JP2004339480A - Radiation-curable ink composition suitable for inkjet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new radiation-curable ink for an inkjet printing which is curable radically and/or cationically. <P>SOLUTION: The radiation-curable ink composition contains at least one kind of an initiator and at least one kind of a polygonal oligomer silsesquioxane (POSS) expressed by the experimental formula: [R(SiO<SB>1.5</SB>)]<SB>n</SB>, wherein, n is 4, 6, 8, 10, 12, 14, 16 or a number greater than 16, each R is independently hydrogen, an inorganic group, alkyl group, alkylene group, aryl group, arylene group or a non-heterocyclic group-containing organic functional derivative of alkyl, alkylene, aryl or arylene group. A method for obtaining a colorless, monochrome or multicolor inkjet image including a stage in which one or more flow of ink drops having the above composition are sprayed on an inkjet ink receiving material and the obtained image is subjected to radiation curing is provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to radiation curable ink compositions containing polyhedral oligomeric silsesquioxanes (POSS).

  Ink jet printing has become the technology of choice for short run printing. A recent overview of the progress and trends of ink jet printing is given in Non-Patent Document 1, the content of which is incorporated herein by reference.

  In ink jet printing, droplets of ink fluid are ejected directly onto the ink receptor surface without physical contact between the printing device and the receptor. The printing device includes a mechanism for electronically storing the print data and ejecting the drops image-wise. Printing is performed by moving the printhead across the paper or vice versa.

  The ejection of the ink drops can be performed in several ways. In the first type of method, a continuous drop stream is created by applying a pressure wave pattern. This method is known as continuous ink jet printing. In a first aspect, the stream of droplets is electrostatically charged, deflected, and collected into droplets that are collected and those that remain uncharged, do not deflect, and form an image. Alternatively, the charged and deflected stream forms an image, and the uncharged undeflected jet is collected. In this variant of continuous ink jet printing, several jets are deflected to different degrees, thus recording the image (multi-deflection system).

  According to the second method, the ink droplets can be formed "on demand" ("DOD" or "drop on demand" method), in which the droplets form an image on a receiver. The printing device ejects the drops only when used, thereby avoiding the complexity of drop charging, deflection hardware and ink collection. In drop-on-demand printing, ink is applied by pressure waves created by the mechanical movement of a piezoelectric transducer (the so-called "piezo method") or by discrete heat pulses (the so-called "bubble jet" or "thermal jet" method). Drops can be formed.

Ink compositions for ink jets typically comprise the following components: dyes or pigments, water and / or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders and preservatives. Agent. Roughly the ink composition:
Water-based inks, drying mechanisms include absorption, penetration and evaporation;
Oil-based inks, drying includes absorption and penetration;
Solvent-based inks, drying mainly involves evaporation;
Hot melt or phase change inks, in which case the ink vehicle is liquid at the injection temperature, but solid at room temperature, drying is replaced by solidification;
UV-curable inks, in which case drying can be displaced by polymerization.

  While the first two types of ink compositions require a somewhat absorbing receiving medium, solvent-based inks, hot melt inks or UV-curable inks are more suitable for non-absorbent substrates.

US Pat. No. 5,077,059 is an important basic patent for ink compositions for ink jets that meet the demand for low solvent content and contain UV-curable compounds. It discloses a jet drop printing method using a radiation curable jet printing ink, which comprises: (a) 5 to 80% of low molecular weight polyfunctional, which polymerizes and cures when irradiated, from one or more orifices; Basic ethylenically unsaturated materials, (b) 0-90%, low molecular weight monofunctional ethylenically unsaturated materials for viscosity control, cured film flexibility and adhesion strength, (c) 0-15% % Of a reactive synergist that enhances the effectiveness of the cure, (d) 0.2-10% of a solvent dye colorant that does not interfere with the effectiveness of the cure, (e) 0.5-15% of a conductive Less than about 15 centipoise, comprising: (f) 0.2-20% of a photoinitiator and (g) 0-30% of a mixture of an organic polar solvent compatible with the mixture. Viscosity, resistivity of about 50-5000 ohm-cm and about Ejecting a radiation curable ink composition having a surface tension of 0 to 70 dynes / cm at a high speed so that the stream of the ink composition flowing out of the ore or orifices breaks into droplets; The stream is passed through a charge ring, thereby charging the drops differently, selectively deflecting the differently charged drops, and positioning to receive a portion of the differently charged drops. Directing them onto a coated paper substrate, depositing at least a portion of the drops in a pattern on the paper substrate, and applying the radiation curable jet printing under a radiation source to the substrate having the pattern deposited thereon. Allow the ink to pass for a sufficient time to cure, thereby creating a pattern on the substrate that is light absorbing, smear resistant and waterproof at infrared wavelengths. Including forming
U.S. Pat. No. 6,037,064 discloses jet ink compositions for making visible indicia of a substrate prepared from a polymerizable resin, a colorant and a solvent, wherein the ink composition has a pH of 1 at 25.degree. 0.5 to 25 mPa. s having a viscosity of less than 4000 ohm-cm and a sound velocity of from 800 to 2,500 meters per second, wherein the ink composition comprises (A) 10 to 70% by weight of (i) a resin. Diglycidyl ether of bisphenol A as the monomer, (ii) polyepoxidized phenol or cresol novolax, (iii) diepoxide ether or ester having two epoxycycloalkyl groups, (iv) polyglycidyl ether of polyhydric alcohol And (v) an epoxy resin selected from the combination thereof, which is liquid at room temperature or has a Durran melting point of less than 100 ° C. and an epoxy equivalent of less than 300; (B) 1 to 12% by weight of an epoxy resin Resin can polymerize rapidly and is exposed to sources of radiation such as ultraviolet light A photoinitiator that provides a Lewis acid effective to initiate the polymerization reaction; (C) less than 2% by weight of a colorant that does not adversely affect the curing of the epoxy resin; Aliphatic alcohols having carbon atoms, alkyl ketones having 2-5 carbon atoms, aromatic hydrocarbons of benzene, toluene and xylene, propylene carbonate, ethylene glycol ether having 3 or 4 carbon atoms, 2-4 Includes solvent blends that are volatile at ambient conditions and contain a solvent selected from alkyl acetates having one carbon atom or a combination of these solvents.

