JP2017179006A - Active energy ray-curable inkjet ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable inkjet ink composition exhibiting stable discharge property, good in adhesion to a substrate and further excellent in high speed curability and a printed matter using the same.SOLUTION: There is provided an active energy ray curable inkjet ink composition containing (A) a hydroxyl group-containing polymerizable compound and acrylic acid 2-(2-vinyloxy ethoxy)ethyl, the hydroxyl group-containing polymerizable compound is specific ether ester having radical polymerizable acrylic unsaturated groups on both terminals and a hydroxyl group in a side chain and viscosity at 25°C is 50 to 3000 Pa S.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable inkjet ink composition that exhibits stable ejection characteristics, has good adhesion to a substrate, and is excellent in high-speed curability, and a printed matter using the same.

  In recent years, active energy ray-curable ink-jet inks that are cured by ultraviolet rays, electron beams, and other radiation have been reduced in cost by simplifying the drying process, reduced volatilization of solvents as an environmental measure, and shortened delivery time by supporting on-demand printing Since it has many merits, the amount of use is increasing.

  Such an active energy ray-curable ink-jet ink has ejection properties, weather resistance, scratch resistance, solvent resistance, flexibility, safety, odor resistance during printing, odor resistance of printed matter, and fixing to printed matter. Various performances such as high performance and low running cost are required. Among them, high-speed curability is one of the performances required for printing with high accuracy and high-speed productivity.

  In order to improve the curing speed, a method is known in which a polymerizable compound having a hydroxyl group exhibiting high-speed curability is used in combination with an ink-jet ink composition, and 2- (2-vinyloxyethoxy) ethyl acrylate and a hydroxyl group are combined. An ink-jet ink composition using a polymerizable compound in combination is disclosed (Patent Document 1).

  However, since the combined amount of the polymerizable compound having a hydroxyl group is a small amount of 10 parts by weight or less in the ink-jet ink composition, there is a problem that the degree of improvement in the curing rate is small.

  Moreover, as a polymerizable compound having a hydroxyl group exhibiting high-speed curability, an epoxy (meth) acrylate compound in which (meth) acrylic acid is reacted with an epoxy compound represented by bisphenol A type diglycidyl ether is known. Inkjet ink composition in which an epoxy (meth) acrylate compound is used in an inkjet ink composition in an amount of 30 to 70 parts by weight and diluted with tripropylene glycol diacrylate, which is a low-viscosity monomer having a viscosity of 10 mPa · s at 25 ° C. The thing is disclosed (patent document 2).

  However, many epoxy (meth) acrylate compounds have a viscosity of more than 3000 mPa · s at 25 ° C. When tripropylene glycol diacrylate is used as a dilution monomer, the viscosity of the ink-jet ink composition is high. There is a problem that it does not fall within the viscosity range for maintaining the discharge stability of the ink.

  Furthermore, a polymerizable compound having a hydroxyl group synthesized from natural materials such as tartaric acid and malic acid is disclosed as a polymerizable compound that exhibits high-speed curability similar to an epoxy (meth) acrylate compound and has a low viscosity. However, there is no description of application to an active energy ray-curable inkjet ink (Patent Document 3).

JP 2004-067991 A JP2011-195724 JP, 2006-030764, A

  The present invention provides an active energy ray-curable inkjet ink composition that exhibits stable ejection characteristics in inkjet printing, has good adhesion to a substrate, and is excellent in high-speed curability, and a printed matter using the same. For the purpose.

As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention is an active energy ray-curable inkjet ink composition comprising a hydroxyl group-containing polymerizable compound (A) and a polymerizable compound (B) other than the hydroxyl group-containing polymerizable compound (A),
The hydroxyl group-containing polymerizable compound (A) is represented by the following general formula (1) or the following general formula (2),
And the viscosity in 25 degreeC is the range of 50-3000 mPa * s,
And a compound having two or more polymerizable groups,
The polymerizable compound (B) relates to an active energy ray-curable inkjet ink composition, characterized in that it comprises 2- (2-vinyloxyethoxy) ethyl acrylate.

General formula (1)

(In formula, R < ¹ > and R < ² > represents a hydrogen atom or a methyl group each independently.
X represents a divalent linking group. )

General formula (2)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group.
Y represents a divalent linking group. )

  The content of the hydroxyl group-containing polymerizable compound (A) is in the range of 30 to 75 parts by weight with respect to 100 parts by weight of the total amount of the hydroxyl group-containing polymerizable compound (A) and the polymerizable compound (B). The present invention relates to an active energy ray-curable inkjet ink composition according to claim 1.

  Furthermore, it is related with the said active energy ray hardening-type inkjet ink composition characterized by including a photoinitiator.

  Furthermore, it is related with the said active energy ray hardening-type inkjet ink composition characterized by including a coloring component.

  The present invention relates to a printed material using the active energy ray-curable inkjet ink composition.

  According to the present invention, an active energy ray-curable inkjet ink composition having stable ejection characteristics in inkjet printing, exhibiting excellent adhesion to a substrate, and excellent in high-speed curability, and the same are used. We were able to provide printed materials.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, the hydroxyl group-containing polymerizable compound (A) used in the active energy ray-curable inkjet ink composition of the present invention will be described.

  The hydroxyl group-containing polymerizable compound (A) is represented by the following general formula (1) or (2), and has two hydroxyl groups, and further has a bifunctional (meth) group having a polymerizable functional group. It is characterized by being an acrylate compound.

General formula (1)

(In formula, R < ¹ > and R < ² > represents a hydrogen atom or a methyl group each independently.
X represents a divalent linking group. )

General formula (2)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group.
Y represents a divalent linking group. )

R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) each independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

  X in the general formula (1) and Y in the general formula (2) are divalent linking groups.

  The divalent linking group is a structure composed of an arbitrary atom or atomic group, and shows a state capable of bonding to the other two different atoms. The two bonded states may be formed from one atom or may be formed from different atoms one by one.

  The divalent linking group is preferably an organic compound, more preferably a hydrocarbon (which may contain an oxygen atom, a nitrogen atom, or a sulfur atom in the structure), a raw material acquisition surface, a synthesis surface, and a performance surface. Desirable from.

  More specifically, examples of the divalent linking group include, but are not limited to, an alkylene group, an alkylene group containing an oxygen atom, and a divalent heterocyclic group.

  An alkylene group is a divalent group formed by removing any two hydrogen atoms of a substituted or unsubstituted, straight, branched, branched, monocyclic or condensed polycyclic alkane having 1 to 20 carbon atoms. It is a group.

