occur. Irradiation can be performed by injecting all colors and exposing them together, but exposure for each color is preferable from the viewpoint of promoting curing.

  There is no restriction | limiting in particular as an inkjet recording device used for this invention, A commercially available inkjet recording device can be used. That is, in the present invention, recording can be performed on a recording medium using a commercially available inkjet recording apparatus.

(Recording medium)
The recording medium to which the ink composition of the present invention can be applied is not particularly limited, and various kinds of non-absorbing resin materials used for ordinary non-coated paper, coated paper, so-called soft packaging, or the like. A resin film formed into a film can be used, and examples of the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film. In addition, examples of the plastic that can be used as a recording medium material include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used as the recording medium.
The ink composition of the present invention has little heat shrinkage at the time of curing and excellent adhesion to the substrate (recording medium), so that the film curls and deforms due to the ink shrinkage and heat generation during the curing reaction. Films that tend to occur, such as PET film, OPS film, OPP film, ONy film, PVC film, and the like that can be shrunk by heat, have an advantage that a high-definition image can be formed.

[Lithographic printing plate]
A preferable application example of the ink composition of the present invention is use in a lithographic printing plate.
The ink composition of the present invention is ejected onto a hydrophilic support using an ink jet recording apparatus or the like, and then irradiated with radiation to cure the ink composition to form a hydrophobic region, thereby forming a hydrophilic support. An image-like hydrophobic ink-receiving region is formed on the body surface. Here, when the printing ink and the aqueous component are supplied, the aqueous component is held in the exposed region of the hydrophilic support, and the printing ink is held in the hydrophobic region, so that the printing process can be performed as it is. it can.
Since the ink composition of the present invention exhibits excellent curability upon irradiation with radiation, the lithographic printing plate of the present invention to which the ink composition is applied has an image portion with excellent printing durability. In addition, an inkjet recording apparatus can be used to form an image portion, and a high-definition lithographic printing plate image portion can be formed directly from digital data.
The ink composition of the present invention described above may be applied as it is to the ink composition used for preparing the lithographic printing plate.

[Support]
The support preferably used in preparing the lithographic printing plate of the present invention will be described.
The support used for the lithographic printing plate of the present invention is not particularly limited as long as it is a dimensionally stable plate-like support. If the material constituting the support has surface hydrophilicity, it may be used as it is, or the surface of the plate-like material constituting the support may be subjected to a hydrophilic treatment.
Examples of the material constituting the support include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), and plastic film (eg, diacetic acid). Cellulose, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film on which the above metals are laminated or deposited Etc. A preferable support includes a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic laminated on a thin film of aluminum or aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.

  Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it is easy to improve hydrophilicity and secure adhesion between the image recording layer and the support. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Also, a transfer method in which the uneven shape is transferred with a roll provided with unevenness in the aluminum rolling step may be used.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.

  The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions for anodizing treatment vary depending on the electrolyte used and cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are preferable. The amount of the anodized film formed is preferably from 1.0 to 5.0 g / m ^2, and more preferably 1.5 to 4.0 g / m ^2. Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

  As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but for further improvement in adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation and the like. If necessary, the surface of the anodized film described in JP-A-2001-253181 and JP-A-2001-322365 may be enlarged or sealed, and the surface may be immersed in an aqueous solution containing a hydrophilic compound. A hydrophilic treatment or the like can be appropriately selected and performed. Of course, these enlargement processing and sealing processing are not limited to those described above, and any conventionally known method can be performed.

[Sealing treatment]
Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Among these, a sealing treatment with an aqueous solution containing an inorganic fluorine compound, a sealing treatment with water vapor, and a sealing treatment with hot water are preferable.

[Hydrophilic treatment]
Examples of the hydrophilization treatment used in the present invention include US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There is an alkali metal silicate method as described in the book. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  The support applied to the lithographic printing plate of the present invention preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer (image part), good printing durability and good stain resistance can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in these examples.

[Example 1]
<< Preparation of pigment dispersion >>
According to the method described below, yellow, magenta, cyan and black pigment dispersions 1 were prepared. The dispersion conditions are adjusted appropriately using a known dispersion device so that the average particle diameter of each pigment particle is in the range of 0.2 to 0.3 μm, and then filtered under heating. Prepared by filtration.