  Patent Document 3 discloses that as a main component, the formula (A):

[Wherein, R ₁ is a hydrogen atom or a methyl group, and n is an integer of 1 to 20]
A polyisocyanate compound having a hydroxyl group-containing (meth) acrylate and having at least two (meth) acryloyl groups and at least two urethane bonds in one molecule. (C) discloses an ultraviolet curable ink composition containing (B) a radically polymerizable low molecular weight compound and (C) a photopolymerization initiator.

  U.S. Pat. No. 6,077,086 provides printing means including a thermal ink jet printing device for delivering ink to a substrate; the thermal ink jet printing device is provided with about 12-80% by weight of an ultraviolet light curable adhesive; Providing an ultraviolet light curable ink composition comprising a combination of 3 to 10% by weight of a dye pigment and about 10 to 40% by weight of a solvent; and removing the ink composition from the thermal ink jet printing apparatus. A printing method comprising: delivering to a substrate; applying the ultraviolet light to the substrate having the ink composition thereon in an amount sufficient to form a permanent image on the substrate from the ink composition. are doing.

  US Pat. No. 5,077,086 discloses that the colorant, the polar conductive component and the conductive component as the main component of the liquid phase comprise one or more polymerizable monomers in which it is soluble, optionally UV-A light-curable. Ink jet inks are disclosed.

  US Pat. No. 6,052,953 discloses non-conductive inks which can be optionally UV-A light curable, comprising a colorant and one or more polymerizable monomers as main components of the liquid phase. I have.

  Patent Document 7 discloses a) comprising at least two types of acrylate resin components, wherein the first acrylate resin component is an aromatic acrylate resin containing at least one side chain carboxyl group, and the second resin acrylate component is acrylic. Disclosed is an ink composition for use in ink jet printing, comprising a resin composition that is a functionalized epoxy monomer or dimer; b) a photoinitiator; and (c) an organic carrier.

  U.S. Pat. No. 6,037,064 discloses an ink containing a pigment, a water-soluble resin, a water-soluble monomer to be cured by application of energy, and a photopolymerization initiator in an aqueous liquid medium.

  US Pat. No. 6,077,086 combines a) water with a content of about 20% to 75% by weight; b) a water-miscible ultraviolet light curable polymerizable material; c) a photoinitiator; and d) a colorant. UV curable ink-jet ink compositions, wherein the viscosity of the ink-jet ink composition is about 2 to 40 centipoise.

  Patent Document 10 discloses an ink-jet ink containing a colorant and a liquid component containing water and at least one compound selected from the group consisting of epoxides and vinyl ethers.

  U.S. Patent No. 6,038,086 discloses a radiation-curable ink jet composition comprising 80% to 95% of a multifunctional alkoxylated and / or polyfunctional polyalkoxylated acrylate monomer material; and a photoinitiator. I have.

Patent Document 12 discloses (A) 100 parts by weight of a compound having an ethylenically unsaturated bond, (B) 0.001 to 5 parts by weight of a general formula (1): D ⁺ .A ₁ ⁻ (1). Wherein D ⁺ is a cationic dye having absorption in the visible light region of 400 to 740 nm, A ₁ ⁻ is a cationic dye having an absorption in the visible light region of 400 to 740 nm, and (C) 0 0.005 to 10 parts by weight of the general formula (2):

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group capable of having a substituent, an aryl group capable of having a substituent, an allyl group capable of having a substituent, An aralkyl group that can have a substituent, an alkenyl group that can have a substituent, an alkynyl group that can have a substituent, a silyl group that can have a substituent, a heterocyclic group, or a halogen atom; Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, a sulfonium cation, an oxosulfonium cation, an iodonium cation or a metal cation]
And (D) 0.01 to 10 parts by weight of an ultraviolet light radical polymerization initiator which generates radicals when absorbing light having a wavelength of 200 to 400 nm, wherein the ultraviolet light The radical polymerization initiator has the general formula (9):

[Wherein, Ar represents an aryl group that can have a substituent, and X represents a phosphinoyl group having a substituent]
Discloses a photocurable composition, which is a compound represented by the formula: U.S. Pat. No. 6,077,064 further discloses, among other monomers that can be used in the photocurable composition: (meth) acrylic polyfunctional polyorganosilsesquioxanes.

  Patent Document 13 discloses an active energy beam-curable composition including a photo-cationic polymerizable substance; a photo-cationic polymerization initiator; and an oxetane compound. U.S. Patent No. 6,077,064 specifically discloses oxetanyl silsesquioxane.

  U.S. Pat. No. 6,086,086 discloses a polyhedral silsesquioxane compound present in a proportion of about 0.1 to 30% by weight based on the total weight of the hot melt ink composition; (b) an ink colorant; (D) a tackifier; and (e) a hot melt ink composition comprising a combination of a viscosity modifier.

  Patent Document 15 discloses that at least one of (a) a compound having two reactive silyl groups and (b) a compound having at least three reactive silyl groups; an acid generation catalyst containing an onium salt; and a pigment or pigment Disclosed is a cure-on-demand curable ink composition comprising a homogeneous mixture of chip storage stability, wherein "curable" means that the reactive silyl group is in the presence of moisture. To form a compound having a silanol group, which reacts in the presence of an activating catalyst to form a -Si-O-Si- bond, or the silanol group reacts in the presence of an activating catalyst. To form a -Si-O-Si- bond. These moisture-curable compositions cure in the presence of moisture to produce a crosslinked material, which can be obtained from the atmosphere, from a substrate, or added to the composition.

  U.S. Pat. No. 6,059,064 discloses a structured hydrophilic surface having ridges and depressions, wherein the surface shows polyhedral oligomeric silicon-oxygen cluster units, which at least partially form a ridge. I do. U.S. Pat. No. 6,037,088 further teaches that polyhedral oligomeric silicon-oxygen cluster units have the structure I

Wherein the groups R are the same or different and are hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group.
Disclosed is a structured hydrophilic surface characterized by a fully condensed silasesquioxane represented by the formula R ₈ Si ₈ O ₁₂ having the formula:

In short, radiation-curable ink compositions generally comprise one or more radiation-curable prepolymers or oligomers, a radiation-curable monomer or a reactive diluent, and optionally one or more photoinitiators. , Coloring agents and other additives. Polymerizable monomers are generally suitable for achieving the low viscosities required for ink jet printing without introducing significant amounts of water or other solvents, but are radiation curable both radically and cationically The problem is to find a suitable monomer for use in a suitable ink.
Prior Art To date, the following are relevant documents relating to the patentability of the present invention:
Patent Document 1, issued December 1, 1981,
Patent Document 2, published on February 9, 1983,
Patent Document 3, issued on July 14, 1987,
Patent Document 4, issued December 18, 1990,
Patent Document 5, published January 8, 1992,
Patent Document 6, published May 5, 1992,
Patent Document 7, issued on December 14, 1993,
Patent Document 9, issued April 22, 1997,
Patent Document 10, June 24, 1997 Patent,
Patent Document 11, published on August 28, 1997,
Patent Document 12, issued on August 29, 2000,
Patent Document 13, published on April 16, 2003,
Patent Document 14, issued on August 7, 2001,
Patent Document 15, issued on October 8, 2002,
Patent Document 16 published on June 26, 2003.
Hue P.S. Le, Journal of Imaging Science and Technology, Vol. 42 (1), Jan / Febr 1998 U.S. Pat. No. 4,303,924 EP-A-0 071 345 U.S. Pat. No. 4,680,368 U.S. Pat. No. 4,978,969 European Patent Application Publication No. 0 465 039 EP-A-0 540 203 U.S. Pat. No. 5,270,368 European Patent Application Publication No. 0 658 607 U.S. Pat. No. 5,623,001 U.S. Pat. No. 5,641,346 WO 97/31071 pamphlet US Patent No. 6,110,987 EP-A-1 302 499 US Patent No. 6,270,561 US Pat. No. 6,461,419 WO 03/052014 pamphlet

Aspects of the Invention One aspect of the present invention is to provide novel radiation curable ink compositions.

  Another aspect of the present invention is to provide novel radiation curable ink compositions that can be cured radically and / or cationically.

  A further aspect of the present invention is to provide a radiation curable ink for ink jet printing, which can be cured radically and / or cationically.

  These and other aspects of the invention will be apparent from the description below.

SUMMARY OF THE INVENTION Surprisingly, it is surprisingly indicated by the following empirical formula [R (SiO _1.5 )] _n , where n = 4, 6, 8, 10, 12, 14, 16, and larger numbers. Wherein each R is independently hydrogen, an inorganic group, an alkyl group, an alkylene group, an aryl group, an arylene group or a non-heterocyclic group-containing organic-functional derivative of an alkyl, alkylene, aryl or arylene group. It has been found that radiation curable ink compositions comprising polyhedral oligomeric silsesquioxanes (POSS) can be radically and / or cationically cured.

Aspects of the invention comprise at least one initiator and at least one polyhedral oligomeric silsesquioxane (POSS) represented by the empirical formula [R (SiO _1.5 )] _n , wherein: And n is 4, 6, 8, 10, 12, 14, 16, or a larger number, and each R is independently hydrogen, an inorganic group, an alkyl group, an alkylene group, an aryl group, an arylene group or an alkyl, alkylene Radiation-curable ink compositions which are non-heterocyclic group-containing organic-functional derivatives of aryl, aryl or arylene groups.

  Aspects of the invention include colorless, comprising jetting one or more streams of ink droplets having the composition described above onto an ink-jet ink receiving material and subjecting the resulting image to radiation curing. It is also realized by a method for obtaining a monochrome or multicolor ink jet image.

Further aspects and advantages of the present invention will become apparent from the description below.
Detailed description of the invention
Definitions The term radiation means all forms of electromagnetic and high energy ionizing radiation, including IR-light, visible light, UV-light, X-rays, gamma rays, beta rays and accelerating electrons.

  The term derivative used in connection with a particular polymer refers to alkyl, alkoxy, alkyloxyalkyl, carboxy, alkylsulfonato and their variants substituted with carboxyester groups.

  The term heterocyclic as used in disclosing the present invention means a cyclic structure consisting of at least four ring atoms, at least one of which is not carbon and does not contain an epoxy group.

  The term photoinitiator includes both cleavable and non-cleavable photoinitiators. Cleavable photoinitiators can independently generate radicals when exposed to UV light. Non-cleavable photoinitiators require the presence of a hydrogen donor (a tertiary amine, often called a synergist or co-initiator) to provide the radicals.

  The term tackifier as used in disclosing the present invention refers to an additive for imparting tack to otherwise non-tacky materials. An example of a widely used tackifier is Cellyn 21-E, a phthalate ester of industrial hydroabiethyl alcohol from Eastman.

  The term aqueous medium means a medium containing water and a water-miscible organic solvent containing 50% to 100% water by weight.

  The term solvent medium means a medium that contains an organic solvent and can also contain water dissolved at a concentration of less than 50% by weight.

  The term colorant includes both dyes and pigments.

  According to the present invention, the term dye means a colorant having a solubility of 10 mg / L or higher in the medium to which it is applied and under the relevant ambient conditions.

  The term pigment is used in DIN 55943, the description of which is hereby incorporated by reference, which is substantially insoluble in the application medium under the relevant ambient conditions and thus contains less than 10 mg / L It is defined as an inorganic or organic, chromatic or achromatic colorant having solubility.

Silsesquioxane Aspects of the invention include at least one initiator and at least one polyhedral oligomeric silsesquioxane (POSS) represented by the following empirical formula [R (SiO _1.5 )] _n. Where n = 4, 6, 8, 10, 12, 14, 16, and a larger number, and each R is independently hydrogen, an inorganic group, an alkyl group, an alkylene group, an aryl group, an arylene group. Alternatively, it is realized by a radiation curable ink composition that is a non-heterocyclic group-containing organic-functional derivative of an alkyl, alkylene, aryl or arylene group.

  The structure of silsesquioxane has been reported as a random, ladder, cage and partial cage structure. Baney et al. In Chemical Review, 1995, 95, 1409-1430 and in the references cited therein, and in Guizhi Li et al. By the Journal of Inorganic and Organometallic Polymers, vol. 11 (3), September 2001, page 123-154 and the references cited therein discuss the synthesis and properties of silsesquioxanes in more detail. Silsesquioxanes having a special cage structure have been called polyhedral oligomeric silsesquioxanes, POSS. Such cage structures are described in the Journal of Inorganic and Organometallic Polymers, Vol. 11 (3), September 2001, page 124, Scheme 1 (structure cf).

  According to a first embodiment of the radiation-curable ink composition according to the invention, the polyhedral oligomeric silsesquioxane contains at least one R-group comprising a curable functional group.