  As the alkylene group, a linear hydrocarbon group having 1 to 10 carbon atoms is preferable, and a linear hydrocarbon group having 1 to 6 carbon atoms is more preferable. Specific examples include the structures exemplified below, but are not limited thereto.

Specific examples of the alkylene group containing an oxygen _{atom, - (CH 2 CH 2 O} ) n -CH 2 CH 2 -, - [CH (CH 3) CH 2 O] n -CH (CH 3) CH 2 -, _{- (C 3 H 6 O)} n -C 3 H 6 -, - [(C = O) -C 5 H 10 O] n - (C = O) -C 5 H 10 -, - [(C = O _{) -C 4 H 8 O] n} - (C = O) -C 4 H 8 -, or, - [(C = O) -C 3 H 6 O] n - (C = O) -C 3 H 6 -, But is not limited thereto. Here, n is an integer of 1 to 10, preferably n is an integer of 1 to 5, and more preferably n is an integer of 1 to 3.

  As the divalent heterocyclic group, any two hydrogen atoms are removed from an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples of the divalent group include, but are not limited to, the structures exemplified below.

  Specific examples of the hydroxyl group-containing polymerizable compound (A) of the present invention described above are shown below, but the structure of the hydroxyl group-containing polymerizable compound (A) of the present invention is not limited thereto.

Table 1

  The hydroxyl group-containing polymerizable compound (A) used in the ink-jet ink composition of the present invention has a viscosity in the range of 50 to 3000 mPa · s at 25 ° C., and has bifunctional hydroxyl groups and bifunctional polymerizable groups. Is a compound. By having this basic structure, it exhibits high-speed curability and is excellent in adhesion to the substrate.

  These can be used singly or in combination, and can be arbitrarily mixed and used depending on the properties required for the cured product. The amount of the hydroxyl group-containing polymerizable compound (A) used is 100 in total of the hydroxyl group-containing polymerizable compound (A) and the polymerizable compound (B) in the ink-jet ink composition containing the polymerizable compound (B) described later. It is preferable to contain in 30-75 weight part with respect to a weight part, and it is more preferable to contain in 40-60 weight part.

  When the amount of the hydroxyl group-containing polymerizable compound (A) used is less than 30 parts by weight, the effect of high-speed curing unique to the hydroxyl group-containing polymerizable compound is not sufficiently exhibited, and a desired curing rate cannot be obtained.

  On the other hand, when the usage-amount of a hydroxyl-containing polymeric compound (A) exceeds 75 weight part, the viscosity of an inkjet ink composition may become high and may not be settled in the viscosity area | region which shows the stable discharge characteristic.

  The reason why the hydroxyl group-containing polymerizable compound (A) of the present invention is preferable is that the reaction for obtaining the hydroxyl group-containing polymerizable compound (A) is easy.

  The hydroxyl group-containing polymerizable compound (A) of the present invention represented by the general formula (1) is an easily synthesized or available diglycidyl ether type epoxy compound or a derivative thereof. And can be synthesized by addition reaction of (meth) acrylic acid.

  As a catalyst used in the addition reaction of (meth) acrylic acid, for example, an organic base such as triethylamine or dibutylamine can be used. JP-A-59-70642 shows that quaternary ammonium salts have a catalytic effect.

  Quaternary ammonium salts and quaternary phosphonium salts are suitable for this reaction in terms of both activity and selectivity in the addition reaction of the epoxy compound used in this reaction with (meth) acrylic acid. Examples of the quaternary ammonium salt include tetrabutylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium bromide, and benzyltriethylammonium bromide. Examples of the quaternary phosphonium salt include tributylmethylphosphonium iodide, tributyloctylphosphonium bromide, And tributylhexadecylphosphonium bromide.

  The amount of the onium salt used is preferably 0.3 mol% or more and 30 mol% or less based on the epoxy compound formation. More preferably, it is 1 mol% or more and 10 mol% or less. If it is less than 0.3 mol, the reaction rate is too slow and it takes too much reaction time. If it exceeds 30 mol%, the purity of the product becomes low, which is not preferable.

  Examples of the solvent used in the addition reaction with (meth) acrylic acid for the epoxy compound include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as toluene, xylene, and chlorobenzene, tetrahydrofuran, 1 Various solvents such as ether solvents such as 1,4-dioxane are used.

  The (meth) acrylic acid used for the addition reaction with acrylic acid to the epoxy compound is preferably 1 to 5 times the molar amount of the glycidiel ether of the epoxy compound. More preferably, it is 1.2 mol times or more and 2 mol times or less. If it is less than 1 mol times, an unreacted diglycidyl ether compound remains, and if it exceeds 5 mol times, a by-product tends to be generated, which is not preferable.

  The reaction temperature is preferably between 50 ° C and 150 ° C. More preferably, it is in the range of 70 ° C to 120 ° C. If it is less than 50 ° C., it takes too much reaction time, and if it exceeds 150 ° C., polymerization of (meth) acrylic acid proceeds, which is not preferable.

  As commercially available products that are epoxy (meth) acrylate compounds corresponding to the hydroxyl group-containing polymerizable compound (A) of the present invention represented by the general formula (1), DENACOL ACRYLATE DA-212, DA-911M DA-920, DM-811, DM-832, DM-851 (all manufactured by Nagase ChemteX Corporation) and the like, but are not limited thereto.

  The hydroxyl group-containing polymerizable compound (A) of the present invention represented by the general formula (2) is an easily synthesized or available acrylate having a halogen with a base for various dicarboxylic acids or derivatives thereof. It can be easily obtained by a synthesis method by a nucleophilic substitution reaction or a synthesis method by a condensation reaction with an acrylate having a hydroxyl group using an acid catalyst or a dehydrating condensing agent (described in JP-A-2006-030764). It can be obtained by using a general organic synthesis reaction such as a reaction using a base and an alkyl halide.

  The photopolymerization initiator of the present invention will be described. The photopolymerization initiator of the present invention is a compound that generates radicals which are active species by irradiation with active energy rays such as ultraviolet rays, and the generated radicals quickly start radical polymerization reaction and cure. can do.

As the photopolymerization initiator of the present invention, a conventionally known photopolymerization initiator can be used. Specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butane, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) ) Acetophenones such as benzyl] phenyl} -2-methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other examples include phenylglyoxylic methyl ester.

