Composition

Abstract

The present invention provides a laser imageable composition comprising an oxyanion of a polyvalent metal and an oligomer, wherein the oxyanion of the polyvalent metal is D 50 The present invention relates to a laser-imageable composition comprising particles having a particle size distribution of 10 μm or less. Methods for formulating the laser-imageable composition and substrates comprising the laser-imageable composition applied to the substrate are also disclosed.

Description

Technical Field

[0001] The present invention relates to a laser image-forming composition. The present invention further relates to a substrate comprising a laser image-forming composition applied to a substrate and a method of forming a laser image-forming composition.

Background Art

[0002] The use of laser image-forming compositions for various information printing to produce human and / or machine-readable elements is known. After applying the laser image-forming composition to a substrate, an image can be formed by applying a suitable stimulus to the laser image-forming composition.

[0003] Laser image-forming compositions can be applied to substrates using a plurality of various known printing processes. Each of these printing processes results in a layer of the laser image-forming composition on the substrate at a specific coating weight. For the application of the laser image-forming composition to the substrate at a low coating weight, the preferred printing process is offset lithography. This high-quality printing technique can apply the laser image-forming composition to the substrate at a coating weight in the range of typically 0.7 to 1.8 gsm (grams per square meter) per layer of the composition. The low coating weight means that this printing process is often commercially preferred from a cost perspective.

[0004] Polyvalent metal oxyanions are known in the art as compounds of laser image-forming compositions. Such compounds can generate high-contrast human and / or machine-readable images when the laser image-forming composition is exposed to a suitable stimulus. However, for polyvalent metal oxyanions used in offset lithographic printing processes, in order to promote high-contrast image formation, multiple layers of the laser image-forming composition must be applied to the substrate. The low coating weights generated by offset lithographic printing techniques mean that a single application of a laser image-forming composition containing a polyvalent metal oxyanion is insufficient to produce high-contrast human and / or machine-readable images. This requirement for multiple layers of the laser image-forming composition is time-consuming and occupies a significant amount of space in the printing apparatus, and as a result, offset lithography is generally not considered commercially viable for laser image-forming compositions containing polyvalent metal oxyanions. Consequently, the printing process for applying a laser image-forming composition containing a polyvalent metal oxyanion to a substrate to generate the desired diverse information in the laser image-forming composition is often limited to printing techniques that deliver laser image-forming compositions with higher coating weights, such as flexographic, gravure, and screen printing.

[0005] Therefore, it is desirable to provide a composition containing a polyvalent metal oxyanion that can result in a high-contrast image that is human and / or machine-readable when the laser image-forming composition is exposed to a suitable stimulus after application of only a single layer of the laser image-forming composition to a substrate by offset lithography at a low coating weight. SUMMARY OF THE INVENTION

[0006] According to a first aspect of the present invention, (a) a polyvalent metal oxyanion and (b) an oligomer comprising a laser image-forming composition, The oxyanion of a polyvalent metal is D 50 There is provided a laser image-forming composition containing particles having a particle size distribution of 10 μm or less.

[0007] According to a second aspect of the present invention, (a) an oxyanion of a polyvalent metal and (b) an oligomer A method of forming a laser image-forming composition containing the same, wherein the oxyanion of the polyvalent metal in the laser image-forming composition is D 50 The method includes a step of combining an oxyanion of a polyvalent metal and an oligomer, and the method provides particles having a particle size distribution of 10 μm or less.

[0008] According to a third aspect of the present invention, there is provided a substrate including a laser image-forming composition applied to the substrate, wherein the laser image-forming composition (a) an oxyanion of a polyvalent metal and (b) an oligomer including the oxyanion of the polyvalent metal is D 50 The substrate includes particles having a particle size distribution of 10 μm or less.

[0009] According to a fourth aspect of the present invention, there is provided a method of forming a substrate having a laser image-forming composition applied to the substrate, the method including a step of applying the laser image-forming composition to the substrate, wherein the laser image-forming composition (a) an oxyanion of a polyvalent metal and (b) an oligomer including the oxyanion of the polyvalent metal is D 50 The method provides particles having a particle size distribution of 10 μm or less.

[0010] According to a fifth aspect of the present invention, there is provided a method of forming an image on a substrate including a laser image-forming composition applied to the substrate, wherein the laser image-forming composition (a) an oxyanion of a polyvalent metal and (b) Oligomer comprising The oxyanion of the polyvalent metal is D 50 A method is provided, comprising particles having a particle size distribution of 10 μm or less, and the method comprising the step of exposing a laser image-forming composition to radiation to form an image on a substrate.

[0011] According to a sixth aspect of the present invention, use of a laser image-forming composition in offset lithographic printing, wherein the laser image-forming composition (a) an oxyanion of a polyvalent metal and (b) an oligomer comprising The oxyanion of the polyvalent metal is D 50 Use is provided, comprising particles having a particle size distribution of 10 μm or less.

[0012] According to a seventh aspect of the present invention, use of a laser image-forming composition in forming an image on a substrate, wherein the laser image-forming composition (a) an oxyanion of a polyvalent metal and (b) an oligomer comprising The oxyanion of the polyvalent metal is D 50 Use is provided, comprising particles having a particle size distribution of 10 μm or less. [Embodiments for Carrying Out the Invention]

[0013] Surprisingly, and advantageously, it has been found that the laser image-forming composition according to the present invention can promote the generation of a high-contrast human and / or machine-readable image on a substrate when applied to the substrate by offset lithographic printing at a low coating weight, including when only a single layer of the laser image-forming composition is applied to the substrate by offset lithographic printing. The laser image-forming composition according to the present invention advantageously also exhibits good environmental resistance and maintains a high-contrast image over a long period of time.

[0014] Even more surprisingly, advantageously, the laser image-forming composition of the present invention can exhibit an enhanced rheology profile during an offset lithographic printing process and has been found to provide improved smoothness of the laser image-forming composition when printed on a desired substrate.

[0015] As used herein, the terms "offset lithographic printing", "lithographic printing" and "offset printing" refer to the latest printing techniques well known to those skilled in the art. These terms may be used interchangeably by those skilled in the art.

[0016] According to a first aspect of the present invention, (a) a polyvalent metal oxyanion and (b) an oligomer A laser image-forming composition comprising: The polyvalent metal oxyanion is D 50 There is provided a laser image-forming composition comprising particles having a particle size distribution of 10 μm or less.

[0017] The polyvalent metal oxyanion may be any suitable oxyanion of a polyvalent metal. As used herein, the term "polyvalent metal oxyanion" encompasses any oxyacid or hydrate of said oxyanion of a polyvalent metal. The hydrate may be a hydrate of the polyvalent metal oxyanion or a hydrate of the corresponding oxyacid of the polyvalent metal. The polyvalent metal oxyanion, or its corresponding oxyacid, may be an anhydride.

[0018] The oxyanion of the polyvalent metal includes any suitable oxyanion (anionic component) of the polyvalent metal that exists with a cationic counterpart. The use of the oxyanion of the polyvalent metal in the composition is disclosed in U.S. Patent No. 7,485,403, the content of which is incorporated herein by reference. The anionic component includes inorganic metal oxyanion compounds such as molybdates, tungstates, chromates, or similar transition metal compounds of mixed oxidation states and mixed inorganic metal oxyanions, including di-, tri-, hexa-, hepta-, octa- and deca-molybdates. Preferably, the accompanying cationic component is an alkali metal or an alkaline earth metal or ammonium. An example of the oxyanion of the polyvalent metal is sodium molybdate. A preferred oxyanion of the polyvalent metal is the ammonium salt of an inorganic metal oxyanion compound. For example, ammonium paratungstate (APT). Particularly preferred as the oxyanion of the polyvalent metal is the ammonium salt of the oxyanion of molybdenum. A particularly preferred oxyanion of the polyvalent metal is ammonium octamolybdate, a commercially available molybdenum composition with CAS number 12411-64-2, NH 4 ) 4 Mo 8 O 26 i.e., "AOM".

[0019] Preferably, the oxyanion of the polyvalent metal is the ammonium salt of the oxyanion of the polyvalent metal, such as the ammonium salt of the oxyanion of molybdenum. More preferably, the oxyanion of the polyvalent metal is ammonium octamolybdate (AOM).