(Yellow pigment dispersion 1)
・ C. I. Pigment Yellow 12 10 parts by mass, polymer dispersant (Solsperse series manufactured by Zeneca) 5 parts by mass, OXT-221 (oxetane compound: manufactured by Toagosei Co., Ltd.) 85 parts by mass

(Magenta pigment dispersion 1)
・ C. I. Pigment Red 57: 1 15 parts by mass / polymer dispersing agent (Solsperse series manufactured by Zeneca) 5 parts by mass / OXT-221 (oxetane compound: manufactured by Toagosei Co., Ltd.) 80 parts by mass

(Cyan pigment dispersion 1)
・ C. I. Pigment Blue 15: 3 20 parts by mass-polymer dispersant (Solsperse series manufactured by Zeneca) 5 parts by mass-OXT-221 (oxetane compound: manufactured by Toagosei Co., Ltd.) 75 parts by mass

(Black pigment dispersion 1)
・ C. I. Pigment Black 7 20 parts by mass, polymer dispersant (Solsperse series manufactured by Zeneca) 5 parts by mass, OXT-221 (oxetane compound: manufactured by Toagosei Co., Ltd.) 75 parts by mass

<Preparation of ink>
The following components were mixed and filtered through a filter to prepare each color ink.
(Yellow ink 1)
(A) a cationically polymerizable compound;
Celoxide 2021 35g
(Epoxy compound: Daicel UCB Co., Ltd.)
OXT-221 55g
(Oxetane compound: manufactured by Toa Gosei Co., Ltd.)
(B) a photoacid generator;
Compound Example (b-27) / (b-32) = 1/2 5 g
(C) a specific base component;
Specific Example (C-2) 0.03 g
(E) a colorant (the pigment dispersion);
Yellow pigment dispersion 1 5g

(Magenta ink 1)
(A) a cationically polymerizable compound;
Celoxide 2021 35g
(Epoxy compound: Daicel UCB Co., Ltd.)
OXT-221 55g
(Oxetane compound: manufactured by Toa Gosei Co., Ltd.)
(B) a photoacid generator;
Compound Example (b-3) 5g
(C) a specific base component;
Specific Example (C-11) 0.03 g
(D) an organic acidic component;
Phenoxyacetic acid 0.03g
(E) a colorant (the pigment dispersion);
Magenta pigment dispersion 1 5g

(Cyan ink 1)
(A) a cationically polymerizable compound;
Celoxide 2021 35g
(Epoxy compound: Daicel UCB Co., Ltd.)
OXT-221 55g
(Oxetane compound: manufactured by Toa Gosei Co., Ltd.)
(B) a photoacid generator;
Compound Example (b-75) 5g
(C) a specific base component;
Specific Example (C-14) 0.03 g
(D) an organic acidic component;
0.03g salicylic acid
(E) a colorant (the pigment dispersion);
Cyan pigment dispersion 1 5g

(Black ink 1)
(A) a cationically polymerizable compound;
Celoxide 2021 35g
(Epoxy compound: Daicel UCB Co., Ltd.)
OXT-221 55g
(Oxetane compound: manufactured by Toa Gosei Co., Ltd.)
(B) a photoacid generator;
Compound Example (b-10) 5g
(C) a specific base component;
Specific Example (C-17) 0.03 g
(D) an organic acidic component;
Cyclohexanecarboxylic acid 0.03g
(E) a colorant (the pigment dispersion);
Black pigment dispersion 1 5g
・ Sensitizer 9,10-dimethoxyanthracene 0.5g

<Inkjet image recording> (Evaluation of multicolor images)
Next, recording on a recording medium was performed using a commercially available inkjet recording apparatus having a piezoelectric inkjet nozzle. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzles of the ink jet head, respectively, and temperature control was performed so that the nozzle portions were always 70 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV-A light is condensed to an exposure surface illuminance of 100 mW / cm ² , and the exposure system, main scanning speed and ejection frequency are adjusted so that irradiation starts 0.1 seconds after ink landing on the recording medium. . Further, the exposure time was variable, and exposure energy was irradiated. In the present invention, dpi represents the number of dots per 2.54 cm.

Each color ink prepared above was ejected in the order of black → cyan → magenta → yellow at an ambient temperature of 25 ° C. and irradiated with ultraviolet rays for each color. In order to eliminate tackiness by palpation, the exposure was performed with a total exposure energy per color of 300 mJ / cm ² as the energy for complete curing. As the recording medium, each color image was recorded on a grained aluminum support, a transparent biaxially stretched polypropylene film having a printability, a soft vinyl chloride sheet, cast coated paper, and commercially available recycled paper. However, in both cases, a high-resolution image without dot bleeding was obtained. Furthermore, even on high-quality paper, the ink was sufficiently cured without causing the ink to turn around, and there was almost no odor due to unreacted monomers. Further, the ink recorded on the film had sufficient flexibility, and even when it was bent, the ink did not crack, and there was no problem in the adhesion test by cellophane tape peeling.