  More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 (manufactured by BASF), Adekaoptomer N1414, Adekaoptomer N1717, EsacureONE (manufactured by Lamberti) ), Esacure 1001M (manufactured by Lamberti), JP-B-59-1281, JP-B-61-9621, and Triazine derivatives described in JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413 Japanese Patent Publication No. 47-1604 and diazonium compound publications described in USP 3,567,453, USP 2,848,328, USP 2,852,379 and USP 2,940,853, an organic azide compound, Ortho-quinonediazides described in Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 55-39162, Japanese Patent Publication No. 59-140203. And “Macro Molecules (MACRO OLECULES), Vol. 10, page 1307 (1977) and various onium compounds including azo compounds described in JP-A-59-142205, JP-A-1-54440, European patent No. 1099851, European Patent No. 126712, “Journal of Imaging Science (J. IMAGE. SCI.)”, Volume 30, page 174 (1986), The titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and ruthenium described in JP-A-2-182701. Transition metals such as Transition metal complexes, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, JP-A-55-127550 and JP-A-60-202437 2,4,5-triarylimidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, Aminoketone compounds described in JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261761, and JP-A-2000-80068. JP 2001-233842 A, JP 2004-534797 A JP, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP 2010-15025, JP 2010-189279, JP 2010-189280, JP 2010-526846, JP 2010-527338. And oxime ester compounds described in JP 2010-527339, USP 3558309 (1971), USP4202697 (1980) and JP-A-61-255858.

  Among these, acetophenones represented by amino ketones, phosphines, and oxime ester compounds are preferably used.

  These can be used singly or in combination of two or more, and can be mixed and used arbitrarily depending on the properties required for the cured product. The amount used when using these photopolymerization initiators is hydroxyl group-containing. It contains in the range of 0.01-200 weight part with respect to 100 weight part of total amounts of the below-mentioned polymerizable compound (B) which can be used together with polymeric compound (A), and contains in the range of 0.1-100 weight part Preferably it is done.

  When the usage-amount of a photoinitiator is less than 0.01 weight part, the quantity of the radical which is an active seed | species generate | occur | produced by active energy ray irradiation is not enough, and a desired cure rate cannot be obtained. On the other hand, when the usage-amount of a photoinitiator exceeds 200 weight part, since there are too many low molecular components in an inkjet ink composition, the characteristic of the hardened | cured material after a polymerization reaction may become inadequate.

  The polymerizable compound (B) in the present invention is a compound that has at least one skeleton capable of radical polymerization in the molecule and is not included in the hydroxyl group-containing polymerizable compound (A). In addition, these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and normal pressure.

  Examples of such a polymerizable compound (B) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides and acid anhydrides. Furthermore, urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and other acrylates, methacrylates, arylates, acid amides, styrenes Other vinyl compounds, radical polymerizable cyclic compounds, oligomers, prepolymers, and the like can be mentioned, but the present invention is not limited to these. Below, the specific example of the polymeric compound (B) in this invention is given.

  Among the polymerizable compounds (B), examples of the acrylates include the following compounds.

Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, acrylic acid-2-hydroxy- 3-allyloxypropyl, 2-acryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, acrylic Acrylic acid 2- (vinyloxy) ethyl, p- nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecandi Methylol diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

Examples of vinyl ether group-containing acrylic esters:
2-vinyloxyethyl acrylate, 3-vinyloxypropyl acrylate, 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl acrylate, 4-vinyloxybutyl acrylate, 1-methyl acrylate 3-vinyloxypropyl, 1-vinyloxymethylpropyl acrylate, 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl acrylate, 1,1-dimethyl acrylate 2-vinyloxyethyl, 3-vinyloxybutyl acrylate, 1-methyl-2-vinyloxypropyl acrylate, 2-vinyloxybutyl acrylate, 4-vinyloxycyclohexyl acrylate, 5-vinyloxypentyl acrylate, Acrylic acid-6-vinyloxyhexyl, acrylic acid -Vinyloxymethylcyclohexylmethyl, acrylic acid-3-vinyloxymethylcyclohexylmethyl, acrylic acid-2-vinyloxymethylcyclohexylmethyl, acrylic acid-p-vinyloxymethylphenylmethyl, acrylic acid-m-vinyloxymethylphenylmethyl , Acrylic acid-o-vinyloxymethylphenylmethyl, acrylic acid-2- (vinyloxyisopropoxy) ethyl, acrylic acid-2- (vinyloxyethoxy) propyl, acrylic acid-2- (vinyloxyethoxy) isopropyl, acrylic Acid-2- (vinyloxyisopropoxy) propyl, acrylate-2- (vinyloxyisopropoxy) isopropyl, acrylate-2- (vinyloxyethoxyethoxy) ethyl, acrylate-2- (vinyloxyethoxyisopropoxy) D Le, acrylic acid 2- (vinyloxy-isopropoxyphenyl) ethyl, acrylate 2- (vinyloxy-isopropoxy-isopropoxyphenyl) ethyl.

Examples of trifunctional acrylates:
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, isocyanuric acid EO-modified ε-caprolactone-modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

  Among the polymerizable compounds (B), the following compounds can be exemplified as methacrylates.

Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, Jill polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate and the like.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol Nord A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO Modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane.

Examples of vinyl ether group-containing methacrylates:
2-vinyloxyethyl methacrylate, 3-vinyloxypropyl methacrylate, 1-methyl-2-vinyloxyethyl methacrylate, 2-vinyloxymethacrylate, 4-vinyloxybutyl methacrylate, methacryl Acid-1-methyl-3-vinyloxypropyl, methacrylic acid-1-vinyloxymethylpropyl, methacrylic acid-2-methyl-3-vinyloxypropyl, methacrylic acid-3-methyl-3-vinyloxypropyl , Methacrylic acid-1,1-dimethyl-2-vinyloxyethyl, methacrylic acid-3-vinyloxybutyl, methacrylic acid-1-methyl-2-vinyloxypropyl, methacrylic acid-2-vinyloxybutyl, methacrylic acid-4 -Vinyloxycyclohexyl, methacrylic acid-5-vinyloxy Pentyl, methacrylic acid-6-vinyloxyhexyl, methacrylic acid-4-vinyloxymethylcyclohexylmethyl, methacrylic acid-3-vinyloxymethylcyclohexylmethyl, methacrylic acid-2-vinyloxymethylcyclohexylmethyl, methacrylic Acid-p-vinyloxymethylphenylmethyl, methacrylic acid-m-vinyloxymethylphenylmethyl, methacrylic acid-o-vinyloxymethylphenylmethyl, methacrylic acid-2- (vinyloxyethoxy) ethyl, methacrylic acid -2- (vinyloxyisopropoxy) ethyl, methacrylic acid-2- (vinyloxyethoxy) propyl, methacrylic acid-2- (vinyloxyethoxy) isopropyl, methacrylic acid-2- (vinyloxyisopropoxy) propyl , Methacrylic -2- (vinyloxyisopropoxy) isopropyl, methacrylic acid-2- (vinyloxyethoxyethoxy) ethyl, methacrylic acid-2- (vinyloxyethoxyisopropoxy) ethyl, methacrylic acid-2- (vinyloxyiso) Propoxyethoxy) ethyl, methacrylic acid-2- (vinyloxyisopropoxyisopropoxy) ethyl.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

  Among the polymerizable compounds (B), examples of the arylate include the following compounds.

  Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

  Among the polymerizable compounds (B), examples of the acid amides include the following compounds.

  Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

  Among the polymerizable compounds (B), examples of the styrenes include the following compounds.

  Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

  Among the polymerizable compounds (B), examples of other vinyl compounds include the following compounds.

  Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, and the like.

  Among the polymerizable compounds (B), examples of the monofunctional N-vinyl compounds include the following compounds.

  N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide.

  Said polymeric compound (B) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., “Nakamura Chemical Co., Ltd.” "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. “Kayarad” and “Kayamar” series manufactured by Nippon Kayaku Co., Ltd. “Acrylic acid / methacrylic acid ester monomer” series manufactured by Nippon Shokubai Co., Ltd., Japan "NICHIGO-UV purple urethane acrylate oligomer" series manufactured by Seikagaku Corporation, "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd., "functional monomer" manufactured by Kojin Co., Ltd. "Series and the like.

  Moreover, radically polymerizable cyclic compounds such as the following three-membered cyclic compounds of vinylcyclopropanes and vinyloxiranes and cyclic ketene acetals are also exemplified as the polymerizable compound (B).

  Examples of the three-membered ring compounds include those described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 17, page 3169 (1979). Vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes described in Macromolecular Chem. Rapid Commun., Vol. 5, p. 63 (1984), Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition ( (Polym.Sci.Polym.Lett.Ed.), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 ( (1985) 2,3-divinyloxiranes.

  Examples of cyclic ketene acetals include, for example, Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 20, p. 3021 (1982) and Journal. 2-Methylene-1,3-dioxepane described in of Polymer Science Letter Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 21, p. 373 (1983). Dioxolanes described in Prepreprints, Vol. 34, page 152 (1985), Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.) , Volume 20 361 (1982), Macromolecular Chem., 183, 1913 (1982) and Macromolecular. Chem., 186, 1543 (1985). 2,7-Dimethyl-2-methylene-1,3- described in 2-methylene-4-phenyl-1,3-dioxepane, described in Macromolecules, Vol. 15, page 1711 (1982). Dioxepane, 5,6-benzo-2-methylene-1,3-diocepan described in Polymer Preprints, Vol. 34, 154 (1985).

  Furthermore, the polymeric compound (B) can also mention the thing as described in the literature shown below. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  As the polymerizable compound (B) of the present invention, in addition to the above monomers, those called oligomers and prepolymers can be used. Specifically, Daicel UCB's “Ebecry” series, “KRM” series, “KRM” series, “IRR” series, “RDX” series, Sartomer's “CN” series, BASF's “Laromer” series, Examples include the “Photomer” series manufactured by Cognis, the “Art Resin” series manufactured by Negami Kogyo, the “Shikko” series manufactured by Nippon Gohsei, and the “Kayarad” series manufactured by Nippon Kayaku.

  As the polymerizable compound (B) of the present invention, only one kind may be used, or a mixture of two or more kinds in any ratio may be used in order to improve desired characteristics.

  In addition, the ink-jet ink composition of the present invention has sufficient sensitivity without using a sensitizer, but in order to further improve sensitivity and improve film properties after curing, a sensitizer may be used in combination. Is possible.

Sensitizers that can be used in combination with the ink-jet ink composition of the present invention include benzophenone derivatives, unsaturated ketone derivatives typified by chalcone derivatives and dibenzalacetone, and typified by benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine Derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squary Derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphy Razine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, Organic ruthenium complexes and the like are listed, and other specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (198 And the dyes and sensitizers described in “Special Functional Materials” (1986, CMC), but are not limited to these. Examples thereof include dyes and sensitizers that absorb light in the infrared region, and two or more of these may be used in any ratio as necessary.
Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxy. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'- Examples include bis (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). However, it is not limited to these.

  The amount of the sensitizer used in the present invention is preferably in the range of 0.01 to 100 parts by weight and more preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  Moreover, the inkjet ink composition of this invention can add a polymerization inhibitor in order to prevent the superposition | polymerization at the time of a preservation | save.

  Specific examples of the polymerization inhibitor that can be added to the inkjet ink composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The agent is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  A surface conditioner can be added to the inkjet ink composition of the present invention for the purpose of improving the adhesion to the substrate. Specific examples of the surface conditioner include BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, and 375 manufactured by BYK-Chemie. 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570, “Tegorad-2100, 2200, 2250, 2500, 2700” manufactured by Tego Chemie. These surface conditioners may be used alone or in combination of two or more as required.

  The surface conditioner that may be used in combination in the present invention is used in the inkjet ink composition in the range of 0 to 5.0% by weight.

  The ink-jet ink composition of the present invention further comprises dyes, organic and inorganic pigments, pigment dispersants, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, and antihalation. Agent, optical brightener, surfactant, colorant, extender, plasticizer, flame retardant, antioxidant, dye precursor, ultraviolet absorber, foaming agent, antifungal agent, antistatic agent, magnetic substance, resin Dispersants such as type dispersants Storage stabilizers such as silane coupling agents and quaternary ammonium chlorides, plasticizers, surface tension modifiers, slipping agents, antiblocking agents, light stabilizers, leveling agents, antifoaming agents, It may be used by mixing with infrared absorbers, surfactants, thixotropic agents, antibacterial agents, fine particles such as silica, other additives imparting various properties, diluent solvents and the like.