[0020] The polyvalent metal oxyanion is the "image-forming compound" of the laser image-forming composition. By the "image-forming compound", after application of the laser image-forming composition to a substrate, when the laser image-forming composition, and thus the polyvalent metal oxyanion, is exposed to suitable radiation, it is intended that the polyvalent metal oxyanion forms an image of distinguishable contrast on the substrate. The image of distinguishable contrast is human and / or machine-readable. In the context of the present invention, the image of distinguishable contrast is the black or its shades including grayscale according to the optical density of the black formed by radiation. By the "image of contrast", "image of high contrast" or similar terms used herein, it is intended that the image formed in the portion of the laser image-forming composition exposed to radiation is different from the background of the laser image-forming composition, i.e., the portion of the laser image-forming composition not exposed to radiation, and any substrate visible through it, and is easily distinguishable. The laser image-forming composition can be white or almost white at the time of formulation, at the time of application to the substrate and before exposure to radiation. Therefore, the portion of the laser image-forming composition not exposed to radiation, i.e., the background of the laser image-forming composition, can remain white or almost white. In the present invention, the effective formation of a high-contrast image is indicated by the ΔODB (Δ optical density black) value. ΔODB is calculated as follows: "absolute" ODB - "background" ODB. "Absolute" ODB is a measure of the optical density of the black of the image. The larger the value, the darker the black formed. "Background" ODB is a measure of the optical density of the black of the background of the laser image-forming composition on the substrate, i.e., the portion of the laser image-forming composition not exposed to radiation, and any substrate visible through it. Therefore, the ΔODB value is a measure of the difference in the optical density of the black of the image with respect to the non-imaged portion of the laser image-forming composition. A larger ΔODB value indicates a higher-contrast image. All ODB measurements may be performed using an X-Rite eXact or SpectroEye spectrophotometer.In the present invention, a ΔODB value of 0.6 or more, for example 0.7 or more, or even 0.8 or more, preferably 1.0 or more is desirable. Such a value indicates the formation of a high-contrast image by the laser image-forming composition of the present invention when exposed to radiation after application of the laser image-forming composition to a substrate by offset lithography.

[0021] The oxyanion of the polyvalent metal is D 50 It contains particles having a particle size distribution of 10 μm or less, for example 7 μm or less. The oxyanion of the polyvalent metal is present in the laser image-forming composition in particulate form, and the particles are D 50 It should be understood by those skilled in the art that it has a particle size distribution of 10 μm or less, for example 7 μm or less. Preferably, the particles of the oxyanion of the polyvalent metal are D 50 It has a particle size distribution of 5 μm or less, for example 4.5 μm or less, for example 4 μm or less, or even 3.5 μm or less. More preferably, the particles of the oxyanion of the polyvalent metal are D 50 It has a particle size distribution of 3 μm or less, for example 2.5 μm or less, or even 2.4 μm or less.

[0022] The particles of the oxyanion of the polyvalent metal have a D in the range of 0.5 to 10 μm, for example 0.5 to 7 μm, or 0.5 to 5 μm, or even 1 to 4 μm, preferably 2 to 3.5 μm, more preferably 2 to 3 μm, and most preferably 2.2 to 2.4 μm. 50 It may have a particle size distribution.

[0023] The particles of the oxyanion of the polyvalent metal may have any suitable D 90 It may have a particle size distribution. The oxyanion of the polyvalent metal is present in the laser image-forming composition in particulate form, and the particles may have any suitable D 90 It should be understood by those skilled in the art that it has a particle size distribution. Preferably, the D of the particles of the oxyanion of the polyvalent metal 90The particle size distribution is 25 μm or less, for example 20 μm or less, or 15 μm or less, or 10 μm or less, or 9.5 μm or less, or even 9 μm or less. More preferably, the D of the particles of the polyvalent metal oxyanion 90 The particle size distribution is 8.5 μm or less, for example 8 μm or less.

[0024] The particles of the polyvalent metal oxyanion may have any suitable D 10 Particle size. The polyvalent metal oxyanion is present in the laser image-forming composition in particulate form, and it should be understood by those skilled in the art that the particles have any suitable D 10 Particle size distribution. Preferably, the D of the particles of the polyvalent metal oxyanion 10 The particle size distribution is 4 μm or less, for example 3 μm or less, for example 2.5 μm or less, or even 2 μm or less. More preferably, the D of the particles of the polyvalent metal oxyanion 10 The particle size distribution is 1.5 μm or less, for example 1 μm or less.

[0025] The D of the particles of the polyvalent metal oxyanion 50 It should be understood by those skilled in the art that a small particle size distribution is beneficial. The laser image-forming composition of the present invention can be applied to a substrate at a reduced coating weight using offset lithographic printing, and as a result, not only can a single application of the laser image-forming composition be required to promote image formation with particularly high contrast, but also the small particle size promotes the improvement of the rheology profile for the laser image-forming composition of the present invention. Furthermore, the increase in the surface area of the particles of the polyvalent metal oxyanion resulting from the particle size distribution value promotes the generation of an image with enhanced contrast when the laser image-forming composition is exposed to radiation. The particles of the polyvalent metal oxyanion having the D 90 And D 10 Particle size distribution also exhibit similar effects.

[0026] The terms "D 50 " and "D 50"Particle size distribution", as used herein, refers to the median particle size of the particles of the polyvalent metal oxyanion, i.e., the particle diameter at 50% of the cumulative distribution. This is the diameter at which 50% of the particle population is seen above and below it. The terms "D 10 " and "D 10 "Particle size distribution", as used herein, refers to the median particle diameter at the 10th percentile, i.e., the diameter at which 10% of the particle population is seen below it. The terms "D 90 " and "D 90 "Particle size distribution", as used herein, refers to the median particle diameter at the 90th percentile, i.e., the diameter at which 90% of the particle population is seen below it.

[0027] It should be understood by those skilled in the art that the particle size distribution measurement is performed using the prepared laser image-forming composition if the prepared laser image-forming composition is suitable for application to a substrate. The particles of the polyvalent metal oxyanion are the only component of the prepared laser image-forming composition in particle or particulate form if the prepared laser image-forming composition is suitable for application to a substrate. The particle size distribution measurements specified or reported herein are measured by a conventional Malvern Mastersizer (trademark) 3000 particle size analyzer from Malvern Instruments in accordance with ISO13320:2009. The D 50 ,"D 90 and D 10 particle size distributions of the laser image-forming composition of the present invention are preferably measured within one month, for example within two weeks, more preferably within one week from the formulation of the laser image-forming composition.

[0028] The particles of the polyvalent metal oxyanion of the present invention have a surface area of 950 m 2 / kg or more, for example 1200 m 2 / kg or more, or 1500 m 2 / kg or more, preferably 2000 m 2 / kg or more, for example 2500 m 2 / kg or more, for example 3000 m 2above / kg, or further 3700 m 2 / kg, more preferably 4000 m 2 may have above / kg.

[0029] The surface area is measured using a Malvern Mastersizer in accordance with ISO standard 13320:2009 for calculating the surface area from particle size distribution data. The surface area of the laser image-forming composition of the present invention is preferably measured within 1 month, for example within 2 weeks, more preferably within 1 week from the formulation of the laser image-forming composition.

[0030] The polyvalent metal oxyanion may be present in the laser image-forming composition according to the present invention in any suitable amount. Preferably, the laser image-forming composition contains 40 to 70 wt%, for example 30 to 60 wt% of the polyvalent metal oxyanion, or further 40 to 60 wt% of the polyvalent metal oxyanion.

[0031] The laser image-forming composition according to the present invention contains an oligomer. The oligomer of the laser image-forming composition may be any suitable oligomer for use in a laser image-forming composition for offset lithographic printing. The oligomer of the laser image-forming composition may be any suitable radiation-curable oligomer, for example a UV-curable oligomer. It should be noted that the laser image-forming composition according to the present invention may contain two or more oligomers.

[0032] The oligomer of the laser image-forming composition acts as a binder for the composition, whereby the composition can be suitable for use as the laser image-forming composition of the present invention. Therefore, the presence of the oligomer promotes the generation of high-contrast images using the laser image-forming composition of the present invention. Further, as will be discussed in more detail below, the selection of the oligomer can enable the production of a laser image-forming composition having enhanced environmental resistance, and as a result, not only can a high-contrast image be generated, but this image can be maintained over a long period of time.

[0033] The oligomer may be a difunctional, trifunctional or tetrafunctional oligomer, or an oligomer with a higher functionality. Preferably, the oligomer is a difunctional, trifunctional or tetrafunctional oligomer. More preferably, the oligomer is a difunctional or trifunctional oligomer. Most preferably, the oligomer is a difunctional oligomer. The selection of an oligomer having a specific functionality is considered at present to mean that the laser image-forming composition of the present invention can exhibit enhanced environmental resistance and that a high-contrast image can be formed and maintained over a long period of time when irradiated with radiation. This is particularly the case when the oligomer is a difunctional or trifunctional oligomer, especially when the oligomer is a difunctional oligomer.

