MX2008000481A - Actinic radiation curable jet-printing ink. - Google Patents

Abstract

An actinic radiation curable jet-printing ink containing a polymerizable monomer component, characterized in that the polymerizable monomer component comprises 95 to 99.99wt% of a monofunctional monomer and 0.01 to 5wt% of a polyfunctional monomer and that a 10-??m thick cured film formed by using the ink exhibits a ductility exceeding 120% when stretched at 170 degree C at a strain rate of 2/min.

Description

CURABLE INK WITH ACTIVE ENERGY BEAM FOR PRINTING BY INK JET TECHNICAL FIELD The present invention relates to a curable ink with active energy beam for inkjet printing. In addition, the present invention also relates to a cured film formed using the curable ink with active energy beam. In addition, the present invention also relates to a printed article comprising the cured film. PREVIOUS BOX Conventionally, active energy beam curable inks for ink jet printing have been supplied to, and are supplied in offset printing, silk screen printing, and as top coating materials. In recent years, the amount of active-energy-curable inks has continued to increase, since such inks allow a simplified drying process and reduced costs, and also offer the environmental advantage of allowing a reduction in the volume of volatilized solvents. . Currently, both water-based inks and solvent-based inks are widely used as ink jet printers. These inkjet inks are used in different situations in accordance with their respective particularities, but their use in industrial applications faces a variety of problems, including restrictions on the printing substrate, a comparatively low level of water resistance, a large amount of energy required to dry the ink, and adhesion of ink components to the print head if the ink volatilizes inside the head. Consequently, the replacement of these inks with curable inks with active energy beam, which can be used with all manner of printing substrates, exhibits favorable water resistance, does not require thermal energy for drying, and exhibits comparatively low levels of volatility, It has waited impatiently. However, even when the cured films forming using conventional curable active energy beam inks are hard, they are often brittle. In addition, because cured films of active energy beam curable inks exhibit significantly less drainage reprocessing properties than conventional solvent based inks, the active energy beam curable inks tend to be unsuitable for high print applications. quality that require training processing. The following types of inks have been proposed in order to address the types of problems described above. Japanese Laid-Open Patent No. H05-21428 describes an ink comprising a dye and from 50 to 95% by weight of polymerizable monomers, wherein the ink comprises a maximum of 70% by weight of monofunctional monomers, a maximum of 70% by weight weight of bifunctional monomers, and from 0 to 10% by weight of trifunctional or higher monomers. The Japanese translation of PCT International Application No. 2004-514014 discloses an ink composition comprising a heterocyclic radiation curable monomer and / or an alkoxylated monomer comprising pendant alkoxylated functionality. In order to alleviate shrinkage during curing, the Japanese translation of PCT International Application No. 2004-518787 discloses an ink composition comprising an oligomer which is a reaction product of an aliphatic polyisocyanate and a radiation curable alcohol which it comprises one or more radiation curable fractions, one or more hydroxyl moieties and one or more polycaprolactone ester moieties, and a reactive diluent.

Japanese Patent Laid-Open No. H06-184484 discloses an ink composition comprising a urethane acrylate oligomer based on polycaprolactone, a vinylcaprolactam and phenoxy acrylate. EXPOSITION OF THE INVENTION It is an object of the present invention to provide an active energy beam curable ink for inkjet printing which exhibits excellent adhesion to plastic substrates which require favorable properties of bending and stretching processing., and also exhibits excellent working capacity and superior abrasion resistance and rub resistance. Additionally, another object of the present invention is to provide a cured film that exhibits excellent adhesion to plastic substrates that require favorable bending and drawing processing properties, and also exhibits excellent workability and superior abrasion resistance and rub resistance. In addition, another object of the present invention is to provide a printed article comprising a cured film with these types of properties. The present invention relates to an ink-curable ink of active energy for ink jet printing comprising polymerizable monomers, wherein with respect to the total of all the polymerizable monomers, the polymerizable monomers comprise from 95 to 99.99% by weight of a monofunctional monomer and from 0.01 to 5% by weight of a polyfunctional monomer, and a cured film of thickness of 10 um formed using active energy beam curable ink exhibits a drawability exceeding 120% when stretched at a temperature of 170 ° C at an effort regime of 2 / m? N. Additionally, another aspect of the present invention relates to an inkjet ink curable for ink jet printing comprising polymerizable monomers, wherein with respect to the total of all polymerizable monomers, the polymerizable monomers comprise from 95 to 99.99 % by weight of a monofunctional monomer and 0.01 to 5% by weight of a polyfunctional monomer, and a cured film of 10 μm thickness formed using the active energy beam curable ink exhibits a storage elastic modulus (E ') within from a scale of 1 x 104 to 5 x 107 Pa at an oscillation frequency of 1 Hz and a temperature within a range of 100 to 150 ° C. In the above-described invention, the Martens hardness of the cured film of thickness of 10 um is preferably not less than 160 N / mm2. Additionally, in the invention described above, the glass transition point of the cured film of thickness of 10 um is preferably not less than 25 ° C. In the previous invention, with respect to the total of all polymerizable monomers, the polymerizable monomers preferably comprise from 50 to 100% by weight of monomers having a cyclic structure. Furthermore, with respect to the total of all polymerizable monomers, the polymerizable monomers preferably comprise from 30 to 99.99% by weight of monomers selected from the group consisting of 2-phenoxyethyl acrylate, ethylene oxide adduct monomers of 2-phenoxyethyl acrylate. -phenoxyethyl, and propylene oxide adduct monomers of 2-phenoxyethyl acrylate. Furthermore, in relation to the total of all polymerizable monomers, the polymerizable monomers preferably comprise from 1 to 30% by weight of 2-hydroxy-3-phenoxypropyl acrylate. Additionally, in the