  The ink-jet ink composition of the present invention can be polymerized by application of heat or energy by an active energy ray such as ultraviolet ray, visible ray, near infrared ray, electron beam, etc., during the polymerization reaction to obtain a desired polymer. However, as a light source for applying energy, irradiation of active energy rays with a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Xenon lamp, deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor-excited solid laser, 365 nm, 375 nm, 385 nm Various light sources such as an LED lamp light source having In this specification, the definition of active energy rays such as ultraviolet rays, visible light, and near infrared rays is based on “Iwanami Physical and Chemical Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the ink-jet ink composition of the present invention can be printed or applied on various substrates, and the substrate on which the ink-jet ink composition of the present invention is printed or applied can be glass, plastic, metal and paper. It can be suitably selected from the group consisting of. Furthermore, a composite substrate composed of a plurality of substrates can also be selected. These substrates may have a flat shape such as a plate, film, or paper, or may have a three-dimensional shape. The plastic film is preferably transparent.

  Examples of the plastic substrate include transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and polyacrylic polymers. Examples of the polyester polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulose polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the polyacrylic polymer include polymethyl methacrylate.

Examples of the plastic substrate include transparent polymers such as polystyrene-based polymers, polyolefin-based polymers, polyvinyl chloride-based polymers, and polyamide-based polymers.
Examples of the polystyrene-based polymer include polystyrene, acrylonitrile / styrene copolymer polymer, and the like. Examples of the polyolefin-based polymer include polyethylene, polypropylene, a polyolefin polymer having a cyclic or norbornene structure, and an ethylene / propylene copolymer polymer. Examples of the polyamide polymer include nylon and aromatic polyamide polymer.

  In addition, polyimide polymer, polysulfone polymer, polyethersulfone polymer, polyether ketone polymer, polyphenyl sulfide polymer, polyvinyl alcohol polymer, polyvinylidene chloride polymer, polyvinyl butyral polymer, polyarylate polymer, poly Examples thereof also include transparent polymers such as oxymethylene polymers, polyepoxy polymers, and blends of the above polymers. In particular, those having a small birefringence are preferably used.

  A coloring component can be added to the ink-jet ink composition of the present invention. A conventionally known pigment can be used as the coloring component. Further, for the purpose of obtaining a desired hue, a dye may be contained within a range in which heat resistance and weather resistance are not lowered. These may be used alone or in combination of two or more in order to obtain a desired color density and hue.

  As the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (for example, acetylene black, channel black, furnace black, etc.) can be used, and two or more kinds of pigments can be mixed and used.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments (eg, azo, disazo, polyazo, etc.), phthalocyanine pigments (eg, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.), anthraquinone type Pigment (for example, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, violanthrone, etc.), quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, cadmium red, Bengara, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen, cobalt Examples include blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

  Examples of the carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” manufactured by Degussa, Inc., “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, 45. , 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ”,“ REGAL 400R, 660R, 330R, 250R ”,“ MOGUL E, L ”, manufactured by Mitsubishi Chemical Corporation,“ MA7, 8, 11, 77, 100, 100R, 100S, 220, 230 "" # 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.

  In the following, pigments that can be used in the ink-jet ink composition of the present invention are indicated by color index (CI) numbers.

  Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 19, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, H.264, 272, etc. can be used, but the present invention is not limited to these.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , But the invention is not limited to the like can be used 177,179,180,181,182,185,187,188,193,194,199.

  Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61 and the like can be used, but are not limited thereto.

  Examples of the green pigment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used, but are not limited thereto.

  Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used, but are not limited thereto.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used, but are not limited thereto.

  Examples of the black pigment include C.I. I. Pigment Violet 1, 6, 7, 12, 20, 31 etc. can be used, but it is not limited to these.

  These pigments can be used by mixing two or more kinds at an arbitrary ratio.

  The amount used in the case of adding the pigment as the coloring component is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the polymerizable compound (B).

  The particle diameter of the pigment is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriate spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. The primary particle diameter refers to the diameter of the smallest unit pigment particle, and is measured with an electron microscope.

  The primary particle diameter of the pigment can be controlled within an appropriate range using a known dispersing device such as a sand mill, a kneader, or a two roll.

  Moreover, when adding a pigment to the inkjet ink composition of this invention, a pigment derivative and a pigment dispersant can be used in order to improve the dispersibility of a pigment and the storage stability of an inkjet ink composition.

  Here, the pigment derivative is a compound in which a substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes.

  Examples of pigment derivatives include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-06-06. What is described in 306301 gazette, Unexamined-Japanese-Patent No. 2001-220520, Unexamined-Japanese-Patent No. 2003-238842 etc. can be used, These can be used individually or in mixture of 2 or more types.

  Examples of the pigment 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 salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate, etc. can be used.

  Specific examples of the pigment dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" manufactured by BYK Chemie, "Disperbyk-101 ( (Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( Polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Saturated acid polycarboxylic acid and silicon system "," Lactimon (long chain amine and unsaturated acid poly) Recarboxylic acid and silicon) ”.

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine), "Efka PX4701," Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane) Oligomer), “Flownon SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersant) manufactured by Enomoto Kasei Co., Ltd. ), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether) Ester type) "and the like.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonyl phenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, manufactured by Lubrizol “Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 35000, 39000, 41000, 53000”, “Nikkor T 106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., etc. It is done.

  The addition amount of the pigment derivative and the pigment dispersant is not particularly limited, but is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment. is there.

  Examples of the dye that may be contained to obtain a desired hue include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. It is done.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include, but are not limited to, Mordant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Examples include, but are not limited to, Disperse Blue 60.

  Other examples of the phthalocyanine dye include C.I. I. Examples of quinoneimine dyes such as Pad Blue 5 include C.I. I. Basic Blue 3, C.I. I. Examples of quinoline dyes such as Basic Blue 9 include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include, but are not limited to, Disperse Yellow 42.

  The amount used in the case of adding these dyes is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the polymerizable compound (B). From the viewpoint of heat resistance and weather resistance, it is not preferable that the amount used is excessive.

  In addition, an organic solvent may be included in the ink-jet ink composition in order to reduce the viscosity of the ink-jet ink composition and improve the wettability of the ink-jet ink composition.

  Organic solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, diethyl diglycol, diethylene glycol dialkyl ether, tetraethylene glycol dialkyl Ether, diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol Monoethyl ether butyrate, ethylene glycol monobutyl ether butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate, dipropylene glycol monomethyl ether Glycol monoacetates such as tyrate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propionate butyrate, ethylene Glycol dipropionate, ethylene glycol acetate dibutyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol acetate dibutyrate, propylene glycol acetate propionate, propylene glycol 1 Cetate butyrate, propylene glycol propionate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, dipropylene glycol propionate butyrate, di Glycol diacetates such as propylene glycol dipropionate and dipropylene glycol acetate dibutyrate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol monobutyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Examples thereof include glycol ethers such as monobutyl ether and tripropylene glycol monomethyl ether, and lactic acid esters such as methyl lactate, ethyl lactate, propyl lactate and butyl lactate. Among these, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethyl diglycol are preferable.