  According to a second aspect of the radiation-curable ink composition according to the present invention, the polyhedral oligomeric silsesquioxane is selected from the group consisting of epoxides, aziridines, acrylates, methacrylates, acrylamides, methacrylamides, olefins and styryl groups. It contains at least one R-group containing a curable functional group.

  According to a third aspect of the radiation-curable ink composition according to the present invention, the silsesquioxane has a special cage structure represented by Formulas I-III or a partial cage structure represented by Formula IV:

In the formula, R1 to R12 represent hydrogen and an inorganic or organic substituent, and at least one of the R1 to R12 groups contains a curable functional group.

Polyhedral oligomeric silsesquioxanes (POSS) have two unique features: (1) The chemical composition (RSiO _1.5 ) is intermediate between the compositions of silica (SiO ₂ ) and silicone (R ₂ SiO). (2) POSS molecules are physically large, ranging from about 1-3 nm. This hybrid (organic / inorganic) composition of the POSS technology allows it to occupy a unique and dramatically enhanced property space for ordinary hydrocarbons and inorganic compounds. An important benefit is that it provides the material preparation with excellent thermal, mechanical and oxidative stability and fire resistance. This is largely due to the inorganic core of the POSS molecule. The organic portion of their composition provides improved compatibility with the resins present, thereby allowing their easy incorporation into ordinary plastics. The POSS-functionalized monomers according to the invention have a hybrid inorganic-organic three-dimensional structure containing 1 to 8 reactive organic functional groups.

  Most POSS-functionalized monomers contain seven non-reactive organic groups along with one unique functional group. By varying the functional groups and the seven non-reactive organic groups, a large number of POSS functionalized monomers can be made to meet almost any requirement. Monofunctional POSS monomers can be introduced by copolymerization or grafting, and multifunctional POSS monomers can be used as effective crosslinkers. POSS-functional monomers react similarly to standard organic monomers in polymerization, grafting and crosslinking reactions. Although they react similarly to simple organic monomers when incorporated into polymeric materials, POSS-functionalized monomers provide significant improvements in the thermal, mechanical and gas separation properties of ordinary plastics.

  Silsesquioxane (POSS) according to the present invention is commercially available from companies such as Hybrid Plastics, Fountain Valley, CA 92708-6117, USA. Representative examples of the compounds corresponding to the general formulas I to IV are shown in Table 1 below, but are not limited thereto. Compared to the state-of-the-art acrylates and methacrylates used in UV-curable inks, the compounds according to the invention have at least one out-of-frame functional group introduced into the molecule and are useful for preparing inks. And new opportunities for printing on non-absorbent substrates such as metal and ceramic surfaces.

  A variety of monomers suitable for use in the radiation curable ink composition according to the present invention are described in US Pat. No. 6,100,417, US Pat. No. 5,942,638, US Pat. No. 5,939,576; U.S. Pat. No. 5,589,562; U.S. Pat. No. 5,484,867; and U.S. Pat. No. 5,412,053; Baney et al. In Chemical Review, 1995, 95, 1409-1430 and by Guizhi Li et al. By the Journal of Inorganic and Organometallic Polymers, Vol. 11 (3), September 2001, page 123-154, and can be prepared according to the synthetic methods described in the above review. In addition, many monomers are available from Hybrid Plastics Inc. , Fountain Valley, California, USA (see code shown in parentheses).

Initiator According to a fourth aspect of the radiation-curable ink composition according to the present invention, the initiator is a photoinitiator.

  The photoinitiator can be classified into a compound suitable for cationic polymerization, a compound suitable for radical polymerization, and a compound for initiating radical and / or cationic polymerization depending on conditions.

  Information on suitable photoinitiators can be found in K. T. Oldring (ed.), "Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints: Vol. 3" Photoinitiator's Foresight Radiation Foresight Radiation Foresight, Inc. Allen, "Photoinitiators for UV and visible Curing of coatings: mechanism and properties", Journal of Photochemistry and Photobiology, Aomori, Japan. y 100 (1996) 101-107; found in JV Koleske, "Aradiation-Cure Primer", Journal of Coatings Technology, Vol 69, No. 866, March 1997, 29-38.

  Disclosures specifically mentioning photoinitiators for cationic polymerization include those described in J.A. V. Crivello, "The Chemistry of Photoacid Generating Compounds", Proceedings of the ACS Division of Polymeric Materials, Science and Engineering. 61, pages 62-66, (1989); V. Crivello and J.M. H. W. Lam Author, "Complex Triarylsulfonium Salt Photoinitiators I.The Identification, Characterization, and Synthesis of a New Class of Triarylsulfonium Salt Photoinitiators," Journal of Polymer Science, Polymer Chemistry Edition, Vol. 18, 2677-2695 (1980); V. Crivello and J.M. H. W. Lam Author, "Complex Triarylsulfonium Photoinitiators II.The Preparation of several New Complex Triarylsulfonium salt and the Influence of Their Structure in Photoinitiated Cationic Polymerization," Journal of Polymer Science, Polymer Chemistry Edition, Vol. 18, pages 2697-2714 (1980); V. Crivello and J.M. H. W. Lam, "Diaryliodonium Salts A New Class of Photoinitiators for Catic Polymerization," Macromolecules, Vol. 10, pages 1307-1315 (1977); V. Crivello, J. et al. L. Lee and D.S. A. Conlon, "Developments in the design and Applications of Novel Thermal and Photochemical Initiators for Catic Polymerization", Makromol. Chem. Macromolecular Symposium, Vol. 13/14, pages 134-160.

  According to a fifth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises diaryl iodonium salts and their derivatives, optionally alkyl and / or aryl substituted, optionally Light selected from the group consisting of triarylsulfonium salts that can be substituted with alkyl and / or aryl and derivatives thereof, and triphenylphosphonium salts that can be optionally substituted with alkyl and / or aryl and derivatives thereof Contains an initiator.

  Yet another photoinitiator suitable for cationic polymerization is C.I. Priou et al. By The Conference Proceedings of Radtech Europe '97, p. Triarylsulfonium-tetrakis (pentafluorophenyl) -borate (RHODORSIL 2074 supplied by Rhone-Poulenc Chimie) described in 314 and onium salts with special light absorbing properties disclosed in WO 97/47660 It is.