above-described invention, the molecular weight of the polyfunctional monomer is preferably less than 2,000, and in addition, the polyfunctional monomer is preferably a bifunctional monomer. In the above invention, the active energy beam curable ink may further comprise a pigment. Ultraviolet radiation can be used as the active energy beam to cure the curable ink with active energy beam. In addition, another aspect of the present invention relates to an ink set comprising at least four of the curable inks with active energy beam above, wherein the pigments contained in each of the curable inks with active energy beam are mutually different Examples of these four curable inks with active energy beam include, for example, yellow, magenta, cyan and black inks. Additionally, another aspect of the present invention relates to a cured film formed using the curable ink with active energy beam described above. In addition, yet another aspect of the present invention relates to a printed article comprising a printing substrate and the above cured film. This request is related to the subject matter described in the previous Japanese Requests No. 2005-214433, filed on July 25, 2005, No. 2005-327135, filed on November 11, 2005, No. 2006- 117696, filed on April 21, 2006, and No. 2006-125751, filed on April 28, 2006. April 2006; the complete contents of which are incorporated by reference herein. BEST MODE FOR CARRYING OUT THE INVENTION In order to ensure that the cured film obtained by inkjet discharge of the curable ink with active energy beam (hereinafter also referred to simply as "the ink") to any of a variety of substrates and the subsequent curing exhibits favorable adhesion to the substrate, high levels of abrasion resistance and rub resistance, favorable stretch properties and flexibility during forming processing such as stretch processing, and favorable adhesion after the termination of said Formation processing, raising the amount of monofunctional monomers and reducing the amount of polyfunctional monomers within the ink are of importance. In addition, ensuring favorable control of the stretch capacity at 170 ° C of the cured film formed using the ink, or favorable control of the elastic modulus (E ') of storage within the temperature range of 100 to 150 ° C are also important The active energy beam curable ink of the present invention comprises polymerizable monomers. These polymerizable monomers include a monofunctional monomer and a polyfunctional monomer. In relation to the total of all polymerizable monomers, the amount of monofunctional monomer is within a range of 95 to 99.99% by weight, and is preferably 95 to 99.9% by weight, and even more preferably 95 to 99% by weight. weight. The amount of the polyfunctional monomer is within a range of 0.01 to 5% by weight, preferably 0.1 to 5% by weight, and even more preferably 1 to 5% by weight. As a result, the cured film formed using the active energy beam curable ink of the present invention exhibits favorable stretch properties, flexibility, abrasion resistance, rub resistance and adhesion. If an ink comprises less than 95% by weight of the monofunctional monomer and more than 5% by weight of the polyfunctional monomer, then the shrinkage during curing is large, and the adhesion of the cured film tends to deteriorate. In addition, in some cases, large amounts of residual stress can develop within the cured film, causing wrinkles and cracks. One method to solve the problem of wrinkles and cracks involves dramatically reducing the value of Tg for the cured film to relieve the effort. However, even when this method solves the problems of wrinkles and cracks, it can cause a reduction in the hardness of the cured film, leading to deterioration in abrasion resistance and rub resistance. Consequently, the Tg value of the cured film preferably is not dramatically reduced. With the active energy beam curable ink of the present invention, a cured 10 μm thick film formed using the ink exhibits a stretch capacity exceeding 120% when stretched at an effort rate of 2 / min under one atmosphere of 170 ° C. Stretch capacity is measured by forming a cured 10-μm thick film on a polycarbonate film substrate, and then stretching both the polycarbonate film substrate and the cured film together. Stretching capacity can be measured using a universal tester such as Tensilon (UCT-1T, manufactured by Orientec Co., Ltd.). The stretching ability is preferably greater than 120% and not more than 300%, even more preferably not less than 150% and not more than 250%, and more preferably not less than 170% and not more than 200%. If the stretch capacity is less than 120%, then the favorable stretching and flexibility properties can not be obtained during forming processing such as stretch processing. Additionally, if the stretch capacity exceeds 300%, then the superior hardness of the cured film is lost, and practical application becomes difficult as a cured film. By ensuring that the proportions of polymerizable monomers contained within the ink fall within the ranges described above, the drawing capacity of the cured film can be increased beyond 120%. Additionally, with the active energy beam curable ink of the present invention, the measurement of the viscoelasticity of a cured film of 10 μm thickness formed using the ink at an oscillation frequency of 1 Hz provides an elastic modulus (E ') Storage for the cured film within a scale from 1 x 104 to 5 x 107 Pa for the temperature scale from 100 to 150 ° C. E 'represents the elastic modulus of storage determined by measuring the dynamic viscoelasticity. The value of E 'can be measured, for example, using an EXSTAR6100 DMS viscoelasticity spectrometer manufactured by Seiko Instruments Inc. The measurement can also be conducted using a typical "Vibron" viscoelasticity measuring device, in which a direct vibration is It imparts to the cured film, and the resulting stress response is measured. An ink of the present invention, which requires higher stretch processing properties, is designed so that the value of E 'is within a scale of 1 x 104 to 5 x 107 Pa. This value for E' is preferably within from a scale of 1 x 105 to 5 to 107 Pa, and even more preferably from 1 x 106 to 4 x 107 Pa. A cured film with an elastic storage modulus that is smaller than the previous scale is capable of achieving processing properties of satisfactory drawing, but the stability of the cured film at elevated temperatures deteriorates, and irregularities may develop on the film surface after heating. In addition, a reduction in the luster of the cured stretched film is also observed, which hinders the practical use of the film. The Martens hardness of a 10 μm thick cut film formed using the active energy beam curable ink of the present invention is preferably not less than 160 n / mm 2.