The ink-jet ink of the present invention is preferably prepared to have a viscosity at 25 ° C. of 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics, particularly from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz.
When the viscosity is less than 5 mPa · s, a decrease in the follow-up property of the discharge is recognized in the high-frequency head. When the viscosity exceeds 50 mPa · s, even if a mechanism for reducing the viscosity by heating is incorporated in the head, the discharge itself A drop occurs, the ejection stability becomes poor, and the ejection cannot be performed at all.

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

  In order to use the ink-jet ink of the present invention, first, the ink-jet ink is supplied to a printer head of a printer for an ink-jet recording system, discharged from the printer head onto a substrate, and then an active energy ray such as an ultraviolet ray or an electron beam is applied. Irradiate. Thereby, the ink-jet ink composition on the printing medium is quickly cured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

  Synthesis examples relating to the compounds described in Table 1 are shown below.

<Synthesis Example 1> Hydroxyl-containing polymerizable compound (A): Synthesis of hydroxyl-containing polymerizable compound (1) 300 g of ethylene glycol diglycidyl ether (Epolite 40E, manufactured by Kyoeisha Chemical Co., Ltd.) in a flask equipped with a thermometer and a condenser. , 31.5 g of tetrabutylammonium bromide as a catalyst, 0.6 g of 4-methoxyphenol and 600 mL of toluene as a polymerization inhibitor were mixed. While maintaining the reaction temperature at 110 ° C., 270 g of acrylic acid was dropped into the mixed solution over 1 hour. Furthermore, after making it react for 1 hour, 300 mL of ethyl acetate was added and extracted. Subsequently, the organic layer was washed with 500 mL of saturated aqueous sodium hydrogen carbonate solution three times and once with 500 mL of saturated brine to remove unreacted acrylic acid. 40 g of anhydrous sodium sulfate was added to the organic layer and stirred, followed by filtration. The obtained solution was concentrated by a rotary evaporator to obtain 450 g of a colorless and transparent liquid hydroxyl group-containing polymerizable compound (1) in a yield of 83%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS).

<Synthesis Example 2> Hydroxyl-containing polymerizable compound (A): Synthesis of hydroxyl-containing polymerizable compound (5) Ethylene glycol diglycidyl ether of Example 1 was converted to 1,6-hexanediol diglycidyl ether (Kyoeisha Chemical Co., Ltd. 1600). In the same manner except that the amount of acrylic acid was changed to 360 g, 500 g of a colorless transparent liquid hydroxyl group-containing polymerizable compound (5) was obtained in a yield of 80%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS).

<Synthesis example 3> Hydroxyl group-containing polymerizable compound (A): Synthesis of hydroxyl group-containing polymerizable compound (16) The ethylene glycol diglycidyl ether of Example 1 was changed to propylene glycol diglycidyl ether (70P manufactured by Kyoeisha Chemical Co., Ltd.). In the same manner except that the amount of acrylic acid was changed to 290 g, 470 g of a colorless transparent liquid hydroxyl group-containing polymerizable compound (16) was obtained in a yield of 83%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS).

<Synthesis example 4> Hydroxyl group-containing polymerizable compound (A): Synthesis of hydroxyl group-containing polymerizable compound (31) A flask equipped with a thermometer, a Dean-Stark tube and a condenser was charged with 300 g of tartaric acid, 696 g of 2-hydroxyethyl acrylate, p. -By adding 17.2 g of toluenesulfonic acid, 1.7 g of 4-methylphenol and 1000 g of toluene and carrying out reflux stirring (110 ° C.) for 4 hours while blowing dry air, an almost theoretical amount of water was added to the Dean-Stark tube. Was confirmed. After cooling the reaction solution to room temperature, 2000 g of ion exchange water was added and stirred, and then the layers were separated using a separatory funnel. The organic layer was washed with 2000 g of saturated multistory water and 2000 g of ion exchange water, and then dried over 200 g of sodium sulfate. After filtration, the solvent was distilled off from the filtrate with an evaporator to obtain 498 g of a colorless transparent liquid hydroxyl group-containing polymerizable compound (31) in a yield of 72%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS).

<Synthesis Example 5> Hydroxyl-containing polymerizable compound (A): Synthesis of hydroxyl-containing polymerizable compound (33) In a flask equipped with a thermometer, Dean-Stark tube, and condenser, 300 g of tartaric acid, 864 g of 4-hydroxybutyl acrylate, p -By adding 17.2 g of toluenesulfonic acid, 1.7 g of 4-methylphenol and 1000 g of toluene and carrying out reflux stirring (110 ° C.) for 4 hours while blowing dry air, an almost theoretical amount of water was added to the Dean-Stark tube. Was confirmed. After cooling the reaction solution to room temperature, 2000 g of ion exchange water was added and stirred, and then the layers were separated using a separatory funnel. The organic layer was washed with 2000 g of saturated multistory water and 2000 g of ion exchange water, and then dried over 200 g of sodium sulfate. After filtration, the filtrate was distilled off with an evaporator to obtain 557 g of a colorless transparent liquid reactive monomer (1) in a yield of 72%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS).

<Example of clear ink composition>

<Examples 1-78, Comparative Examples 1-6> Preparation of polymerizable composition A clear ink composition was obtained by the formulation shown in Table 2. Using the obtained polymerizable composition, viscosity evaluation, curability evaluation, and adhesion evaluation were performed by the following methods. The results are shown in Table 2.

<Viscosity evaluation>
Measurement was performed using an E-type viscometer (Toki Sangyo TV-25 viscometer). The active energy ray-curable inkjet ink of the present invention is preferably prepared so that the viscosity at 25 ° C. is 5 to 50 mPa · s. Judgment criteria are as follows.

Judgment criteria ◎: 5 to 40 mPa · s
○: 41-50
×:> 50 mPa · s

<Curability evaluation test>
The prepared polymerizable composition was applied using a K control coater so that the wet film thickness was 10 μm, thereby preparing a coating film. The coated material was irradiated with ultraviolet rays as an active energy ray at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (metal halide lamp 100 W / cm1 lamp). The surface of the reaction cured product after irradiation was rubbed with a cotton cloth, and irradiation was repeated until the film was not damaged, and the curability was determined. The smaller the number of irradiations, the better the curability. Judgment criteria are as follows.