[0034] The functionality of an oligomer refers to the number of its polymerizable groups. The functionality of an oligomer represents the number of bonds that the repeating unit of the oligomer forms with other oligomers within the polymer. The functionality of an oligomer affects the formation and degree of cross-linking of the polymer. As used herein, the term "bifunctional" and similar terms refer to an oligomer having two reactive sites, i.e., two polymerizable groups, capable of forming two bonds with other oligomers within the polymer. As used herein, the term "trifunctional" and similar terms refer to an oligomer having three reactive sites, i.e., three polymerizable groups, capable of forming three bonds with other oligomers within the polymer. As used herein, the term "tetrafunctional" and similar terms refer to an oligomer having four reactive sites, i.e., four polymerizable groups, capable of forming four bonds with other oligomers within the polymer. The term "greater functionality" refers to an oligomer having more than four reactive sites, e.g., up to six reactive sites.

[0035] The oligomer may be selected from, but is not limited to, the following: epoxy oligomers including modified epoxy oligomers; urethane oligomers; silane or silicon oligomers; epoxy (meth)acrylate oligomers (e.g., vinyl ester oligomers) and modified epoxy (meth)acrylate oligomers (e.g., modified vinyl ester oligomers), alkyl (meth)acrylate oligomers such as methyl (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polyester (meth)acrylate oligomers, acid-functional (meth)acrylate oligomers, (meth)acrylate oligomers including amine (meth)acrylate oligomers; polyester urethane acrylate oligomers; and urethane (meth)acrylate oligomers.

[0036] "(Meth)acrylate" includes both acrylate and methacrylate, and the parentheses indicate that the components therein may be used optionally. Usually, when used herein, (meth)acrylate preferably refers to acrylate. Epoxy oligomers and epoxy (meth)acrylate oligomers include, but are not limited to, oligomers formed by combining phenol and formaldehyde (novolac route); and oligomers formed from epoxy group-containing compounds such as epichlorohydrin (ECH) and bisphenol A (BPA), noting that the latter may be optionally substituted with other substances such as aliphatic glycols, phenol, and o-cresol novolac. Further reaction with acrylic group-containing compounds such as (meth)acrylic acid can promote the formation of epoxy (meth)acrylate oligomers.

[0037] As used herein with respect to epoxy oligomers and epoxy (meth)acrylate oligomers, by "modified" it is intended that the epoxy groups of the epoxy oligomer or epoxy (meth)acrylate oligomer have undergone further chemical modification (other than those for generating the (meth)acrylate groups of the epoxy (meth)acrylate oligomer). Such chemical modifications can be caused by reactions including, but not limited to, addition polymerization reactions, dimerization, esterification, and hydrogenation. It should be understood that these modifications change the reactivity, adhesion, flexibility, chemical resistance, hardness, and shrinkage characteristics of the oligomers.

[0038] Specific examples of suitable oligomers include, but are not limited to, oligomers of the trade name "Genomer", all available from Rahn AG, such as Genomer 3414 and 3480 (polyether acrylate oligomers), Genomer 5271 (amine acrylate oligomer), Genomer 2263 (epoxy acrylate oligomer (vinyl ester)), Genomer 2281 (modified epoxy acrylate oligomer), and Genomer 4312 (polyester urethane acrylate oligomer).

[0039] Preferably, the oligomer is selected from epoxy oligomers, modified epoxy oligomers, urethane oligomers, polyether (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester urethane (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof. More preferably, the oligomer is selected from polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester urethane (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof. Even more preferably, the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof. Even more preferably, the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof. Even more preferably, the oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof. Most preferably, the oligomer is an epoxy (meth)acrylate oligomer.

[0040] Such a selection of oligomers with respect to chemical properties is currently thought to mean that the laser image-forming composition can exhibit enhanced environmental resistance and that upon irradiation with radiation, an image with high contrast can be formed and maintained over a long period. This is particularly the case when the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, more particularly when the oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof, and even more particularly when the oligomer is an epoxy (meth)acrylate oligomer.

[0041] Preferably, the oligomer is selected from epoxy oligomers, modified epoxy oligomers, urethane oligomers, polyether (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester urethane (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and the oligomer is trifunctional or difunctional, preferably difunctional. More preferably, the oligomer is selected from polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester urethane (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and the oligomer is difunctional or trifunctional, preferably difunctional. More preferably, the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and the oligomer is trifunctional or difunctional, preferably difunctional. More preferably, the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and the oligomer is trifunctional or difunctional, preferably difunctional. More preferably, the oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof, and the oligomer is difunctional or trifunctional, preferably difunctional. More preferably, the oligomer is an epoxy (meth)acrylate oligomer, and the oligomer is trifunctional or difunctional, preferably difunctional. Most preferably, the oligomer is a difunctional epoxy (meth)acrylate oligomer.Such a selection of oligomers means that the laser image-forming composition can exhibit enhanced environmental resistance, and that upon irradiation with radiation, an image with high contrast can be formed and maintained over a long period of time. This is particularly the case when the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and when the oligomer is difunctional, particularly when the oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof, and when the oligomer is difunctional, more particularly when the oligomer is an epoxy (meth)acrylate oligomer, and when the oligomer is difunctional, even more particularly when the oligomer is a difunctional epoxy (meth)acrylate oligomer.

[0042] The oligomer may be present in the laser image-forming composition according to the present invention in any suitable amount. Preferably, the laser image-forming composition contains 10 to 50 wt%, for example 20 to 50 wt%, or even 25 to 45 wt% of the oligomer.

[0043] The laser image-forming composition according to the present invention may further contain a monomer. Advantageously, it has been found that when present, the monomer can promote the generation of high-quality, high-contrast images when the laser image-forming composition is irradiated with radiation. Further, the presence of the monomer in the laser image-forming composition of the present invention makes a wider range of oligomers available, particularly with respect to viscosity. As will be discussed in more detail below, oligomers of increased viscosity may be utilized. The use of a monomer in combination with an oligomer in the laser image-forming composition of the present invention enhances the rheology profile of the laser image-forming composition during the offset lithography printing process and can result in improved smoothness when applied to a desired substrate. The use of oligomers of greater viscosity enables an enhanced rheology profile to be achieved, i.e., a greater shearing effect is exhibited. The monomer may be any suitable monomer for use in a laser image-forming composition for offset lithography printing. The monomer of the laser image-forming composition may be any suitable radiation-curable monomer, such as a UV-curable monomer. It should be noted that the laser image-forming composition according to the present invention may contain two or more monomers.

[0044] It is currently further contemplated that the presence of the monomer also further enhances the hardness, flexibility, gloss, chemical resistance and adhesion properties of the laser image-forming composition of the present invention.

[0045] The monomer may be a monofunctional, difunctional, trifunctional or tetrafunctional monomer, or a monomer with a greater functionality. Preferably, the monomer is a difunctional, trifunctional or tetrafunctional monomer, or a monomer with a greater functionality. More preferably, the monomer is a difunctional or trifunctional monomer. Most preferably, the monomer is a difunctional monomer. Such a selection of the monomer is considered advantageous in promoting the generation of high-quality, high-contrast images and further contributing to the improvement of the hardness, flexibility, gloss, chemical resistance and adhesion properties of the laser image-forming composition of the present invention. This is especially the case when the monomer is selected to be a difunctional or trifunctional monomer, especially when the monomer is selected to be a difunctional monomer.

[0046] The functionality of a monomer refers to the number of its polymerizable groups. The functionality of a monomer represents the number of bonds that the repeating unit of the monomer forms with other monomers within the polymer. The functionality of a monomer affects the formation and degree of crosslinking of the polymer. As used herein, the term "monofunctional" and similar terms refer to a monomer having only one reactive site, i.e., one polymerizable group, and capable of forming one bond with other monomers within the polymer. As used herein, the term "difunctional" and similar terms refer to a monomer having two reactive sites, i.e., two polymerizable groups, and capable of forming two bonds with other monomers within the polymer. As used herein, the term "trifunctional" and similar terms refer to a monomer having three reactive sites, i.e., three polymerizable groups, and capable of forming three bonds with other monomers within the polymer. As used herein, the term "tetrafunctional" and similar terms refer to a monomer having four reactive sites, i.e., four polymerizable groups, and capable of forming four bonds with other monomers within the polymer. The term "greater functionality" refers to a monomer having more than four reactive sites, for example up to six reactive sites.