In the present invention, Martens hardness has been used to indicate hardness. When evaluating the hardness of a cured film, evaluating only the materials of the cured film is usually impossible, and the hardness value is usually affected by factors such as the substrate material to which the ink has been applied, the adhesion between that substrate and the cured film, and the film thickness of the cured film. The Martens hardness, which is measured by pressing a fractional penetrator to the surface of the cured film, and then calculating the hardness based on the resulting depth and the load used, is used within the recent DIN standards (Deutsches Institut fur Normung eV), as a technique that, compared to other techniques, is able to measure the hardness of the actual cured film itself. A microhardness tester can be used for Martens hardness measurement. However, there are no particular restrictions on the device used to measure Martens hardness, and the measurement can also be conducted using a measuring device commonly known as a "nanopenetrator", or any other suitable device. The Martens hardness is even more preferably not less than 160 N / mm2 and no more than 1,000 N / mm2, and more preferably is not less than 200 N / mm2 and not more than 800 N / mm2. If this value is less than 160 N / mm2, then the cured film lacks superior hardness, and may be unsuitable for certain applications, whereas if the value exceeds 1,000 N / mm2, then the cured film becomes excessively hard and the processing Stretching can be impossible. The glass transition point of a cured 10 μm thick film formed using the active energy beam curable ink of the present invention is preferably not less than 25 ° C. The glass transition point (or glass transition temperature) indicates the maximum temperature for the determined Tan d value of the previous dynamic viscoelasticity measurement. The glass transition point even more preferably is not less than 25 ° C and not more than 150 ° C. If this value is less than 25 ° C, then the surface of the cured film tends to retain tack at room temperature, whereas if the value exceeds 150 ° C, then the stretching process has to become difficult. In the present invention, polymerizable monomers refer to polymerizable monomers that function as active energy beam curable reaction components. Specifically, the polymerizable monomers are molecules containing ethylenically unsaturated double bonds. These active-energy beam curable reaction components exclude components such as the initiators, pigments and additives described below. In the present invention, ensuring that the polymerizable monomers include from 50 to 100% by weight of monomers having a cyclic structure enables a more favorable cured film to be formed. This proportion is preferably 60 to 100%, and even more preferably 90 to 100% by weight. Examples of monofunctional monomers having a cyclic structure include cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzoyl acrylate, methyl phenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, tetrahydrofurfuryl acrylate modified with caprolactone, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate. , 2-phenoxyethyl acrylate (or ethylene oxide and / or propylene oxide acid monomers thereof), acryloylmorpholine, isobornyl acrylate, phenoxyethylene glycol acrylate, vinyl caprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate and monoacrylate of 1,4-cyclohexanedimethanol, even though the above monomers should not be considered as being limited thereto.