Judgment criteria ◎: 1 to 3 times ○: 4 to 6 times ×: 7 times or more

<Adhesion evaluation>
The prepared polymerizable composition was coated on various films (PET film, treated PE film, treated PP film, treated OPP film) using a K control coater so that the wet film thickness was 10 μm. Produced. The coating film was irradiated with 10 Pass ultraviolet rays at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (metal halide lamp 100 W / cm1 lamp) to obtain a cured film. The adhesion was evaluated by a cross-cut cellophane adhesive tape peeling test. 100 mask loss cuts were put on the cured film, and evaluation was performed based on the number of cells peeled off when the cellophane adhesive tape was forcibly peeled. The smaller the number of peeled masses, the better the adhesion to the substrate. Judgment criteria are as follows.

◎: Number of peeled cells 10 or less ○: Number of peeled cells 11 to 89
X: 90 or more squares peeled

Table 2

The raw materials in Table 2 are shown below.
VEEA: acrylic acid 2- (2-vinyloxyethoxy) ethyl TPGDA: tripropylene glycol diacrylate HPA: hydroxypropyl acrylate DA-250: PO-modified bisphenol A diglycidyl ether diacrylate (manufactured by Nagase ChemteX Corporation)
DA-931: Polypropylene glycol diglycidyl ether diacrylate (manufactured by Nagase ChemteX Corporation)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF)

  The clear ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention maintains a viscosity suitable for use as an ink-jet ink, and can be cured at high speed by ultraviolet irradiation, and also has excellent substrate adhesion. It was revealed that an excellent cured product was obtained (Examples 1 to 78).

  The clear ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention in the range of 25 wt% to 75 wt% maintains a viscosity suitable for use as an ink jet ink, and is further markedly accelerated by ultraviolet irradiation. In addition, a cured product having excellent substrate adhesion can be obtained, which is more preferable (Examples 1 to 76).

  Furthermore, the clear ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention has the same high-speed curability and excellent substrate adhesion as those before the photopolymerization initiator reduction even when the photoinitiator amount is reduced by 50%. Expresses sex (Examples 6, 64).

  The clear ink composition not containing the hydroxyl group-containing polymerizable compound (A) is inferior in both curability and substrate adhesion in any amount of photopolymerization initiator (Comparative Examples 1, 2, 6).

  Since DA-250 similar to the hydroxyl group-containing polymerizable compound (A) of the present invention has a too high viscosity, when 50 parts by weight is used, stable ejection characteristics cannot be maintained when used with inkjet ink (Comparative Example). 4). On the other hand, when 5 parts by weight of DA-250 is used, the high-speed curability and the base material adhesion characteristic of the hydroxyl group-containing polymerizable compound cannot be sufficiently exhibited (Comparative Example 3).

  Since DA-931 similar to the hydroxyl group-containing polymerizable compound (A) of the present invention has a molecular weight that is too large, the DA-931 is thickened, and furthermore, the high-speed curability that is characteristic of the hydroxyl group-containing polymerizable compound cannot be fully exhibited ( Comparative Example 5).

  As shown in the results of the above-mentioned viscosity evaluation, curability evaluation, and substrate adhesion evaluation, the clear ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention can be inkjetted by using an appropriate amount. It has been found that when used in an ink, it has an excellent viscosity, can be remarkably fast polymerized, and exhibits excellent adhesion to a substrate.

<Examples of inkjet ink composition>

  First, yellow, magenta, cyan, and black pigment dispersions comprising a pigment, a pigment dispersant, and a polymerizable compound (B) were prepared.

<Preparation of Pigment Dispersion A>
The composition of Pigment Dispersion A is shown in Table 3. After stirring the polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and the mixture is stirred until uniform using a high speed mixer or the like. The obtained mill base was dispersed in a horizontal sand mill for about 1 hour to prepare a cyanine pigment dispersion.

<Preparation of Pigment Dispersion B>
The formulation of Pigment Dispersion B is shown in Table 4. For pigment dispersion B, a black pigment dispersion was produced by the same production method as for pigment dispersion A.

<Preparation of Pigment Dispersion C>
The formulation of Pigment Dispersion C is shown in Table 5. After stirring the polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and the mixture is stirred until uniform using a high speed mixer or the like. The obtained mill base was dispersed in a horizontal sand mill for about 2 hours to prepare a magenta pigment dispersion.

<Preparation of Pigment Dispersion D>
The formulation of Pigment Dispersion D is shown in Table 6. After stirring the polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and the mixture is stirred until uniform using a high speed mixer or the like. The obtained mill base was dispersed in a horizontal sand mill for about 1.5 hours to prepare a yellow pigment dispersion.

<Examples 79 to 118, Comparative Examples 7 to 11>
In the formulation of Tables 7 to 9, the ingredients are added with stirring sequentially from the top of the table, gently mixed until the polymerizable compound and the photopolymerization initiator are dissolved, and then filtered through a 1 μm membrane filter. Ink jet ink compositions were obtained by removing coarse particles. In addition, a compounding quantity is a weight part.

<Continuous discharge property>
The ink obtained is a Kyocera head (nominal 14 pl / 1 drop) or Konica.
A KM512 head (nominal 42 pl / 1 drop) was used, and continuous stable ejection evaluation was performed at a voltage of 10 to 12V. In this evaluation, discharge was continuously performed from all nozzles, printing was performed on PVC every 10 minutes, and the state of printing was observed. The content of the evaluation was that when the printing interval varied, it was determined that the liquid droplets were unevenly flying, and the head clogging was determined to occur where the dots were missing. Evaluation continued until 120 minutes. Judgment criteria are as follows.

◎: When good discharge is possible up to 120 minutes ○: When good discharge is possible up to 60 minutes ×: When uneven flight or clogging occurs within 30 minutes

<Intermittent discharge>
Using the inkjet ejection evaluation apparatus, intermittent ejection performance was similarly evaluated. In this evaluation, after stopping the discharge for 30 minutes after discharging, printing was performed on plain paper, and the state of printing was observed. The content of the evaluation was that when the printing interval varied, it was determined that the liquid droplets were unevenly flying, and the head clogging was determined to occur where the dots were missing. Judgment criteria are as follows.