[0047] Suitable monomers include, but are not limited to, (meth)acrylate monomers including acrylated epoxy monomers, acrylated polyurethane monomers, acrylated polyester monomers, acrylated epoxyified oil monomers, acrylated polyether monomers, and mixtures thereof.For example, suitable monomers include monofunctional (meth)acrylate monomers such as caprolactone acrylate (CA), phenoxybenzyl acrylate (PBA), 0-phenylphenol EO acrylate (OPPEA), 4-tert-butylcyclohexyl acrylate (TBCHA), benzyl acrylate (BZA), biphenylmethyl acrylate (BPMA), tetrahydrofurfuryl acrylate (THFA), ethoxyethoxyethyl acrylate (EOEOA), stearyl acrylate (SA), octadecyl acrylate (ODA), cyclic trimethylolpropane formal acrylate (CFTA), ethoxylated 4-nonylphenol acrylate (NP4EOA), 3,3,5-trimethylcyclohexyl acrylate (TMCHA), isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), lauryl acrylate (LA), isodecyl acrylate (IDA), phenol (EO) acrylate (PH(EO)A), nonylphenol (EO)4 acrylate (NP(EO)4A), nonylphenol (EO)8 acrylate (NP(EO)8A), 2-(2-ethoxyethoxy)ethyl acrylate (EOEOA), benzyl methacrylate (BZMA), isodecyl methacrylate (IDMA), phenoxyethyl methacrylate (PHEMA), tetrahydrofurfuryl methacrylate (THFMA), stearyl methacrylate (SMA), methoxy PEG600 methacrylate (MPEG600MA), phenoxyethyl acrylate (PEA); difunctional (meth)acrylate monomers such as 1,6-hexanediol dimethacrylate (HDDMA), 1,4-butanediol dimethacrylate (BDDMA), neopentyl glycol dimethacrylate (NPGDMA), ethylene glycol dimethyl acrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate (T4EGDMA), bisphenol A (EO). 3 dimethacrylate (BPA(EO)3DMA), bisphenol A (EO) 4Dimethacrylate (BPA(EO)4DMA), bisphenol A (EO) 10 Dimethacrylate (BPA(EO)10DMA), bisphenol A (EO) 30 Dimethacrylate (BPA(EO)30DMA), 1,3-butylene glycol dimethacrylate (BGDMA), polyethylene glycol 200 dimethacrylate (PEG200DMA), polyethylene glycol 400 dimethacrylate (PEG400DMA), ethoxylated polypropylene glycol dimethacrylate (PPG700(EO)6DMA); trifunctional (meth)acrylate monomers such as trimethylolpropane triacrylate (TPMTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO)3TA), trimethylolpropane (EO) 6 Triacrylate (TMP(EO)6TA), trimethylolpropane (EO) 9 Triacrylate (TMP(EO)9TA), trimethylolpropane (EO) 15 Triacrylate (TMP(EO)15TA), glycerin (PO) 3 Triacrylate (GPTA), pentaerythritol acrylate (PETA), trimethylolpropane (PO) 3 Triacrylate (TMP(PO)3TA), tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA), trimethylolpropane trimethylacrylate (TMPTMA), ethoxylated (EO) 5 Pentaerythritol tetraacrylate (PPTTA), trimethylolpropane triacrylate (TMPTA); and tetrafunctional (meth)acrylate monomers or monomers with a higher functionality, such as pentaerythritol (EO) n Tetraacrylate (PE(EO)nTTA), ditrimethylolpropane tetraacrylate (DTMPTTA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), including but not limited to these.

[0048] "EO", as used herein, refers to an ethoxy group, and any subsequent subscript numbers together indicate the number of linked ethoxy groups. "EO n " refers to a product containing a mixture of ethoxy chain lengths.

[0049] Specific examples of suitable monomers include commercially available acrylated polyether monomers such as Laromer TPGDA (tripropylene glycol diacrylate) available from BASF, monomers with the trade name "Miramer" such as Miramer M320 (glyceryl propoxytriacrylate - GPTA), Miramer M3130 (trimethylolpropane EO 3 triacrylate - TMP(EO) 3 TA), and Miramer M3190 (trimethylolpropane EO 9 triacrylate - TMP(EO) 9 TA); commercially available acrylated polyester monomers including monomers with the trade name Miramer M300 (trimethylolpropane triacrylate - TMPTA) available from Rahn AG; and commercially available aliphatic acrylate monomers such as monomers with the trade name Miramer M122 (lauryl acrylate - LA), but are not limited thereto.

[0050] As discussed previously, the selection of monomers can make a wider range of oligomers available and facilitate the generation of high - quality, high - contrast images. Preferably, the monomers are tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9It is selected from (TA). More preferably, the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 It is selected from (TA). Most preferably, the monomer is tripropylene glycol diacrylate (TPGDA).

[0051] By such a selection of the monomer, when the radiation-sensitive imaging composition is irradiated with radiation, it is possible to generate an image with particularly high-quality contrast. This is especially the case when the monomer is selected to be tripropylene glycol diacrylate (TPGDA).

[0052] Preferably, when the monomer is present in the radiation-sensitive imaging composition according to the present invention, the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or combinations thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9It is selected from (TA). More preferably, the oligomer is selected from epoxy (meth) acrylate oligomers and modified epoxy (meth) acrylate oligomers, or a combination thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 (TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 It is selected from (TA). More preferably, the oligomer is selected from epoxy (meth) acrylate oligomers and modified epoxy (meth) acrylate oligomers, or a combination thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 (TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 It is selected from (TA). More preferably, the oligomer is an epoxy (meth) acrylate oligomer, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 (TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9It is selected from (TA). More preferably, the oligomer is an epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA). By selecting the specified oligomer and monomer, when the laser image-forming composition is irradiated with radiation, it is possible to generate a high-quality, high-contrast image. In addition, the selection of the specified oligomer and monomer means that the laser image-forming composition can exhibit enhanced environmental resistance, and a high-contrast image is formed and maintained over a long period when irradiated with radiation. When the laser image-forming composition usually selects such an oligomer and monomer, it also exhibits improved hardness, flexibility, gloss, chemical resistance and adhesion properties. This is especially the case when the oligomer is selected to be an epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 Selected from TA), especially when the oligomer is selected to be an epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA).

[0053] Preferably, when the monomer is present in the laser image-forming composition according to the present invention, the oligomer is selected from bifunctional or trifunctional oligomers, preferably bifunctional oligomers, such as bifunctional or trifunctional epoxy (meth) acrylate oligomers, modified epoxy (meth) acrylate oligomers, and amine (meth) acrylate oligomers, or combinations thereof, and the monomer is a bifunctional or trifunctional monomer, such as tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO)3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 TA). More preferably, the oligomer is selected from difunctional or trifunctional oligomers, preferably difunctional oligomers, such as difunctional or trifunctional epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof, and the monomer is selected from difunctional or trifunctional monomers, such as tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 TA). More preferably, the oligomer is a difunctional oligomer, such as a difunctional epoxy (meth)acrylate oligomer, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9It is selected from (TA). More preferably, the oligomer is a bifunctional epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA). By selecting the specified oligomer and monomer, when the laser image-forming composition is irradiated with radiation, it becomes possible to generate a high-quality, high-contrast image. In addition, the selection of the specified oligomer and monomer means that the laser image-forming composition can exhibit enhanced environmental resistance, and when irradiated with radiation, a high-contrast image is formed and maintained over a long period. The laser image-forming composition usually also exhibits improved hardness, flexibility, gloss, chemical resistance, and adhesion properties when such oligomers and monomers are selected. This is especially the case when the oligomer is selected to be a bifunctional epoxy (meth) acrylate oligomer and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), especially when the oligomer is selected to be a bifunctional epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA).

[0054] The monomer may be present in the laser image-forming composition according to the present invention in any suitable amount. Preferably, when present, the laser image-forming composition contains 10 to 50 wt%, for example 10 to 40 wt%, or further 10 to 30 wt%, or 10 to 25 wt% of the monomer.

[0055] The oligomer of the laser image-forming composition of the present invention is selected such that the printing viscosity of the laser image-forming composition reaches a level suitable for offset lithographic printing. Moreover, the oligomer of the laser image-forming composition is selected such that, by its ability, wetting, dispersion suspension, and stabilization of the polyvalent metal oxyanion therein are made possible.