Of these, examples of preferred monomers that offer particular suitability for ink jet printing include cyclohexyl acrylate, methylphenoxyethyl acrylate, 2-phenoxyethyl acrylate (or ethylene oxide and / or propylene oxide adduct monomers thereof), acryloylmorpholine, isobornyl acrylate, vinylcaprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate and monoacrylate 1,4-cyclohexanedimethanol. In addition, from the safety and performance viewpoints of the cured film, the use of methylphenoxyethyl acrylate, 2-phenoxyethyl acrylate (or ethylene oxide and / or propylene oxide adduct monomers thereof), acryloylmorpholine, acrylate of isobornyl, vinylcaprolactam, 2-hydro-3-phenoxypropyl acrylate and 1,4-cyclohexanedimethanol monoacrylate is particularly preferred. Additionally, examples of polyfunctional monomers having a cyclic structure include dimethyloltriciclodecane diacrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethyloldicyclopentane diacrylate, ethoxylated isocyanuric acid, tri (2-hydroxyethyl) isocyanurate triacrylate and tri (meth) arylyl isocyanurate, even though the above monomers should not be considered as being limited thereto. Of these examples of preferred monomers offering particular suitability for ink jet printing include dimethyloltricyclodecane diacrylate, propoxylated di (meth) acrylate debisphenol A and ethoxylated bisphenol A di (meth) acrylate. In the present invention, the polymerizable monomers preferably comprise, relative to the total of all polymerizable monomers, from 30 to 99.99% by weight of monomers selected from the group consisting of 2-phenoxyethyl acrylate, ethylene oxide adduct monomers. of 2-phenoxyethyl acrylate, and propylene oxide adduct monomers of 2-phenoxyethyl acrylate. This proportion is even more preferably from 40 to 99.99% by weight, and more preferably from 50 to 99.99% by weight. Furthermore, in the present invention, the polymerizable monomers preferably comprise, relative to the total of all polymerizable monomers, from 1 to 30% by weight of 2-hydroxy-3-phenoxypropyl acrylate. This proportion is even more preferably from 1 to 20% by weight. If the ink contains these monomers that have cyclic structures, then the adhesion improves. The reasons for this improvement are not entirely clear, but it is thought that the cyclic structure portion (ie, the surface) is bound to the substrate, increasing the strength of van der Waals. The monofunctional and polyfunctional monomers can each use either a single monomer, or if necessary, a combination of two or more different monomers. In addition, a monomer that does not have a cyclic structure can also be used, either alone, or in combination with the monomer having a cyclic structure. Specific examples of monofunctional monomers having no cyclic structure include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, dipropylene glycol acrylate, β-carboxyethyl acrylate, ethyldiglyc acrylate, trimethylolpropane formal monoacrylate , imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, β-carboxy polyprolactone monoacrylate and N-vinylformamide, even though the above monomers should not be considered as being limited thereto. Additionally, specific examples of polyfunctional monomers that do not have cyclic structure include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di (meth) acrylate 1, 6-hexanediol, ethoxylated 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonandiol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-l, 3-propanediol diacrylate, neopentyl glycol diacrylate of hydroxypivalic acid, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate hydroxypivalic acid, triacrylate ethoxylated phosphoric acid, ethoxylated tripropylene glycol diacrylate, trimethylolpropane diacrylate modified with neopentyl glycol, pentaerythritol diacrylate modified with stearic acid, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolprophane triacrylate, glyceryl triacrylate propoxylated, tetramethylolmethane tetraacrylate, pentaerythritol tetraacrylate, tetracryl ditrimethylolpropane, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexa acrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentadrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, oligoacrylate pentaerythritol, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, di (meth) acrylate propylene glycol, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate, even though the above monomers should not be considered as being limited to the same. These monofunctional and polyfunctional monomers can each use either a single monomer or, if necessary, a combination of two or more different monomers. Additionally, regardless of the existence of a cyclic structure mentioned above, if improved stretching processing properties are required, then the use of a bifunctional monomer such as the polyfunctional monomer is preferred. The use of only one bifunctional monomer as the polyfunctional monomer is particularly desirable. Further, in order to allow an ink of the present invention to be prepared as a low viscosity ink, and to ensure favorable prolonged thermal stability of the printed image, these polyfunctional monomers preferably comprise monomers with a molecular weight of less than 2,000. The use of a polyfunctional monomer that does not contain monomers with a molecular weight of 2,000 or more, ie, a polyfunctional monomer comprising only monomers with a molecular weight of less than 2,000, is particularly desirable. The active energy beam of the present invention refers to a beam of energy that influences the orbits of the electron within the irradiated article, and generates radicals, cations or anions or the like that act as the striker for a polymerization reaction. Examples of this active energy beam include an electron beam, ultraviolet radiation and infrared radiation, even when there are no particle restrictions, as long as the energy beam is capable of inducing the polymerization reaction. The ink of the present invention refers to a liquid that is printed or coated onto a substrate surface. In those cases where the ink of the present invention does not contain coloring components, the ink can be used in coating applications. Both simple coating and coating in layers that is carried out together with an ink comprising a coloring component can be conducted. In the case of coating in layers, either an ink of the present invention or a conventional colored ink can be used as the ink comprising a coloring component. Additionally, in order to raise the hardness of the film lasted, and impart to the film with superior durability such as abrasion resistance, superior properties of formation or superior design features such as a controlled level of luster, various fillers or resin components may also be added to the ink. Examples of suitable fillers include acceptor pigments such as calcium carbonate, barium sulfate, spherical silica, and hollow silica, and resin beads and the like. There are no particular restrictions on the resin components, as long as the resin is inactive during radiation with the active energy beam. Examples of suitable resins include polyurethane resins, vinyl chloride-based resins (such as polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymers and ethylene-vinyl acetate copolymers), polyester resins, resins of poly (meth) acrylate, polyketone resins, polyvinyl-based resins (such as polyvinylacetal resins, polyvinylbutyral resins and polyvinylpyrrolidone resins), and cellulose-based resins (such as CAB resins or CAP resins). In those cases where these types of fillers or resin components are added, the types of material added and the mixing amounts are preferably determined with due consideration of the resultant ink jet suitability. In addition, other printing methods such as silk screen printing, gravure printing or offset printing, or other coating methods such as spraying coating methods or methods in which a separately formed coating layer (such as a film) ) is transferred by lamination can also be used. These printing methods are particularly preferred in those cases where the ink comprises a filler or resin component. On the other hand, in those cases where the ink of the present invention comprises a coloring component, the ink can be used as a material to display graphics, signs or photographs or the like. Conventionally, dyes or pigments are the most widely used coloring components. Of the various possible pigment components, specific examples of carbon blacks include Special Black 350, 250, 100, 550, 5, 4, 4a and 6, and Printex U, V, 140U, 140V, 95, 90, 85, 80 , 75, 55, 45, 40 P, 60, L6, L, 300, 30, 3, 35, 25, A and G, all manufactured by Degusta AG, Regal 400R, 660R, 330R and 250R and Mogol E and L, all manufactured by Cabot Corporation, and MA7, 8, 11, 77, 100, 100R, 100S, 220 and 230, and # 2700, # 2650, # 2600, # 200, # 2350, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 45L, # 44, # 40 , # 33, # 332, # 30, # 25, # 20, # 10, # 5, CR9, 5 and # 260, all manufactured by Mitsubishi Chemical Corporation. In addition, in the present invention, yellow, magenta or cyano inks, or inks of other colors such as white may employ the types of pigments used in inks for conventional printing and coating applications. If necessary, the pigments can also be selected on the basis of their coloring properties or resistance to light or the like.