◎: When good discharge can be performed ○: Even if uneven flight or clogging occurs immediately after standing, it recovers within 1 minute, and after that, good discharge can be performed ×: Partial flight or clogging occurs, If it does not recover after that and good discharge cannot be performed

<Curability evaluation test>
Using an ink jet ink composition, the ink was ejected onto PVC under an ink droplet amount of 14 pl and a printing condition of 600 × 600 dpi by an ink jet ejection device loaded with a Kyocera head. After discharge, UV irradiation was performed at 150 W / cm from Harrison Toshiba Lighting, 1 metal halide lamp, conveyor speed 50 m / min, and the surface of the reaction cured product after irradiation was rubbed with a cotton cloth and repeatedly irradiated until the film was not damaged. The curability was determined. The smaller the number of irradiations, the better the curability. Judgment criteria are as follows.

Judgment criteria ◎: 1 to 3 times ○: 4 to 6 times ×: 7 times or more

<Adhesion test>
Using the ink jet ink composition, the ink was ejected onto PET under the printing conditions of an ink droplet amount of 14 pl and 600 × 600 dpi by an ink jet ejecting apparatus loaded with a Kyocera head. After the discharge, a cured film was obtained by irradiation with 10 Pass ultraviolet light at 150 W / cm from Harrison Toshiba Lighting, one metal halide lamp, and a conveyor speed of 10 m / min. The adhesion was evaluated by a cross-cut cellophane adhesive tape peeling test. 100 mask loss cuts were put on the cured film, and evaluation was performed based on the number of cells peeled off when the cellophane adhesive tape was forcibly peeled. The smaller the number of peeled masses, the better the adhesion to the substrate. Judgment criteria are as follows.

A: Number of peeled cells 10 or less ○: Stripped cells 11 to 89
X: 90 or more squares peeled

Table 7

Table 8

Table 9

The raw materials in Tables 7 to 9 are shown below.
VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate TPGDA: tripropylene glycol diacrylate HPA: hydroxypropyl acrylate DA-250: PO-modified bisphenol A diglycidyl ether diacrylate (manufactured by Nagase ChemteX Corporation)
DA-931: Polypropylene glycol diglycidyl ether diacrylate (manufactured by Nagase ChemteX Corporation)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF)
Irg819: Irgacure 819 (manufactured by BASF)
Irg369: Irgacure 369 (manufactured by BASF)
EsaOne: EsacureOne (manufactured by Nippon Shibel Hegner)
BYK-UV3510: BYK-UV3510 (silicon resin manufactured by BYKChemie)
BHT: BHT Swanox (made by Seiko Chemical Co., Ltd.)
Phenothiazine: Phenothiazine (Seiko Chemical Co., Ltd.)

  The inkjet ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention exhibits good discharge characteristics, and can be cured at high speed by ultraviolet irradiation with active energy rays, and has excellent substrate adhesion. It became clear that the hardened | cured material was obtained (Examples 79-118).

  The ink-jet ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention in the range of 25% by weight to 75% by weight exhibits excellent discharge characteristics, and can be markedly cured at high speed by ultraviolet irradiation. Moreover, since a cured product having excellent substrate adhesion is obtained, it is more preferable (Examples 79 to 116).

  Furthermore, the ink-jet ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention has the same high-speed curability and excellent substrate adhesion as those before the photopolymerization initiator reduction, even when the photoinitiator amount is reduced by 50%. Expresses sex (Examples 85, 86, 93, 94, 104, 105, 112, 113).

  The ink-jet ink composition not containing the hydroxyl group-containing polymerizable compound (A) has neither excellent curability nor substrate adhesion in any amount of the photopolymerization initiator (Comparative Examples 7, 8, and 11).

  Since DA-250 similar to the hydroxyl group-containing polymerizable compound (A) of the present invention has a too high viscosity, when 50 parts by weight is used, stable ejection characteristics cannot be maintained in the ink jet ink (Comparative Example 9).

  Since DA-931 similar to the hydroxyl group-containing polymerizable compound (A) of the present invention has a too high molecular weight, it cannot sufficiently exhibit the high-speed curability that is characteristic of the hydroxyl group-containing polymerizable compound (Comparative Example 10).

  As shown in the results of the above-described viscosity evaluation, curability evaluation, and substrate adhesion evaluation, the ink-jet ink composition containing the hydroxyl group-containing polymerizable compound (A) of the present invention is an ink jet by using an appropriate amount. It has been revealed that the ink has excellent viscosity for ink ejection, can be remarkably fast polymerized, and exhibits excellent adhesion to the substrate.

  As shown in the results of the above viscosity evaluation, curability evaluation, and substrate adhesion evaluation, the clear jet ink composition containing an appropriate amount of the hydroxyl group-containing polymerizable compound (A) of the present invention has an excellent viscosity, and It was revealed that remarkably fast polymerization was possible and, furthermore, excellent adhesion to the substrate was exhibited.

  From the above, the inkjet ink composition of the present invention is excellent in ejection characteristics by using an appropriate amount of the hydroxyl group-containing polymerizable compound (A) characterized by having a bifunctional hydroxyl group and a bifunctional polymerizable group. In addition, it was possible to provide an ink-jet ink composition having a low viscosity and a remarkably fast polymerization rate and having excellent substrate adhesion.

Claims (5)

An active energy ray-curable inkjet ink composition comprising a hydroxyl group-containing polymerizable compound (A) and a polymerizable compound (B) other than the hydroxyl group-containing polymerizable compound (A),
The hydroxyl group-containing polymerizable compound (A) is represented by the following general formula (1) or the following general formula (2),
And the viscosity in 25 degreeC is the range of 50-3000 mPa * s,
The polymerizable compound (B) contains 2- (2-vinyloxyethoxy) ethyl acrylate, an active energy ray-curable inkjet ink composition.
General formula (1)

(In formula, R < ¹ > and R < ² > represents a hydrogen atom or a methyl group each independently.
X represents a divalent linking group. )
General formula (2)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group.
Y represents a divalent linking group. )   The content of the hydroxyl group-containing polymerizable compound (A) is in the range of 30 to 75 parts by weight with respect to 100 parts by weight of the total amount of the hydroxyl group-containing polymerizable compound (A) and the polymerizable compound (B). The active energy ray-curable inkjet ink composition according to claim 1, wherein:   The active energy ray-curable inkjet ink composition according to claim 1, further comprising a photopolymerization initiator. Furthermore, a coloring component is included, The active energy ray hardening-type inkjet ink composition in any one of Claims 1-3 characterized by the above-mentioned. A printed matter using the active energy ray-curable inkjet ink composition according to claim 3 or 4.