[0056] The printing viscosity of the laser image-forming composition of the present invention may be 10 - 600 Pa·s (10,000 - 600,000 cP), for example 55 - 500 Pa·s (55,000 - 500,000 cP), or further 80 - 400 Pa·s (80,000 - 400,000 cP). Preferably, the printing viscosity is 100 - 400 Pa·s (100,000 - 400,000 cP), more preferably 100 - 300 Pa·s (100,000 - 300,000 cP). Those skilled in the art should understand that these printing viscosity ranges are appropriate for use in offset lithographic printing.

[0057] The printing viscosity of the laser image-forming composition of the present invention is measured at 22°C. The printing viscosity is measured using a Brookfield DV2T Viscometer. Usually, a No. 7 spindle (RV spindle set) is used, and the rotation speed is selected to be suitable for each individual laser image-forming composition. Usually, the rotation speed is selected from speeds of 2, 10, 12, 20, 40, 60, and 100 rpm. The printing viscosity is the viscosity of the laser image-forming composition if it is appropriate for coating on a substrate, that is, if it is appropriate for coating on a substrate by offset lithographic printing. The printing viscosity of the laser image-forming composition of the present invention is preferably measured within 1 month, for example within 2 weeks, more preferably within 1 week from the formulation of the laser image-forming composition.

[0058] As discussed above, the laser image-forming composition of the present invention may further contain a monomer. In addition to the viscosity of the oligomer, it should be understood by those skilled in the art that the viscosity of this optional monomer also contributes to the overall printing viscosity of the laser image-forming composition. Therefore, the viscosity of the oligomer used in the laser image-forming composition of the present invention may vary depending on the presence / absence of the monomer in the laser image-forming composition. As discussed above, the presence of the monomer in the laser image-forming composition of the present invention enables the use of a wider range of oligomers, particularly oligomers with increased viscosity. This enhances the rheology profile of the laser image-forming composition of the present invention during the offset lithography printing process and results in improved smoothness when applied to the desired substrate.

[0059] When the laser-reactive composition of the present invention does not contain monomers, the oligomer may typically have a viscosity of 200 Pa·s or less (200,000 cP or less), for example 160 Pa·s or less (160,000 cP or less), or 100 Pa·s or less (100,000 cP or less), preferably 80 Pa·s or less (80,000 cP or less). When the laser-reactive composition of the present invention does not contain monomers, the lower limit of the viscosity of the oligomer may be 1 Pa·s (1,000 cP), preferably 3 Pa·s (3,000 cP), so that the oligomer may have a viscosity of 1 to 200 Pa·s (1,000 to 200,000 cP), for example 1 to 160 Pa·s (1,000 to 160,000 cP), or 1 to 100 Pa·s (1,000 to 100,000 cP), preferably 1 to 80 Pa·s (1,000 to 80,000 cP), or the oligomer may have a viscosity of 3 to 200 Pa·s (3,000 to 200,000 cP), for example 3 to 160 Pa·s (3,000 to 160,000 cP), or 3 to 100 Pa·s (3,000 to 100,000 cP), preferably 3 to 80 Pa·s (3,000 to 80,000 cP). Alternatively, when the laser-image-forming composition of the present invention further contains monomers, the viscosity of the oligomer may exceed the case where no monomers are present in the laser-image-forming composition. Thus, when the laser-image-forming composition of the present invention further contains monomers, the oligomer may have a viscosity of 50 Pa·s or more (50,000 cP or more), for example 100 Pa·s or more (100,000 cP or more), or 200 Pa·s or more (200,000 cP or more), or even 1,000 Pa·s or more (1,000,000 cP or more). When monomers are present in the laser-image-forming composition, it should be understood by those skilled in the art that an equilibrium is achieved between the viscosities of the oligomer and monomer components, and as a result, the printing viscosity of the laser-image-forming composition is suitable for use in offset lithographic printing.

[0060] The viscosity of the oligomer is measured at 25°C. The viscosity of the oligomer may be measured using a Brookfield DV2T Viscometer. The spindle and rotational speed are selected to be suitable for the individual oligomer. Spindle 7 (RV spindle set) may be used, and the rotational speed may be selected from speeds 2, 10, 12, 20, 40, 60, and 100 rpm.

[0061] Thus, within the scope of the present invention, (a) the oligomer may have a viscosity of 200 Pa·s or less (200,000 cP or less), such as 160 Pa·s or less (160,000 cP or less), or 100 Pa·s or less (100,000 cP or less), or 80 Pa·s or less (80,000 cP or less), D 50 A laser image-forming composition comprising a polyvalent metal oxyanion and an oligomer containing particles having a particle size distribution of 10 μm or less, and (b) the oligomer may have a viscosity of 50 Pa·s or more (50,000 cP or more), such as 100 Pa·s or more (100,000 cP or more), or 200 Pa·s or more (200,000 cP or more), or even 1,000 Pa·s or more (1,000,000 cP or more), D 50 It should be understood that both a laser image-forming composition comprising a polyvalent metal oxyanion, an oligomer, and a monomer containing particles having a particle size distribution of 10 μm or less are included.

[0062] The monomers of the laser image-forming composition of the present invention are selected such that the printing viscosity of the laser image-forming composition is maintained at a level suitable for offset lithographic printing. It should be understood by those skilled in the art that an equilibrium is achieved between the viscosities of the oligomer and monomer components, and as a result, the printing viscosity of the laser image-forming composition is appropriate for use in offset lithographic printing, i.e., the printing viscosity is adjusted to an acceptable printing viscosity for offset lithographic printing. Thus, monomers may be introduced into the laser image-forming composition. Further, as discussed above, the presence of monomers in the laser image-forming composition of the present invention allows for the use of a wider range of oligomers, particularly oligomers of increased viscosity. This enhances the rheology profile of the laser image-forming composition of the present invention during the offset lithographic printing process and results in improved smoothness when applied to the desired substrate.

[0063] The monomers used in the laser-reactive composition according to the present invention usually have a viscosity of 1.8 Pa·s or less (1,800 cP or less), preferably 0.8 Pa·s or less (800 cP or less), or more preferably 0.1 Pa·s or less (100 cP or less), for example 0.05 Pa·s (50 cP or less), and more preferably 0.02 Pa·s or less (20 cP or less). The monomers used in the laser-reactive composition according to the present invention may have a lower viscosity limit of 0.01 Pa·s (10 cP), preferably 0.015 Pa·s (15 cP). As a result, the monomers may have a viscosity of 0.01 to 1.8 Pa·s (10 to 1,800 cP), preferably 0.01 to 0.8 Pa·s (10 to 800 cP), or more preferably 0.01 to 0.1 Pa·s (10 to 100 cP), for example 0.01 to 0.05 Pa·s (10 cP to 50 cP), and more preferably 0.01 to 0.02 Pa·s (10 to 20 cP). Alternatively, the monomers may have a viscosity of 0.015 to 1.8 Pa·s (15 to 1,800 cP), preferably 0.015 to 0.8 Pa·s (15 to 800 cP), or more preferably 0.015 to 0.1 Pa·s (15 cP to 100 cP), for example 0.015 to 0.05 Pa·s (15 cP to 50 cP), and more preferably 0.015 to 0.02 Pa·s (15 cP to 20 cP). As described above, in order for oligomers with a higher viscosity to be usable in the laser image-forming composition of the present invention, it is preferable to use monomers with a low viscosity. When the laser image-forming composition of the present invention is irradiated with radiation, not only does it promote the formation of a high-quality, high-contrast image by the laser image-forming composition of the present invention, but when oligomers with a higher viscosity are used, the rheology profile of the laser image-forming composition can increase. A combination of oligomers with a higher viscosity and monomers with a lower viscosity is beneficial for printing and the laser image-forming ability of the laser image-forming composition of the present invention.

[0064] Preferably, the monomers are tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO)3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 TA), selected from the group consisting of, having a viscosity of 0.01 to 1.8 Pa·s (10 to 1,800 cP), preferably 0.01 to 0.8 Pa·s (10 to 800 cP), or more preferably 0.01 to 0.1 Pa·s (10 to 100 cP), for example 0.01 to 0.05 Pa·s (10 cP to 50 cP), more preferably 0.01 to 0.02 Pa·s (10 to 20 cP). More preferably, the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9 TA), i.e., selected from bifunctional or trifunctional monomers, having a viscosity of 0.01 to 0.1 Pa·s (10 to 100 cP), for example 0.01 to 0.05 Pa·s (10 cP to 50 cP), more preferably 0.01 to 0.02 Pa·s (10 to 20 cP). Most preferably, the monomer is tripropylene glycol diacrylate (TPGDA), i.e., a bifunctional monomer, having a viscosity of 0.01 to 0.05 Pa·s (10 cP to 50 cP), more preferably 0.01 to 0.02 Pa·s (10 to 20 cP).