A coating material used in typical printing applications such as silk screen printing, engraving printing or offset printing may also be layered on the ink layer comprising a coloring component of the present invention. In addition, the ink layer comprising a coloring component of the present invention can be coated with a separately formed coating layer (such as a film) using a lamination transfer, or coated with spray coating material. The proportion of the pigment relative to the total weight of the ink is preferably within a range of 0.2 to 15 parts by weight of the yellow, magenta, cyan or black organic pigment per 100 parts by weight of the ink. In the case of white titanium oxide, the proportion is preferably within a range of 5 to 40 parts by weight per 100 parts by weight of the ink. In addition, the ink of the present invention can also use a dispersant to disperse and stabilize the filler and pigment. There are a multitude of dispersants, including polymer dispersants and low molecular weight dispersants, and these may be selected in accordance with the required dispersibility. The pigment derivatives can also be used as dispersion aids. Additionally, in those cases where ultraviolet radiation is used as the active energy beam, the ink usually contains a photopolymerization initiator. This photopolymerization initiator can be freely selected in accordance with the curing regime, the properties of the cured film and the coloring component. Specifically, molecular dissociation initiators or hydrogen abstraction initiators are particularly suitable as the photoradical polymerization initiator in the present invention. Specific examples include isobutyl benzoin ether, 2-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one. , oxide debis (2,4,6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine, 1 1, 2-octanedione and 1- (4- (phenylthio) -2- (o-benzoyloxime)). Examples of other molecular dissociation initiators that can be used in combination with the above initiators include 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydox-2-methyl-1-phenylpropan-1-one, 1- (4 -isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one. In addition, the photopolymerization initiators of hydrogen abstraction such as benzophenone, 4-phenylbenzophenone, isophthalone and 4-benzyl-4'-methyl-diphenylsufurote can also be used in combination with the above initiators. The amount of the photopolymerization initiator is preferably within a range of 5 to 205 by weight of the ink. With the above photoradical polymerization initiator, an amine which is not subjected to an addition reaction with the above polymerizable monomers can also be added as a sensitizer, and suitable examples of this amine include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, and 4,4'-bis (diethylamino) venomophenone. The above-described photoradical polymerization initiator and sensitivity, of course, are preferably selected from those materials which exhibit excellent solubility within the polymerizable monomers, and do not inhibit the transmission of ultraviolet light. The amount of the sensitizer is preferably on the scale from 0 to 5% by weight of the ink. In addition, in those cases where the electronic beam is used as the active energy beam, the active energy beam curable ink can be prepared as an electron beam curable ink excluding the foregoing initiator and sensitizer. In the present invention, a polymerization inhibitor such as hydroquinone, p-methoxyphenyl, 5-butylcatechol, pyrogallol obutilhyhydroxytoluene is preferably added to the ink in an amount within a range of 0.01 to 5% by weight in order to improve the stability of the ink during time, and improve the stability of the ink within the inkjet discharge apparatus. In addition, additives to impart all kinds of functions can also be added to the ink. Examples of these additives include one or more conventionally used plasticizers, wetting modifiers, surface tension modifiers, antifoaming agents, slip agents, anti-blocking agents, ultraviolet light inhibitors, photostabilizers and antioxidants such as dibutylhydroxytoluene, one or more of which are Can add in accordance with the need. Dispersants, dispersion aids and additives may be selected in accordance with the intended application, and no particular restrictions are specified within the present invention. The ink of the present invention can be used within a set comprising a plurality of inks containing different pigments, such as a set comprising 4, 5, 6 or 7 different inks. Examples of games containing four inks include ink sets comprising yellow, magenta, cyan and black inks, and ink sets comprising yellow, magenta, gray and white inks. The ink of the present invention is printed onto a printing substrate using an ink jet discharge apparatus. There are no particular restrictions on the printing substrates that can be used with the present invention, and suitable substrates include polycarbonate, rigid vinyl chloride, flexible vinyl chloride, polystyrene, polystyrene foam, polymethyl methacrylate (PMMA), polypropylene, polyethylene , polyethylene terphthalate (PET), plastic substrates comprising mixtures or modified products of the above substrates, glass, metal substrates such as stainless steel, and wood. The ink that has been discharged by ink jet to the printing substrate becomes a cured film by irradiation with an active energy beam. There are no particular restrictions on the thickness of the cured film formed on the printing substrate using the ink of the present invention, and an appropriate thickness can be selected in accordance with the intended application. The film thickness is preferably within a range of 4 to 50 μm, still more preferably 5 to 50 μm, and more preferably 7 to 40 μm. A cured film used to evaluate the ink properties can be prepared, for example, using the following method. First, the ink of the present invention is solidly printed onto a substrate with releasable release capacity such as polyethylene, using an ink jet discharge apparatus. Subsequently, the solid printed ink is subjected to ultraviolet light irradiation using an ultraviolet irradiation apparatus (120 W / cm, a high pressure mercury lamp, conveyor speed: 5 m / min, 1 pass), thus forming a cured film of 10 um in thickness. This cured film can be cut to size if necessary.