  Photoinitiators suitable for radical polymerization include LUCIRIN LR8953 (from BASF), IRGACURE 819 and 907 (from Ciba-Geigy), DAROCUR 4865 (from Ciba-Geigy) and isopropylthioxanthones, such as QUANTACURE ITX (Rahn) Is included. Useful polymeric or oligomeric photoinitiators for radical polymerization are described in Visconti et al. And W.S. Davies et al. Are copolymerizable photoinitiators as discussed in Radure Coatings and Inks, Curing and Performance Conference (Harrogate, 22-23 June 1998), respectively. Examples of such photoinitiators are, for example, ESACURE KIP 150, ESACURE KT 37 and KT 55 (from Lamberti) and acrylated IRGACURE 2959 or IRGACURE 2959 modified melamine acrylates (from Ackros Chemicals).

  Still other suitable initiators are disclosed in the following patents, which are incorporated herein by reference: US Pat. No. 4,683,317, US Pat. U.S. Pat. No. 4,378,277, U.S. Pat. No. 4,279,717, U.S. Pat. No. 4,480,368, U.S. Pat. No. 4,443,495, U.S. Pat. No. 303,924; U.S. Pat. No. 4,751,102; U.S. Pat. No. 4,334,970; U.S. Pat. No. 5,270,368; U.S. Pat. No. 724, EP 0 540 203, EP 0 568 607 and EP 0 659 039.

  According to a sixth aspect of the radiation-curable ink composition according to the present invention, the initiator is a photoinitiator, and the radiation-curable ink further contains a co-initiator, also called an initiator synergist. The initiator synergist is preferably of the amine type, for example of the aminobenzoate type.

  According to a seventh embodiment of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises a co-form of the aminobenzoate type together with a main photoinitiator selected from the group consisting of benzophenone and xanthone / thioxanthone compounds. -Contains an initiator. More examples can be found in the Oldring reference cited above. Apart from curing with UV-light, it is also possible to use a visible light curing system, for example using a camphorquinone dimethylaminoethyl methacrylate (DMAEMA) system.

  According to an eighth embodiment of the radiation-curable ink composition according to the invention, the radiation-curable ink is further provided in an amount of 0.2 to 20% by weight of the ink, preferably 1 to 10% by weight of the ink composition. Contains a photoinitiator.

  According to a ninth embodiment of the radiation-curable ink composition according to the present invention, the radiation-curable ink is further provided in an amount of 0.2 to 20% by weight of the ink, preferably 1 to 10% by weight of the ink composition. Contains a co-initiator.

Colorant According to a tenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one colorant. Any colorant can be used to impart the desired color to the ink.

  According to an eleventh aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one dye.

  According to a twelfth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one pigment.

  According to a thirteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one inorganic pigment.

  According to a fourteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one colorant, wherein the colorant is a dispersed pigment or a solid solution of the pigment.

  According to a fifteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises a combination of at least one pigment and at least one dye.

  A variety of organic and inorganic dyes and pigments, alone or in combination, can be selected for use in the ink compositions of the present invention. The pigment particles must be small enough to allow free flow of the ink through the ink jet printing device, especially at the injection nozzle, which usually has a diameter in the range of 10 μm to 50 μm. Pigment particle size also has an effect on the stability of the pigment dispersion, which is important throughout the life of the ink. It is desirable to use small particles also for maximum color density.

  According to a sixteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises 5 nm to 15 μm, preferably 5 nm to 5 μm, more preferably 5 nm to 1 μm and particularly preferably 5 nm to 300 nm. It contains at least one pigment having an average particle size. Pigment particle sizes outside these ranges can, of course, be used as long as the objects of the invention are achieved.

  Very fine dispersions of pigments and their preparation are described, for example, in EP 0 776 952, US Pat. No. 5,538,548, the contents of which are incorporated herein by reference. No. 5,443,628, EP 0 259 130, US Pat. No. 5,285,064, EP 0 429 828 and European Patent No. 0 526 198.

  The pigment can be black, cyan, magenta, yellow, red, blue, green, brown, mixtures thereof, and the like. Suitable carbon black pigments include Cabot Co. Regal 400R, Mogul L, Elftex 320 or Degussa Co. Black FW18, Special Black 250, Special Black 350, Special Black 550, Printex 25, Printex 35, Printex 55, Printex 55, Printex 150T and Pigment Black 7 from Carbon Black. Suitable non-carbon black pigments include C.I. I. Pigment Yellow 17, C.I. I. Pigment Blue 27, C.I. I. Pigment Red 49: 2, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 81: 3, C.I. I. Pigment Red 81: x, C.I. I. Pigment Yellow 83, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Violet 23, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 61, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 52: 1, C.I. I. Pigment Violet 1, C.I. I. Pigment White 6, C.I. I. Pigment Blue 15, C.I. I. Pigment Yellow 12, C.I. I. Pigment Blue 56, C.I. I. Pigment Orange 5, C.I. I. Pigment Black 7, C.I. I. Pigment Yellow 14, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Yellow 55, C.I. I. Pigment Red 41, C.I. I. Pigment Orange 34, C.I. I. Pigment Blue 62, C.I. I. Pigment Red 22, C.I. I. Pigment Red 170, C.I. I. Pigment Red 88, C.I. I. Pigment Yellow 151, C.I. I. Pigment Red 184, C.I. I. Pigment Blue 1: 2, C.I. I. Pigment Red 3, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Red 23, C.I. I. Pigment Red 112, C.I. I. Pigment Yellow 126, C.I. I. Pigment Red 169, C.I. I. Pigment Orange 13, C.I. I. Pigment Red 1-10, 12, C.I. I. Pigment Blue 1: X, C.I. I. Pigment Yellow 42, C.I. I. Pigment Red 101, C.I. I. Pigment Brown 6, C.I. I. Pigment Brown 7, C.I. I. Pigment Brown 7: X, C.I. I. Pigment Black 11, C.I. I. Pigment Metal 1, C.I. I. Pigment Metal 2, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 180, C.I. I. Pigment Red 122, C.I. I. Pigment Red 184, a crosslinked aluminum phthalocyanine pigment and a solid solution of the pigment.

  Suitable pigments are described in Industrial Organic Pigments, Production, Properties, Applications, second edition, W.M. Herbst, K .; Hunger; VCH, 1997. Additional examples of suitable pigments are disclosed in U.S. Patent No. 5,389,133.