[Examples 2 to 6, Reference Examples 1 to 3 , Comparative Examples 1 and 2]
<Preparation of ink>
The following components were mixed and filtered through a filter to prepare ink compositions (magenta inks 2-1 to 2-8) of Examples 2 to 6 and Reference Examples 1 to 3 . Further, in the ink composition of Example 6, the ink composition of Comparative Example 1 (magenta ink 2-) was used in the same manner as in Example 6 except that it did not contain (c) the specific base component and (d) the organic acidic component. 9) was obtained. Further, in the ink composition of Example 6, compared in the same manner as in (c) instead of a specific base component in comparison base component (10), and the other containing no (d) is an organic acid component, Example 6 Example 2 ink composition (magenta ink 2-10) was obtained.

(Magenta ink 2-1 to 2-10)
(A) Cationic polymerizable compound (compound described in Table 1) 90 g
(B) Photoacid generator (compound described in Table 1) 5 g
・ (C) Specific base component (or comparative base component) 0.03 g
(The specific examples shown in Table 1, added as necessary)
・ (D) Organic acid component 0.03g
(Organic acidic components listed in Table 1, added as necessary)
(E) Colorant (magenta pigment dispersion 1) 5 g
・ Sensitizer (Sensitizer listed in Table 1, added as necessary) 0.5 g

The details of the (a) cationic polymerizable compound described in Table 1 are as follows.
Cationic polymerizable compound (1):
Celoxide 2021 (epoxy: manufactured by Daicel UCB Co., Ltd.) / OXT-221 (oxetane: manufactured by Toagosei Co., Ltd.) = 35/55 mixture Cationic polymerizable compound (2):
Celoxide 3000 (epoxy: manufactured by Daicel UCB) / OXT-211 (oxetane: manufactured by Toagosei Co., Ltd.) = 50/40 mixture Cationic polymerizable compound (3):
Bisphenol A-diglycidyl ether / OXT-221 (Oxetane: manufactured by Toagosei Co., Ltd.) = 40/50 mixture Cationic polymerizable compound (4):
Celoxide 2021 (epoxy: manufactured by Daicel UCB) / OXT-101 (oxetane: manufactured by Toagosei Co., Ltd.) = 55/35 mixture

The details of the organic acidic components listed in Table 1 are as follows.
Organic acidic component (5): Phenoxyacetic acid Organic acidic component (6): Cyclopentanecarboxylic acid Organic acidic component (7): Salicylic acid

The details of the sensitizer described in Table 1 are as follows.
Sensitizer (8): 9,10-dimethoxyanthracene Sensitizer (9): Pyrene

Details of the comparative base component described in Table 1 are as follows.
Comparative base component (10): Octylamine

  In the ink compositions prepared in the above examples and comparative examples, the ink viscosity at the ejection temperature is 7 to 20 mPa.s. It was within the range of s.

[Inkjet image recording] (single color image evaluation)
In the ink jet image recording method described in Example 1, the ink compositions of Examples 2 to 6, Reference Examples 1 to 3, and Comparative Examples 1 and 2 prepared as described above (magenta inks 2-1 to 2- A magenta image was printed in the same manner as in Example 1 except that only 10) was used.

[Evaluation of inkjet image]
Next, for each of the ink compositions of Examples and Comparative Examples (magenta inks 2-1 to 2-10), the sensitivity required for curing, storage stability, and penetration in commercially available recycled paper was determined according to the method described below. Evaluation of ink property, ink bleeding on a grained aluminum support, and adhesion to a grained aluminum support.

1. Measurement of Curing Sensitivity The amount of exposure energy (mJ / cm ² ) that eliminates stickiness on the image surface after UV irradiation was defined as curing sensitivity. The smaller the value, the higher the sensitivity.

2. Storage stability evaluation After the ink composition thus prepared was stored at 75% RH and 60 ° C. for 3 days, the ink viscosity at the injection temperature was measured, and the increase in the ink viscosity was determined as the viscosity ratio after storage / before storage. Expressed in If the viscosity does not change and is close to 1.0, the storage stability is good, and if it exceeds 1.5, clogging may occur at the time of injection, which is not preferable.