[0065] Preferably, the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 Triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 Triacrylate (TMP(EO) 9selected from TA), having a viscosity of 0.015 to 0.8 Pa·s (15 to 800 cP), or further 0.015 to 0.1 Pa·s (15 cP to 100 cP), for example 0.015 to 0.05 Pa·s (15 cP to 50 cP), preferably 0.015 to 0.02 Pa·s (15 cP to 20 cP). More preferably, the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 selected from TA), i.e., a difunctional or trifunctional monomer, having a viscosity of 0.015 to 0.1 Pa·s (15 cP to 100 cP), for example 0.015 to 0.05 Pa·s (15 cP to 50 cP), preferably 0.015 to 0.02 Pa·s (15 cP to 20 cP). Most preferably, the monomer is tripropylene glycol diacrylate (TPGDA), i.e., a difunctional monomer, having a viscosity of 0.015 to 0.05 Pa·s (15 cP to 50 cP), preferably 0.015 to 0.02 Pa·s (15 cP to 20 cP).

[0066] The viscosity of the monomer is measured at 25°C. The viscosity of the monomer may be measured using a Brookfield DV2T Viscometer. The spindle and rotation speed are selected to be suitable for each individual monomer. The 7th spindle (RV spindle set) may be used, and the rotation speed may be selected from speeds 2, 10, 12, 20, 40, 60 and 100 rpm.

[0067] The laser image-forming composition according to the present invention may further contain a stabilizer. It should be noted that the laser image-forming composition may contain two or more stabilizers. Suitable stabilizers include, but are not limited to, the following: hydroquinone, methoxymethylhydroquinone, 4-benzoquinone, 4-methoxyphenol (mequinol), phenothiazine, mono-tert-butylhydroquinone, catechol, 4-tert-butylcatechol, benzoquinone, 2,5-di-tert-butylhydroquinone, 2,5-p-dimethyl-p-benzoquinone, anthraquinone, 2,6-di-tert-butylhydroxytoluene, organic phosphite, methacrylated phosphate ester, 4-hydroxyanisole, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum, 2-phenoxyphenyl acrylate, and HALS (hindered amine light stabilizer) compounds including derivatives of tetramethylpiperidine, or combinations thereof.

[0068] Suitable stabilizers also include commercially available stabilizer products such as Genorad 20 commercially available from Rahn AG. Such commercially available stabilizer products may also include a carrier for the stabilizer in which the stabilizer can be dissolved.

[0069] The stabilizer may be present in the laser image-forming composition according to the present invention in any suitable amount. Preferably, when present, the laser image-forming composition contains 0.1 to 5 wt%, for example 0.1 to 3 wt%, or further 0.1 to 1 wt% of the stabilizer.

[0070] The laser image-forming composition according to the present invention may further contain a photoinitiator. It should be noted that the laser image-forming composition may contain two or more photoinitiators. Suitable photoinitiators include, but are not limited to: Norrish type I photoinitiators, such as phosphine oxides, hydroxyacetophenones, aminoacetophenones and benzyl ketals; Norrish type II photoinitiators including benzyl formate, substituted benzophenones, benzophenones and thioxanthones; and hybrid Norrish I / II type photoinitiators, such as benzophenone phosphine oxide. It should be understood by those skilled in the art that Norrish type II photoinitiators may be used alone or together with an amine synergist as a hydrogen donor. Preferably, the photoinitiator is selected from Norrish type I photoinitiators or hybrid Norrish I / II type photoinitiators. More preferably, the photoinitiator is a Norrish type I photoinitiator, such as hydroxyacetophenone or phosphine oxide. Even more preferably, the photoinitiator is phosphine oxide. Most preferably, the photoinitiator is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO).

[0071] The term "Norrish type I photoinitiator", as used herein, refers to a photoinitiator characterized by a cleavage reaction of the original photoinitiator into two radical fragments. Irradiation with UV light results in homolytic bond cleavage and the generation of two highly reactive radical species. These radicals then initiate polymerization. Norrish type I photoinitiators are irreversibly incorporated into the polymer matrix. Examples of Norrish type I photoinitiators, all commercially available from Lambson, include, but are not limited to, 2-hydroxy-2-methyl-1-phenylpropan-1-one (SpeedCure 73), 1-hydroxycyclohexyl phenyl ketone (SpeedCure 84), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropan-1-one (SpeedCure 2959), 2,2-dimethoxy-1,2-diphenylethanone (SpeedCure BKL), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (SpeedCure 97), 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone (SpeedCure BDMB), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SpeedCure TPO), ethyl 2,4,6-trimethylbenzoyl phenylphosphinate (SpeedCure TPO-L) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (SpeedCure BPO).

[0072] The term "Norrish type II photoinitiator", as used herein, refers to a photoinitiator that requires a hydrogen donor (co-initiator) to react when irradiated with UV light. Most commonly, these hydrogen donors are amines (amine synergists). Upon UV irradiation, the Norrish type II photoinitiator abstracts a hydrogen atom from the utilized synergist to form two radicals. These radicals can then initiate a polymerization reaction, similar to Norrish type I photoinitiators. Norrish type II photoinitiators are not usually incorporated during the reaction, while the synergist is incorporated. Examples of Norrish type II photoinitiators include, but are not limited to, benzophenone (SpeedCure BP), 4-methylbenzophenone (SpeedCure MBP), methyl-2-benzoylbenzoate (SpeedCure MBB), 4,4'-bis(diethylamino)benzophenone (SpeedCure EMK), 4-benzoyl-4'-methyldiphenyl sulfide (SpeedCure BMS), 4-phenylbenzophenone (SpeedCure PBZ), 2-isopropylthioxanthone (SpeedCure 2-ITX), 1-chloro-4-propoxythioxanthone (SpeedCure CPTX), 2,4-diethylthioxanthone (SpeedCure DETX), methylbenzoylformate (SpeedCure MBF), polymeric benzophenone (SpeedCure 7005) and polymeric thioxanthone (SpeedCure 7010), all commercially available from Lambson. Examples of suitable amine synergists include, but are not limited to, 2-butoxyethyl-4-(dimethylamino)benzoate (SpeedCure BEDB), 2-(dimethylamino)ethyl benzoate (SpeedCure DMB), ethyl-4-(dimethylamino)benzoate (SpeedCure EDB), 2-ethylhexyl-4-(dimethylamino)benzoate (SpeedCure EHA), 4,4'-bis(diethylamino)benzophenone (SpeedCure EMK) and polymeric amine synergist (SpeedCure 7040), all commercially available from Lambson.

[0073] The term "Norrish I / II type photoinitiator", as used herein, refers to a hybrid of both Norrish type I and type II photoinitiators. Such photoinitiators can generate radicals via homolytic bond cleavage and further hydrogen abstraction to generate radicals. A suitable example of a Norrish I / II type photoinitiator is ethyl(3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl)phosphinate (SpeedCure XKM) commercially available from Lambson.

[0074] The photoinitiator may be present in the laser image-forming composition according to the invention in any suitable amount. Preferably, when present, the laser image-forming composition contains 1 to 10 wt%, such as 1 to 8 wt%, or even 2 to 6 wt% of the photoinitiator.

[0075] The ratio of the stabilizer to the photoinitiator present in the laser image-forming composition may be from 1:3 to 1:9, such as from 1:3 to 1:6, or from 1:4 to 1:5. Preferably, the ratio of the stabilizer to the photoinitiator is 1:4. Such a ratio enables easier curing of the composition while also providing improved long-term storage stability for the composition.