The monofunctional / polyfunctional monomer ratio is controlled in the ink of the present invention. In addition, to achieve both strength and favorable drawing processing properties for the resulting cured film, the stretch capacity or elastic modulus (E ') of storage of the cured film of the ink of the present invention is also controlled. Further, in the ink of the present invention, if required, the monomer structure can be specified, the composition of monomers having a specified structure can be controlled, and the Tg value of the cured film can be controlled. As a result, an active energy beam curable ink can be provided which exhibits excellent adhesion to substrates, and particularly to polycarbonates, exhibits superior bending and drawing properties, as well as superior levels of abrasion resistance and rub resistance. In addition, appropriate monomers may be selected within the ink of the present invention. As a result, the viscosity of the ink can be kept low, and erosion of the head member by the ink can be prevented. Additionally, low molecular weight polyfunctional monomers can be selected and used within the ink of the present invention. As a result, the generation of satellite drops, which tends to occur during ink discharge, can be suppressed, allowing attractive printed articles to be printed for extended periods. EXAMPLES As follows there is a description of specifics of the present invention, based on a series of examples, even though the present invention is by no means limited by these examples. In the examples, "parts" refer to "parts by weight". First, a pigment dispersion A was prepared with the formulation shown below. Dispersion A was prepared by adding the pigment and dispersant to the monomer, conducting the mixing with a high speed mixer or the like until a uniform mixture was obtained, and then dispersing the grinding base thus obtained in a horizontal sand mill during about one hour. Leonor Blue FG-7400G (a phthalocyanine pigment, manufactured by Toyo King Mfg. Co., Ltd.): 30 parts Solsperse 32000 (a pigment dispersant, manufactured by The Lubrizol Corporation): 9 parts - Phenoxyethyl Acrylate: 61 parts Additionally, a pigment dispersion B was prepared with the formulation shown below. The dispersion was prepared using the same production method as that used for dispersion A. - Novoperm Yellow P-HG (a benzimidazolone compound, manufactured by Clarinat Ltd.): 35 parts Solsperse 24000 (a pigment dispersant, manufactured by The Lubrizol Corporation): 7 parts - Phenoxyethyl Acrylate: 58 parts In addition, a C dispersion of pigment was prepared with the formulation shown below. The dispersion was prepared using the same production method as that used for dispersion A. - Hostaperm Red E5B02 (a pigment dispersant, k manufactured by Ciariant Ltd): 20 parts Solsperse 24000 (a pigment dispersant, manufactured by the Lubrizol Corporation) : 6 parts - Phenoxyethyl Acrylate: 74 parts Additionally, a D dispersion of pigment was prepared with the formulation shown below. The dispersion was prepared using the same production method as that used for dispersion A. - Special Black 350 (a carbon black pigment Manufactured by Degusta AG): 30 parts - Solsperse 32000 (a pigment dispersant, manufactured by Degusta AG ): 30 parts - Phenoxyethyl acrylate: 64 parts Additionally, a pigment dispersion E was prepared with the formulation shown below. The dispersion was prepared using the same production method as that used for dispersion A. - Tipaque PF740 (a white pigment, silica treatment): 1.0%, 2.0% alumina treatment, manufactured by Ishihara Sangyo Kaisha, Ltd.): 40 parts Ajisper PB821 (a pigment dispersant), manufactured by Aj inomoto-Fine-Techno Co. , Inc.): 2 parts - Phenoxyethyl acrylate: 58 parts Example 1 The raw materials shown in Table 1 were mixed together in sequence, starting with the material in the upper block of the frame. After mixing for two hours, all the raw materials, except for the pigment, were confirmed as being dissolved, and the mixture was then filtered through a membrane filter, thereby removing the coarse particles and completing the preparation of the ink. Thick particles can cause head blockages. Using an ink discharge apparatus, the ink was discharged to a polycarbonate substrate (Panlite, manufactured by Teijin Ltd., thickness: 1 mm) in sufficient quantity to generate a film thickness of 10 um. After discharge, the ink was cured by ultraviolet irradiation using an ultraviolet irradiation apparatus manufactured by Harrison Toshiba Lighting Co. , Ltd. (1200 W / cm, a high pressure mercury lamp, conveyor speed: 5 m / min, 1 pass), thus forming a cured film (film thickness: 10 um). In addition, in order to measure the physical properties of the cured film alone, a cured film (film thickness: 10 um) was also prepared under the same conditions as above, discharging the ink to a polyethylene substrate and then curing the ink. After standing for 24 hours, the cured film was gently peeled off from the polyethylene substrate. Example 2 to Example 5 Using the same method as example 1, inks were prepared using the formulations shown in Table 1, and the inks were then printed and cured to form films formed. Comparative Examples 1 to 4 Using the same method as Example 1, inks were prepared using the formulations shown in Table 1, and the inks were then printed and cured to form cured films. Evaluation Methods (Stretch Capacity) The cured film on the polycarbonate substrate was drilled to a lever form, together with the substrate, using a