  According to a seventeenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises Pigment Yellow 1, 3, 128, 109, 93, 17, 14, 10, 12, 13, 83. , 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22, 23, 17, 210, 170, 188, 185, 146, 144, 176, 57: 1, 184. , 202, 206, 207; Pigment Blue 15: 3, Pigment Blue 15: 2, Pigment Blue 15: 1, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 15: 6, and a carbon selected from Pigment Blue 16; Few Both containing one of the pigment.

  Pigments may or may not be used in the form of a dispersion containing a dispersant, also called a pigment stabilizer. Suitable dispersants include those of the polyester, polyurethane or polyacrylate type, especially in the form of high molecular weight block copolymers, and are typically introduced at a concentration of from 2.5% to 100% by weight of the pigment. You. Suitable dispersants include DISPERBYK type (from BYK Chemie) and SOLSPERSE type (from Zeneca). A detailed list of suitable non-polymeric as well as some polymeric dispersants can be found in McCutcheon's Functional Materials, North American Edition, Manufacturing Conferencing Publishing. , Glen Rock, N.M. J. Pp. 110-129 (1990). Further suitable pigment stabilizers are described in DE 196 36 382, U.S. Pat. No. 5,720,802, U.S. Pat. No. 5,713,993, PCT / GB95 / 02501, U.S. Pat. It is disclosed in U.S. Pat. No. 5,085,689 and British Patent No. 2303376.

  According to an eighteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises from 0.5 to 20 weight percent pigment in the ink composition.

According to a nineteenth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises from 0.5 to 20 weight percent of the dye in the ink composition.

According to a twentieth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further contains 0.5 to 20 weight percent of a colorant in the ink composition.

Can be used in combination with the monomers of the present invention
Other Monomers, Oligomers or Reactive Diluents According to a twenty-first aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one photopolymerizable compound.

  According to a twenty-second aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one photocrosslinkable compound.

  In the radiation curable ink composition according to the present invention, various photopolymerizable and photocrosslinkable compounds can be used in combination with the monomer of the present invention.

  Suitable photopolymerizable compounds are described in German Patent Application No. 400 52 231, German Patent Application No. 3516256, German Patent Application DE 3,516,256, the contents of which are incorporated herein by reference. Patent Application No. 3516257, German Patent Application No. 36 32 657, US Pat. No. 4,629,676, US Pat. No. 6,294,592, WO 97/31071. Includes monomers disclosed in pamphlets and US Pat. No. 6,300,388.

  According to a twenty-third aspect of the radiation-curable ink composition according to the present invention, radiation-curable inks are further described in US Pat. No. 6,310,115, the disclosure of which is incorporated herein by reference. It contains at least one photopolymerizable compound selected from the group consisting of vinyl ether methacrylate and vinyl ether acrylate as disclosed in the specification. Representative examples of such compounds are shown in Table 2.

According to a twenty-fourth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises:

At least one photopolymerizable compound selected from the group consisting of:

  According to a twenty-fifth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one polymer.

  According to a twenty-sixth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one prepolymer comprising one or more polymerizable functional groups.

  According to a twenty-seventh aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one oligomer comprising one or more polymerizable functional groups.

  According to a twenty-eighth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one reactive diluent comprising one or more polymerizable functional groups. I do.

  According to a twenty-ninth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises a second photopolymerizable monomer, oligomer or prepolymer.

  According to a thirtieth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink is further comprised of a group consisting of amino-modified polyether acrylate, urethane acrylate, polyester acrylate, polyether acrylate and epoxy acrylate. Contains a selected second photopolymerizable monomer.

  Prepolymers and reactive diluents suitable for use in radiation-curable compositions such as the ink compositions of the present invention are described, for example, in "Chemistry & Technology of UV and EB formulation for coatings, inks and paints" Vol. 2: Prepolymers and Reactive diluents for UV and EB curable formations. Unsaturated urethane (meth) acrylates, epoxy (meth) acrylates as described in "Ed.G.WEBSTER-SITA Technology-London (1996) and the periodicals" Coating "9/88, pp. 348-353. , Polyol acrylate, polyether (meth) acrylate and polyester (meth) acrylate.

  Other suitable prepolymers and oligomers belong to the class of the aliphatic and aromatic polyester-urethane acrylates. The structure of polyester-urethane acrylate is described in the pamphlet "Radiation Cure Coatings" by John R. Constanza, A .; P. Silveri and Joseph A. Vona, published by Federation of Society for Coatings Technology, 1315 Walnut St. Philadelphia, PA 19107 USA (June 1986) p. 9. It will be clear that all these monomers, prepolymers, polymers and oligomers mentioned can be used in the mixture.

  Preferred second oligomers for use in combination with the monomers of the present invention are Cray Valley Co. Amino-modified polyether acrylate known as CN 501 from Sci.

  In a particular embodiment, the second monomer, oligomer or prepolymer not belonging to the invention is the main compound involved in the radiation curing, and the monomers according to the invention are so-called for reducing the viscosity of the final ink preparation. Functions as a "reactive diluent".

Other Additives According to a thirty-first aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink composition further contains water as a solvent.

  According to a thirty-second aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink composition further comprises water and / or at least one organic solvent.

  Suitable organic solvents include alcohols, fluorinated solvents and dipolar aprotic solvents. Preferred solvents are methanol, ethanol, propanol, 1-butanol, 1-pentanol, 2-butanol, t. -Butanol, glycol, glycol ether, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 2,4-pentanedione and hexafluoroacetone.

  According to a thirty-third aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink composition does not contain a tackifier.

  According to a thirty-fourth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one conductive or semiconductive polymer.

  According to a thirty-fifth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises a substituted polyaniline, an unsubstituted polyaniline, a polypyrrole, a substituted polythiophene [eg, poly (ethylenedioxythiophene) ) (PEDOT)], unsubstituted polythiophenes, substituted poly (phenylene vinylene) s [eg MEH-PPV], unsubstituted poly (phenylene vinylene) s [eg PPV] and polyfluorenes [eg PF6] At least one conductive or semiconductive polymer.

  According to a thirty-sixth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises at least one antioxidant.

  The radiation-curable ink composition according to the present invention comprises a biocide, a buffer, an anti-mold agent, a pH adjuster, a conductivity adjuster, a chelating agent, an anti-rust agent, a polymerization inhibitor, a light stabilizer, One or more additives such as antioxidants and surfactants, photoinitiator stabilizers may also be included. Such additives can be included in the ink jet inks of the present invention in any desired effective amount.