[0076] The laser image-forming composition according to the present invention may further contain a near-infrared (NIR) absorber. It should be understood by those skilled in the art that when NIR rays are usually used to promote image formation, the NIR absorber is used, and the NIR absorber can enhance the absorption of NIR rays. Examples of suitable NIR absorbers include, but are not limited to, the following: inorganic copper salts such as copper (II) hydroxide phosphate (CHP); organic NIR dyes and pigments such as N,N,N’,N’-tetrakis(4-dibutylaminophenyl)-p-benzoquinone bis(iminium hexafluoroantimonate); non-stoichiometric inorganic compounds such as indium tin oxide, zinc oxide, tungsten bronze, and inorganic compounds of the formula MxWyOz (where M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1; and 2.2 ≦ z / y ≦ 3.0) including reduced-doped tungsten oxide, reduced antimony tin oxide, or doped metal oxides such as aluminum-doped zinc oxide (AZO) and fluorine-doped tin oxide (FTO); conductive polymers such as polypolystyrene sulfonic acid (PEDOT); and combinations thereof.Preferably, the NIR absorber is selected from inorganic copper salts such as copper (II) hydroxide phosphate (CHP) and non-stoichiometric inorganic compounds such as indium tin oxide, zinc oxide, tungsten oxide (tungsten bronzes), and inorganic compounds of the following formula MxWyOz (where M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I; W is tungsten; O is oxygen; 0.001 ≦ x / y ≦ 1; and 2.2 ≦ z / y ≦ 3.0). Preferably, when present, the laser image-forming composition contains 0.05 to 25 wt%, for example 0.05 to 20 wt% of the NIR absorber. When near-infrared light is to be used as the radiation for forming the image, the near-infrared absorber is preferably present in the laser image-forming composition.

[0077] The laser image-forming composition may further contain an additive or a combination of additives. Suitable additives should be well known to those skilled in the art. Examples of suitable additives include, but are not limited to: polymers; light or energy absorbers; UV absorbers; surfactants; wetting agents; drying accelerators; dyes such as pigments; colorants; fluorescent agents; plasticizers; optical brighteners; oxidizing or reducing agents; stabilizers; light stabilizers such as hindered amines; rheology modifiers such as thickeners or diluents; amine synergists; matting agents; activated clay; anti-settling agents; anti-sagging agents; dispersants; surface-modifying additives; slip additives; leveling agents; fillers; water retention agents; adhesion promoters; acid or base scavengers; retarders; defoamers; anti-foaming agents; and combinations thereof. Preferably, when present, the laser image-forming composition contains 0.1 to 10 wt%, for example 0.25 to 7.5 wt%, more preferably 0.5 to 5 wt% of the additive or a combination thereof.

[0078] Preferably, the laser image-forming composition does not contain any additional binder component. By "additional binder component" is meant any component other than oligomers and optional monomers that can act as a binder for the laser image-forming composition of the present invention. In particular, this includes components that have been pre-reacted, such as resins, for example acrylic resins, if introduced into the composition during formulation. The laser image-forming composition of the present invention does not contain pre-reacted components. The laser image-forming composition of the present invention does not contain resins. The oligomer and optional monomer components of the laser image-forming composition of the present invention are reactive binders, i.e., they react only upon formulation of the composition. They are not pre-reacted components, such as resins.

[0079] Preferably, the laser image-forming composition of the present invention does not contain pigments, such as titanium dioxide.

[0080] The laser image-forming composition of the present invention is suitable for use in offset lithography printing processes and techniques.

[0081] According to a second aspect of the present invention, there is provided a method of forming a laser image-forming composition according to the present invention, the method comprising the step of combining a polyvalent metal oxyanion and an oligomer.

[0082] The method of forming a laser image-forming composition according to the present invention (a) forming a composition comprising a polyvalent metal oxyanion and an oligomer, and (b) grinding the composition to obtain a laser image-forming composition comprising a polyvalent metal oxyanion and an oligomer, wherein the polyvalent metal oxyanion is D 50 comprising particles having a particle size distribution of 10 μm or less. may include.

[0083] Instead, the method for forming a laser image-forming composition according to the present invention comprises: (a’) pulverizing an oxyanion of a polyvalent metal to obtain particles having a particle size distribution of 10 μm or less, and 50 and (b’) combining the oxyanion of the polyvalent metal containing particles having a particle size distribution of 10 μm or less with an oligomer. (b’)D 50 The step may include. It may include.

[0084] When the laser image-forming composition further contains a monomer, the monomer may be combined with the oxyanion of the polyvalent metal containing particles having a particle size distribution of 10 μm or less and the oligomer in step (b’). 50 It may be combined with an oxyanion of a polyvalent metal containing particles having a particle size distribution of 10 μm or less and an oligomer.

[0085] Preferably, the method for forming a laser image-forming composition according to the present invention comprises: (a) forming a composition containing an oxyanion of a polyvalent metal and an oligomer, and (b) pulverizing the composition to obtain a laser image-forming composition containing an oxyanion of a polyvalent metal and an oligomer, wherein the oxyanion of the polyvalent metal contains 50 Particles having a particle size distribution of 10 μm or less, step including.

[0086] When the laser image-forming composition further contains a monomer, the monomer may be combined with the oxyanion of the polyvalent metal and the oligomer in step (a) before pulverization to form a composition. Alternatively, the monomer may be introduced into the composition after step (b). Preferably, when the laser image-forming composition further contains a monomer, the monomer is combined with the oxyanion of the polyvalent metal and the oligomer in step (a) before pulverization to form a composition.

[0087] The grinding of particles of the polyvalent metal oxyanion, or the composition (and hence the particles of the polyvalent metal oxyanion), may be carried out using any suitable process. Suitable grinding processes should be well known to those skilled in the art. Preferably, in the context of the present invention, the particles of the polyvalent metal oxyanion, or the composition, are ground using three-roll grinding on a three-roll mill and mechanical bead grinding techniques. To achieve the desired particle size, the particles or composition of the polyvalent metal oxyanion may be passed through the machine once. However, preferably, the particles or composition of the polyvalent metal oxyanion are passed through the machine at least twice, more preferably three or more times, until the desired particle size distribution for the particles of the polyvalent metal oxyanion is obtained.

[0088] In the method of forming a laser image-forming composition according to the present invention, the grinding of particles of the polyvalent metal oxyanion, or the composition (and hence the particles of the polyvalent metal oxyanion), may be carried out using an Exakt 50 (laboratory) or Buehler SDT-800 (commercial) unit.

[0089] In the method of forming a laser image-forming composition according to the present invention, when the particles of the polyvalent metal oxyanion and the oligomer are combined, it should be understood by those skilled in the art that the particles of the polyvalent metal oxyanion should be sufficiently wetted, dispersed and stabilized in the oligomer during the production of the laser image-forming composition.

[0090] In the method of forming a laser image-forming composition according to the present invention, the laser image-forming composition may have any of the properties that are preferred or any of the above properties with respect to the laser image-forming composition according to the present invention.

[0091] The laser image-forming composition according to the present invention may be applied to any suitable substrate. It should be understood that the components of the laser image-forming composition may vary depending on the substrate to which the laser image-forming composition is applied.

[0092] Accordingly, according to a third aspect of the present invention, there is provided a substrate comprising the laser image-forming composition according to the present invention applied to a substrate.

[0093] In a substrate comprising the laser image-forming composition according to the present invention applied to a substrate, the laser image-forming composition may have any of the preferred or optional properties described above with respect to the laser image-forming composition according to the present invention.

[0094] It should be understood by those skilled in the art that the laser image-forming composition according to the present invention can be applied to a substrate at a low coating weight using an offset lithography printing process. Thus, the substrate can be any substrate suitable for use in offset lithography.

[0095] Examples of suitable substrates onto which the laser image-forming composition of the present invention can be applied include polymer and recycled polymer materials such as polyethylene terephthalate (PET), polyethylene (PE), low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), polypropylene (PP), oriented polypropylene (OPP), biaxially oriented polypropylene (BOPP), unoriented polypropylene (CPP), polyamide (PA) such as nylon, polyvinyl chloride (PVC), or combinations thereof; cellulose; glass; plastics; metals and metal foils such as tinplate; cloth; paper, both gloss paper and textured paper; coated paper such as polymer-coated paper; cardboard, carton board, board paper, thick paper, and equivalent recycled analogs, or combinations thereof; ceramics; food and pharmaceuticals; or combinations thereof including but not limited to polymer-lined paper or polymer-impregnated paper. Suitable substrates include multilayer constructs formed from the materials and substrates listed above. The polymer and recycled polymer materials may be in the form of polymer foils or film substrates.

[0096] Preferably, the substrate onto which the laser image-forming composition is applied is selected from plastics, polymer films and foils, foldable cartons and carton board, metals and metal foils, paper, corrugated board and cardboard and equivalent recycled analogues.