3. Permeability evaluation with respect to commercially available recycled paper For images printed on commercially available recycled paper, the permeability was evaluated according to the following criteria.
○: Almost no penetration and no residual monomer odor Δ: Slight penetration and slight residual monomer odor X: Clearly the ink penetrates the back side and the residual monomer odor is strong

4). Evaluation of Ink Bleeding on Grained Aluminum Support An image printed on a grained aluminum support was evaluated for ink bleeding according to the following criteria.
○: No blur between adjacent dots Δ: Slightly blur dots ×: Dot blurs and the image is clearly blurred

5). Evaluation of Adhesiveness on Grained Aluminum Support The printed image created above is 11 samples vertically and horizontally at 1 mm intervals on the printed surface according to JIS K 5400 and a sample that does not scratch the printed surface at all. Make 100 samples of 1 mm square grids, paste cellophane tape on each printing surface, quickly peel off at a 90 degree angle, and print images remaining without peeling or grids The situation was evaluated according to the following criteria.
○: No peeling of the printed image was observed even in the cross cut test. Δ: Some ink peeling was observed in the cross cut test, but almost no peeling was observed unless the ink surface was scratched. Easy to peel off with cellophane tape

[Evaluation as a planographic printing plate]
On the grained aluminum support produced as described above, images were formed by printing with the ink compositions (magenta inks 2-1 to 2-10) of Examples and Comparative Examples. Using this as a lithographic printing plate, the image and printing durability were evaluated.

a. Evaluation of Image A lithographic printing plate produced using the ink compositions of Examples and Comparative Examples was applied to a Heidel KOR-D machine, and ink [VALUES-G Beni for Sheetfed (Dainippon Ink Co., Ltd.)] and A dampening solution [Ecolity 2 (manufactured by Fuji Photo Film Co., Ltd.)] was supplied for printing. The printed matter after printing 100 sheets was visually evaluated according to the following criteria.
◯: An image free from white spots in the image area and unstained non-image area was obtained.
Δ: Slight white spots in the image area and / or slight stains were observed in the non-image area.
X: White spots in the image area and / or stains in the non-image area were observed, and there was a problem in practical use.

b. Evaluation of printing durability Printing was continued as it was, and a relative comparison was made by using the number of printed sheets as a printing durability index (Comparative Example 1 was set to 100). A larger numerical value is preferable because it provides higher printing durability.
These evaluation results are shown in Table 1.

From Table 1, the ink composition of each example is cured with high sensitivity to radiation irradiation, can form a high-quality image in terms of image formation on paper, and has good storage stability. there were. Thus, in the present invention, it can be seen that both curing sensitivity, suppression of bleeding on a non-permeable support and storage stability of ink have been achieved.
On the other hand, the ink composition of Comparative Example 1 that does not contain the specific base component (c) has a problem in storage stability, and the permeability to recycled paper, the bleeding on the aluminum support, and the curing sensitivity are slightly higher. I found it inferior. In addition, the ink composition of Comparative Example 2 containing (c) the comparative base component (10) instead of the specific base component: octylamine is inferior in storage stability, has low curing sensitivity, and is also recycled paper. It was found to be slightly inferior to the permeability to aluminum and the bleeding on the aluminum support.
Further, it was found that the lithographic printing plate on which an image was formed with the ink composition of the present invention can form a high quality image and has good printing durability.

Claims (9)

(A) a cationically polymerizable compound, (b) a compound that generates an acid upon irradiation with radiation, and (c) two basic nitrogen atoms in which atoms are bonded via a linking group having 2 or 3 carbon atoms. at least have a ink the basic nitrogen atom and hydrogen ions and polyfunctional amine compounds can coordinate, and (d) pKa, characterized in that it contains an organic acidic component showing a value of 2-6 composition object.   The ink composition according to claim 1, wherein the polyfunctional amine compound (c) is at least one compound selected from the following compounds (C-1) to (C-27).

The ink composition according to claim 1 or 2, further comprising (e) a colorant. 4. The ink composition according to claim 3 , wherein the colorant (e) is a pigment or an oil-soluble dye. The ink composition according to any one of claims 1 to 4 , wherein the ink composition is for inkjet recording. A step of ejecting the ink composition according to any one of claims 1 to 5 onto a recording medium by an ink jet printer, and a step of curing the ejected ink composition by irradiation with radiation. An ink jet recording method. A printed matter obtained by ejecting the ink composition according to any one of claims 1 to 5 on a recording medium with an ink jet printer and then irradiating the ink composition to cure the ink composition. A hydrophobic region is formed by ejecting the ink composition according to any one of claims 1 to 5 onto a hydrophilic support and then irradiating the ink composition to cure the ink composition. A method for producing a lithographic printing plate characterized by the above. A hydrophobic region formed by ejecting the ink composition according to any one of claims 1 to 5 on a hydrophilic support and then irradiating the ink composition to cure the ink composition. A lithographic printing plate with.