  Suitable pH adjusters include, but are not limited to, acid and alkali metal hydroxides, for example, bases including lithium hydroxide, sodium hydroxide and potassium hydroxide. The amount included will, of course, depend on the particular ingredients included.

  Suitable photoinitiator stabilizers include those disclosed in EP 0 465 039. Preferred surfactants are of the non-ionic type, such as FLUORAD FC430 (from 3M Corp.). Such surfactants, when present, are preferably included in an amount of 0.1% to 10% by weight of the total ink composition.

Dendrimer According to a thirty-seventh aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink further comprises a dendrimer.

Dendrimers are the starburst molecules of STARBURST ^™ . The topology consists of an initiator core such as nitrogen, ethyleneimine, etc., consisting of a suitable number of arms attached to the core, e.g. 2-4 arms, each arm consisting of a repeating unit, the repeating unit in each arm Consists of an inner layer considered to be the generation of the dendrimer, as well as terminal groups attached to the outermost generation, such as primary amines, which dendrimers are described, for example, in US Pat. 466, 4,631,337, 4,558,120, 4,568,737 and 4,587,329 and Tomalia et al. Authors, Angewandte Chemie, Int. Ed. Engl. 29, 138 (1990). The size and shape of the STARBURST ^™ dendrimer molecule and the functional groups present in the dendrimer molecule can be controlled by the choice of the initiator core, the number of generations, and the repeating units used in each generation.

  The choice of dendrimer component can affect the properties of the dendrimer. The type of initiator core can affect the shape of the dendrimer, for example, resulting in a sphere-shaped dendrimer, a cylinder- or rod-shaped dendrimer or an elliptical-shaped dendrimer. The sequential construction of the generations determines the size of the dendrimer and its internal properties. Examples of suitable core materials include ammonia, polyfunctional alcohols such as pentaerythritol or tris- (hydroxymethyl) ethane, 1,1,1-tris- (4'-hydroxyphenyl) ethane, polyfunctional groups And the like. Examples of such amines include, for example, ethylene amines and linear polyethylene imines. The chemical functionality of the repeating unit in the inner layer may include, for example, ethers such as amidoamines such as aminoethylacetamide, imines such as diethylenediimine or those obtained from materials such as 3,5-dihydroxyethylbenzyl alcohol. Can be included. The terminal functional group includes, for example, an amino group, a hydroxyl group, a carboxylic acid group, a carboxylate, an ester, an amide, a phosphate, a sulfonate and the like. The synthesis of dendrimers usually involves initial reaction of the monomer with the initiator core, followed by thorough reaction of the resulting functional groups with difunctional compounds such as diamines, including, for example, ethylenediamine, to produce the next generation of reactive groups. This is done by a divergent approach involving obtaining an amino group. Thus, for example, ethylenediamine can be suitably first reacted with methyl acrylate to give a compound such as N, N, N ', N'-tetra (methoxycarbonylethyl) ethylenediamine. The compound described above can be reacted with ethylenediamine in the next step to obtain an amidoamine dendrimer having zero generation numbers, a molecular weight of 517 and four primary amino groups on the surface. Repetition of the above two-step procedure results in subsequent generations.

  Another synthetic route is described in Hawker et al. Author, J. et al. Amer. Chem. Soc. , 112, 7638 (1990) using a convergent growth synthesis.

  Dendrimers can have other groups or segments in addition to the amino group. For example, a dendrimer may have a dye covalently attached thereto, or it may have certain functional groups grafted thereon. Preferred dendrimers for use in preparing the ink compositions of the present invention include the dendrimers disclosed in US Pat. No. 6,312,679.

  The dendrimer can be grafted with, for example, an alkylene oxide oligomer or polymer, wherein the alkylene has from 1 to 12 carbon atoms and the degree of polymerization of the alkylene oxide ranges from about 2 to about 100. The amount of grafting can be within any suitable range, preferably less than 50% of the amino groups, more preferably less than 10% of the amino groups. Grafting of the ethylene oxide on the dendrimer can be performed by any suitable means known to one of ordinary skill in the art. For example, polyethylene glycol monomethyl ether of a suitable molecular weight is converted to polyethylene glycol monomethyl ether p-toluenesulfonate, suitably by reaction with p-toluenesulfonyl chloride and pyridine, and the sulfonate is then converted by one of ordinary skill in the art. Under suitable conditions known in the art. Midland, Mich. Dendritech, Inc. To obtain a grafted dendrimer.

Other preferred dendrimers for use in preparing the ink compositions of the present invention include those having terminal amine functionality on the surface. More preferably, the dendrimer has a molecular weight in the range of about 300 to about 100,000, a generation number of 0 to 10, a surface amine group concentration of about 3 to about 4100, and a molecular diameter of about 1 nm to about 1000 nm. More preferred dendrimers are those having a terminal primary amine function. More preferably, the dendrimer has a molecular weight in the range of about 500 to about 30,000, a generation number of 0 to about 5, a surface group concentration of about 4 to about 150, and a molecular diameter of about 1 nm to about 150 nm. It is also preferred that the dendrimer has a low polydispersity index (Mw / Mn), preferably in the range of about 1.1000 to about 1.0001, more preferably in the range of about 1.001 to about 1.0001. Examples of dendrimers produced by the divergent approach include Dendritech, Inc. And STARBURST ^™ dendrimers available from the US. Dendrichtech Inc. These dendrimers are primary amine-terminated surface functional groups and are polyamidoamines (PAMAMs) made from an ethylenediamine core and an ordered copolymer of ethylenediamine and methyl acrylate. They have a polydispersity index of 1.0007.

  The dendrimer is present in the ink composition in an amount sufficient to provide sufficient adhesion of the ink components to the printing surface and also to provide sufficient water resistance and cold and hot humidity resistance. The amount of dendrimer is preferably in the range of about 0.1% to about 10% by weight of the ink composition, more preferably in the range of about 0.5% to about 2%, and even more preferably about 1%. % To about 2% by weight.

Physical Properties of Radiation-Curable Ink Composition In preparing the radiation-curable ink composition of the present invention, certain physical properties must be satisfied. For example, an ink composition for use in ink jet recording must have suitable viscosity and surface tension properties.

  According to a thirty-eighth embodiment of the radiation-curable ink composition according to the present invention, the radiation-curable ink has a viscosity of 1 mPa. s.

  According to a thirty-ninth aspect of the radiation-curable ink composition according to the present invention, the radiation-curable ink has a surface tension of 20 to 72 mN / m, preferably 20 to 60 mN / m.