puncture cutter (manufactured by Dumbbell Co., Ltd.), thereby forming a Test piece (15 x 120 mm). The test piece obtained in this way was heated to 170 ° C and then subjected to a stress test, with the substrate still fixed, using a Tensilon (UCT-1T, manufactured by Orientec Co., Ltd.). Because the securing of the fracture point of the cured film based on the variation of tension obtained from the load cell was difficult, the fracture point was taken as being the point where the surface of the cured film was visually confirmed from have fractured. (Hardness) The hardness of the cured film prepared on the polycarbonate substrate was measured using a Fischerscope H100C hardness meter (manufactured by Fischer Instruments Co., Ltd.). The measurement was conducted using a Vickers indenter (a square-based pyramid made of diamond with an apex angle of 136 °), and was performed in a controlled chamber at a temperature of 25 ° C using an indentation depth of 1 μm and a Indentation time of 30 seconds. The values obtained by repeating the same measurement at 10 random locations through the same cured film surface were averaged, and the Martens hardness value was then determined. (Elastic Storage Module, Glass Transition Temperature) The cured film prepared on the polyethylene substrate was allowed to stand for 24 hours and then cut precisely to a width of 5 mm and a length of 30 mm, and the film cured then it was gently peeled from the substrate and was measured using a DMS6100 8fabircado apparatus by Seiko instruments Inc.). The measurement conditions included a measurement vibration amplitude of 1 Hz, a heating rate of 2 ° C / min and a temperature scale of -30 to 180 ° C. The maximum upper temperature for Tan d was determined from the resulting profile and used as the glass transition temperature. In addition, the value of E 'for the scale from 100 to 150 ° C was read from the profile.

(Adhesion) The cured film on the polycarbonate substrate was cross cut at 1 mm intervals to form a 100 frame grid, and a cellophane tape adhered to the frames. After rubbing the surface of the cellophane tape with an eraser to ensure that the cellophane tape was bonded satisfactorily to the cured film, the cellophane tape was peeled off at a 90 ° angle. The adhesion was evaluated on the basis of the degree of adhesion of the cured film to the substrate. The evaluation criteria were as shown below. A: Absolutely no detachment of the 100 frames was observed. B: even when all the tiles remained fixed, some damage was visible to the edges of the squares C: from 1 to 49 of the 100 squares came off? D: from 50 to 99 of the 100 squares were removed E: all 100 pictures came off. In Examples 1 to 5, because the proportion of monofunctional monomer was not less than 95% and the stretching capacity exceeded 120%, or because the monofunctional monomer ratio was not less than 9% and the value of E 'was controlled within a scale of 1 x 104 to 5 x 107 Pa, were able to obtain inks with superior adhesion, work capacity, abrasion resistance and rub resistance. In addition, as a result of controlling the martens hardness to a value of not less than 160 N / mm2, inks with superior abrasion resistance and rub resistance were obtained. In any case, because the stretch capacity exceeds 120%, the cured films exhibit superior process stretching ability to the cured films obtained using ink jet printing, conventional silk stencil or offset UV printing techniques, what represents a significant technical improvement. Because the inks of Examples 1 to 5 do not contain oligomers, they exhibit a low viscosity and superior discharge stability, and were also found not to cause head corrosion. Further, in Comparative Examples 1 to 4, because the mixing amount of the polyfunctional monomer was high and the drawing capacity was 120% or less, or because the mixing amount of the polyfunctional monomer was high and the value of E 'was also designed to be elevated, cracking or rupture occurred not only during the stretching process that required a large degree of deformation, but also during processing such as drilling or bending processes that required comparatively small deformation. In addition, the adhesion was also low for the comparative examples 2 and 4, and the hardness value was low for the comparative examples 3 and 4, meaning that the abrasion resistance and rub resistance were lower, and none of them was suitable for use within real production processes. Additionally, when the inks of Examples 1 to 4 were combined as a set, and process printing was conducted (yellow, magenta, cyan, black), the stretch capacity was 100%. Additionally, the value for Martens hardness was 195 N / mm2. The ability to stretch, abrasion resistance and rub resistance and the like all exhibited satisfactory performance. Further, even when an ink in the ink set comprising the inks of examples 1 to 4 was replaced with an ink of one of the comparative examples 1 to 4, and the process printing was then conducted, then the stretch ability It did not reach 70%. Only those cases in which all the color inks used within the ink set exhibited satisfactory stretch ability resulted in an adequate level of stretch capacity for the ink set, and said ink sets exhibited superior stretch processing properties. In addition, the printed articles obtained by conducting printing using the inks described in Examples 1 to 5 were subjected to layer coating using the ink of any of Reference Examples 1 or 2, which did not contain coloring component. All the resulting printed articles exhibited a high degree of stretch ability exceeding 120%, and showed excellent stretch processing properties. The cured products obtained using the active-energy beam curable inks for ink-jet printing in accordance with the present invention exhibited superior workability, excellent abrasion resistance and superior rub resistance and adhesion. As a result, potential applications for UV printing, which has conventionally suffered from workability problems, can be greatly expanded. The active energy beam curable ink for ink jet printing in accordance with the present invention is particularly suitable for interior or exterior printing applications where processing is used to enhance attractiveness, printing to CD or DVD discs or the like. similar, and printing to waterproof substrates focused on printing to flexible substrates. [Picture 1] Kayarad R-128H: 2-hydroxy-3-f-enoxopropyl acrylate (manufactured by Nippon Kayaku Col., Ltd.) PEG400 diacrylate: nonaethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) = Kayarad R-551: ethoxylated or propoxylated bisphenol A diacrylate (manufactured by Nippon Kayaku Co., Ltd.) Irg907: 2-methyl-l- [4- (methyl) phenyl] -2-morpholinopropan-l-one (manufactured by Ciba Specialty Chemicals Inc. ) Irg819: bis (2,, ß-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Cdiba Specialty Chemicals Inc.) BHT: dibutylhydroxytoluene (manufactured by Roida, Ltd.) Solbin CL: modified vinyl chloride resin - vinyl acetate ( manufactured by Nissin Chemical Industry Co., Ltd.) Mixing Quantities (Parts) INDUSTRIAL APPLICABILITY In accordance with an ink jet-curable active ink for inkjet printing of the present invention, a cured film and printed article can be obtained which exhibit excellent stretch and adhesion processing properties of the cured film, as well as superior abrasion resistance and rub resistance. The active energy beam curable ink for ink jet printing according to the present invention can be favorably used within applications involving conducting printing to flexible substrates, and applications in which the substrate is subjected to deformation after the printing. inkjet printing.

Claims (15)

1. CLAIMS 1.- An active energy beam curable ink comprising polymerizable monomers, wherein in relation to a total of all the polymerizable monomers, the polymerizable monomers comprise from 95 to 99.99% by weight of a monofunctional monomer and from 0.01 to 5 % by weight of a polyfunctional monomer, and a cured 10-μm thick film formed using the active energy beam curable ink exhibits a stretch capacity exceeding 120% when stretched at a temperature of 170 ° C at a rate of effort of 2 / m? n.
2. 2. - An active energy beam curable ink comprising polymerizable monomers, wherein in relation to the total of all the polymerizable monomers, the polymerizable monomers comprise from 95 to 99.99% by weight of a monofunctional monomer and from 0.01 to 5% in weight of a polyfunctional monomer, and a cured 10-μm thick film formed using the active energy beam curable ink exhibits a storage elastic modulus (E ') within a scale of 1 × 10 4 to 5 × 10 7 Pa to a oscillation frequency of 1 Hz and a temperature within a range of 100 to 150 ° C.
3. 3. The active energy beam curable ink according to any of claim 1 or 2, wherein a Martens hardness of the cured film of 10 um in thickness is not less than 160 N / mm2.
4. 4. The active energy beam curable ink according to any of claims 1 to 3, wherein a glass transition point of the cured film of 10 um in thickness is not less than 25 ° C.
5. 5. An active energy beam curable ink according to any of claims 1 to 4, wherein with respect to a total of all the polymerizable monomers, the polymerizable monomers comprise from 50 to 100% by weight of monomers having a cyclical structure.
6. 6. The active energy beam curable ink according to any of claims 1 to 5, wherein with respect to a total of all the polymerizable monomers, the polymerizable monomers comprise from 30 to 99.99% by weight of a selected monomer of the group consisting of 2-phenoxyethyl acrylate, ethylene oxide adduct monomers of 2-phenoxyethyl acrylate, and propylene oxide adduct monomers of 2-phenoxyethyl acrylate.
7. 7. The active-energy beam curable ink according to any of claims 1 to 6, wherein with respect to a total of all the polymerizable monomers, the polymerizable monomers comprise from 1 to 30% by weight of acrylate of 2. -hydroxy-3-phenoxypropyl.
8. 8. The active energy beam curable ink according to any of claims 1 to 7, further comprising a pigment.
9. 9. The active energy beam curable ink according to any of claims 1 to 8, wherein the active energy beam is ultraviolet radiation.
10. 10. The active energy beam curable ink according to any of claims 1 to 9, wherein a molecular weight of the polyfunctional monomer is less than 2,000.
11. 11. The active energy beam curable ink according to any of claims 1 to 10, wherein the polyfunctional monomer is a bifunctional monomer.
12. 12. An ink set comprising at least four active energy beam curable inks according to any of claims 8 to 11, wherein the pigments contained within each of the curable inks with active energy beam are mutually different
13. 13. - An ink set according to claim 12, wherein the four active energy beam curable inks are yellow, magenta, cyan and black inks.
14. 14. A cured film formed using the active energy beam curable ink according to any of claims 1 to 11.
15. 15. A printed article comprising a printing substrate and the cured film according to claim 14.