Methods for Obtaining Ink-Jet Images Aspects of the present invention are directed to jetting one or more streams of ink drops having the composition described above onto an ink-jet ink-receiving material and subjecting the resulting image to radiation curing. Implemented by a method for obtaining a colorless, monochrome or multicolor ink jet image, including steps.

  According to a first aspect of the method for obtaining an ink-jet image according to the present invention, radiation curing is performed with at least one ultraviolet light source and / or at least one electron beam source.

  According to a second aspect of the method for obtaining an ink-jet image according to the present invention, curing is a radical polymerization process.

  According to a third aspect of the method for obtaining an ink-jet image according to the present invention, the curing is a cationic polymerization process.

  According to a fourth aspect of the method for obtaining an ink-jet image according to the present invention, the ink-jet ink-receiving material comprises paper, coated paper, polyolefin-coated paper, paperboard, wood, composite board, plastic, It is selected from the group consisting of coated plastics, canvases, textiles, metals, glass, vegetable textiles, leather, magnetic materials and ceramics or supports provided with an ink-receiving layer.

  According to a fifth aspect of the method for obtaining an ink-jet image according to the present invention, the ink-jet receiving material comprises an ink-receiving layer containing a microporous pigment or a polymer blend.

Radiation Curing Apparatus Equipment for radiation curing is known to those skilled in the art and is commercially available. For example, the curing is performed using a medium pressure mercury vapor lamp with or without electrodes or a pulsed xenon lamp. These UV light sources are usually equipped with cooling equipment, equipment for removing the ozone generated and possibly nitrogen inflow, and for removing air from the surface of the product to be cured during the radiation treatment. In the region of 200 to 400 nm, an intensity of 40 to 240 W / cm is usually used. Examples of commercially available ultraviolet medium-to-pressure electrodeless mercury vapor lamps are available from Fusion UV systems Ltd. , UK model VPS / I600 curing system. Pulsed Xenon flash lamps are commercially available from IST Strahlentenchik GmbH, Nuertingen, Germany. Using the Fusion model, metal halide doped Hg vapor or XeCl excimer lamps can also be used, each of which has its unique UV emission spectrum. This allows more freedom in the preparation of the cured composition: more efficient curing is possible with lamps having the most suitable spectral properties.

  Curing of the ink composition can also be performed using high energy ionizing radiation such as X-rays, gamma rays, beta rays and accelerating electrons.

Ink-jet printheads The radiation-curable ink compositions according to the present invention can be used with any ink-jet printhead, but preferably with a piezoelectric printhead that can be heated to accommodate various viscosities. Used together. Typical examples include Spectra Inc. Epson, Brother, Xaar Ltd. , As well as the print head from Trident International "Inkjet Technology and Product Development Strategies, S.F.Pond, Torrey Pines research, 2000" and "Proceedings IS &T's International Conference on Digital Production Printing and Industrial Applications", 2001, Antwerp, Belgium For example, the print head designs described on pages 230 to 234 are included. The radiation-curable ink composition can be used with any type of nozzle plate, such as a nozzle plate based on silicon, polyimide, silicon nitride.

Industrial Applicability The radiation-curable ink compositions according to the invention can be used in ink-jet printing and other printing applications to which radiation curing is applied, such as flexographic printing and liquid electrophotography.

  The radiation-curable ink compositions according to the invention are used for the production of printing plates, such as in computer-to-plate applications, and for the display of displays such as printed circuit boards (PCB) and OLED's. It can also be used for manufacturing.

  The present invention will now be illustrated by the following examples, but is not limited thereto.

Components used in the radiation curable ink compositions disclosed in the examples:
TPGDA = tri (propylene glycol) diacrylate DPGDA = di (propylene glycol) diacrylate TMPTA = trihydroxymethylpropane triacrylate CN501 = CRAYNOR ^™ CN501, Cray Valley Co. From amino-modified polyether acrylates.

  The solubility of some compounds of the present invention was determined in several reactive diluents and oligomers, such as TPGDA, TMPTA and CN501, and the results are shown below in Table 3.

  The following clear inks were prepared:

  10 g of Irgacure 500 and 5 g of NMDA were added to each ink preparation, and the resulting ink composition was coated on an unprimed 175 μm thick transparent PET polyester film using a bar coater and a 10 μm wire bar. .

  The coated film was cured using a Fusion DRSE-120 conveyor equipped with a Fusion VPS / I600 lamp (D bulb), which transported the film at a speed of 20 m / min under a UV lamp on a conveyor belt. . The percentage of the maximum power of the lamp to cure the film was used as a measure for sensitivity.

  Cure was evaluated by a scratch test using a cotton pad. If the coating did not remain visually unchanged after scratching, the cure was considered incomplete. Table 4 summarizes the ink sensitivities.

  As is evident from Table 4, all inks cured easily.

The present invention includes any feature or combination of features or generalizations thereof, implicitly or expressly disclosed herein, whether or not it relates to the presently claimed invention. be able to. In view of the foregoing description, it will be apparent to one skilled in the art that various modifications may be made within the scope of the present invention.

Claims (5)

Comprising at least one initiator and at least one polyhedral oligomeric silsesquioxane (POSS) represented by the following empirical formula [R (SiO _1.5 )] _n , where n = 4,6 , 8, 10, 12, 14, 16 and higher numbers, wherein each R is independently hydrogen, an inorganic group, an alkyl group, an alkylene group, an aryl group, an arylene group or an alkyl, alkylene, aryl or arylene group. A radiation curable ink composition which is a non-heterocyclic group-containing organic-functional derivative.   The radiation curable ink composition according to claim 1, wherein the polyhedral oligomeric silsesquioxane comprises at least one R-group comprising a curable functional group. The curable polyhedral oligomeric silsesquioxane (POSS) has a special cage structure represented by Formulas I-III or a partial cage structure represented by Formula IV:

[Wherein, R1 to R12 represent hydrogen, an inorganic or organic substituent, and at least one of the R1 to R12 groups contains a curable functional group]
Radiation curable ink composition according to claim 2.   Radiation curable ink composition according to any of claims 1 to 3, wherein said initiator is a photoinitiator.   A colorless method comprising jetting one or more streams of ink drops having the composition according to any of claims 1 to 4 onto an ink-jet ink receiving material and subjecting the resulting image to radiation curing. For obtaining monochromatic or multicolor ink jet images.