[0097] The laser image-forming composition of the present invention may be applied to a non-metallic substrate. In such cases, examples of suitable substrates onto which the laser image-forming composition of the present invention may be applied include polymer and recycled polymer materials such as polyethylene terephthalate (PET), polyethylene (PE), low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), polypropylene (PP), oriented polypropylene (OPP), biaxially oriented polypropylene (BOPP), cast polypropylene (CPP), polyamide (PA) such as nylon, polyvinyl chloride (PVC), or combinations thereof; cellulose; glass; plastics; cloth; paper, both glossy paper and textured paper; coated paper such as polymer-coated paper; corrugated board, carton board, board paper, cardboard, and equivalent recycled analogues, or combinations thereof; ceramics; food and pharmaceuticals; or combinations thereof such as polymer-lined paper or polymer-impregnated paper, but are not limited thereto. Suitable substrates include multilayer constructs formed from the materials and substrates listed above. The polymer and recycled polymer materials may be in the form of polymer foils or film substrates.

[0098] When the substrate onto which the laser image-forming composition is applied is a non-metallic substrate, the substrate is preferably selected from plastics, polymer films and foils, foldable cartons and carton board, paper, corrugated board and cardboard and equivalent recycled analogues.

[0099] The laser image-forming composition according to the present invention, or a substrate comprising the laser image-forming composition of the present invention coated on a substrate, may be suitable for end uses such as labels (adhesive or wrap-around type), and / or consumer goods; packages, such as disposable packages including containers for food and hot or cold beverages and folding cartons; folding cartons; coated paper; can ends; decorative metal products; blister pack packages; and medical and diagnostic devices and related packages; and outdoor products such as billboards. The laser image-forming composition according to the present invention, or a substrate comprising the laser image-forming composition of the present invention coated on a substrate, may be used for coding and printing, tagging and tracking and subsequent customization or personalization purposes.

[0100] In a fourth aspect of the present invention, there is provided a method of forming a substrate comprising the laser image-forming composition of the present invention coated on a substrate, the method comprising the step of coating a substrate with the laser image-forming composition according to the present invention.

[0101] In the method of forming a substrate comprising the laser image-forming composition of the present invention coated on a substrate, the laser image-forming composition may have any of the properties preferred or described above with respect to the present invention. In addition, the substrate comprising the laser image-forming composition of the present invention coated on a substrate may have any of the properties preferred or described above with respect to the present invention.

[0102] The laser image-forming composition according to the present invention is preferably applied to a substrate by an offset lithographic printing process.

[0103] The laser image-forming composition according to the present invention may be applied to a substrate up to any suitable coating weight achievable using an offset lithographic printing process. It should be understood that the coating weight of the laser image-forming composition on the substrate affects the optical density of the image formed and thus the contrast of the image formed with the background of the laser image-forming composition.

[0104] The laser image-forming composition may be applied to the substrate to an appropriate thickness for an offset lithography printing process, such as 0.5 to 3 μm, or 0.5 to 2.0 μm, such as 0.5 to 1.1 μm, or 0.5 to 1.0 μm. This thickness may be formed by applying one or more layers of the laser image-forming composition to the substrate. Preferably, this thickness is formed by applying a single layer of the laser image-forming composition to the substrate.

[0105] The thickness may be measured by any suitable method. Suitable measuring methods should be well known to those skilled in the art. Usually, the thickness defined herein may be measured using a micrometer or a coating thickness gauge. Such equipment should be well known to those skilled in the art.

[0106] The laser image-forming composition may be applied to the substrate to a coating weight of 0.7 to 2 gsm (grams per square meter), such as 0.7 to 1.8 gsm, or 0.7 to 1.7 gsm. Preferably, the laser image-forming composition is applied to a coating weight of 0.8 to 1.5 gsm, such as 0.8 to 1.2 gsm. This coating weight may be caused by applying one or more layers of the laser image-forming composition to the substrate. Preferably, this coating weight is caused by applying a single layer of the laser image-forming composition to the substrate.

[0107] The coating weight may be measured by any suitable method. Suitable measuring methods should be well known to those skilled in the art. Preferably, the coating weight is measured by weighing a substrate with and without the laser image-forming composition applied thereto having the same area and comparing the two weights. Usually, this is the average of several data sets.

[0108] Even when only a single layer of the laser image-forming composition of the present invention is applied to a substrate by offset lithography, a high-contrast image can be formed, that is, as discussed above, it should be understood that ΔODB of 0.6 or more is achieved.

[0109] The laser image-forming composition according to the present invention may be applied to a substrate as a single layer or in multiple layers, that is, once or more than once. Preferably, 1 to 3 layers of the laser image-forming composition are applied. More preferably, 1 to 2 layers of the laser image-forming composition are applied. Most preferably, the laser image-forming composition is applied as a single layer.

[0110] The laser image-forming composition may be applied directly to the substrate, that is, in a state where there is no layer disposed / applied between the laser image-forming composition and the substrate.

[0111] The laser image-forming composition may be applied to the substrate on top of a primer or as a primer layer, as an undercoat or overcoat. The laser image-forming composition may be applied to the substrate on top of a base color coating layer and / or on top of or under a protective varnish layer. The laser image-forming composition may be applied to at least a part or the whole of the outer surface of the substrate.

[0112] After the application of the laser image-forming composition according to the present invention to the substrate, the laser image-forming composition may be cured using radiation. Preferably, the laser image-forming composition is cured using radiation after the application of the laser image-forming composition to the substrate. More preferably, the laser image-forming composition is cured using UV rays (100 to 400 nm). The UV rays may be irradiated onto the laser image-forming composition using any suitable source, such as a UV laser source or a UV lamp, such as a mercury lamp that provides UV rays, or an ionizing radiation source, such as an LED or an electron beam source.

[0113] The laser image-forming composition according to the present invention may be used to form an image on a substrate.

[0114] Accordingly, according to a fifth aspect of the present invention, there is provided a method of forming an image on a substrate comprising a laser image-forming composition according to the present invention applied to the substrate, the method comprising the step of exposing the laser image-forming composition to radiation to form an image on the substrate.

[0115] In the method of forming an image on a substrate comprising a laser image-forming composition according to the present invention applied to the substrate, the laser image-forming composition may have any of the preferred or optional properties described above with respect to the present invention. In addition, the substrate comprising the laser image-forming composition according to the present invention applied to the substrate may have any of the preferred or optional properties described above with respect to the present invention.

[0116] The term "image" encompasses, but is not limited to, logos, marks, graphics, diagrams, pictures, symbols, characters, numbers, codes, such as linear barcodes, 2D data matrices, QR codes, Digimarc codes, and text incorporating alphanumeric and symbols, for example. In the context of the present invention, this is understood to be the manipulation of a laser image-forming composition comprising an oxyanion of a polyvalent metal as an image-forming compound that facilitates the formation of an image. The image formed is human and / or machine-readable and may be used for coding and printing, tagging and tracking, and subsequent customization or personalization purposes. The density of the image is measured by the ΔODB value as discussed above.

[0117] In the context of the present invention, the radiation is irradiated after application of the laser image-forming composition to the substrate and usually subsequent curing. Accordingly, the image is formed after application of the laser image-forming composition to the substrate and usually subsequent curing.

[0118] It should be understood by those skilled in the art that the radiation selected is the radiation necessary to form a distinguishable black color in the "image-forming compound", i.e., the oxyanion of the polyvalent metal.

[0119] As used herein, "radiation" and similar terms refer to energy in the form of waves or particles, and in particular to electromagnetic radiation, such as ultraviolet (UV), visible, near-infrared (NIR), and infrared (IR), particle radiation, such as alpha (α), beta (β), neutron radiation, and plasma. The wavelength ranges of the various regions of the electromagnetic spectrum are known to those skilled in the art.

[0120] The radiation may be selected from ultraviolet (UV) rays having a wavelength of 10 to 400 nm, visible rays having a wavelength of 400 to 700 nm, infrared (IR) rays having a wavelength of 700 nm to 1 mm, and near-infrared (NIR) rays having a wavelength of 700 to 1600 nm. Preferably, the radiation is visible rays having a wavelength of 400 to 700 nm, infrared (IR) rays having a wavelength of 9000 to 12000 nm (irradiated using a CO 2 laser), infrared (IR) rays having a wavelength of 700 nm to 1 mm, and near-infrared (NIR) rays having a wavelength of 700 to 1600 nm. More preferably, the radiation is infrared (IR) rays having a wavelength of 9000 to 12000 nm (irradiated using a CO 2 laser), such as 9300, 9600, 10200, or 10600 nm (irradiated using a CO 2 laser), infrared (IR) rays having a wavelength of 700 nm to 1 mm, and near-infrared (NIR) rays having a wavelength of 700 to 1600 nm. Most preferably, the radiation is infrared (IR) rays having a wavelength of 9000 to 12000 nm (irradiated using a CO 2 laser), such as 9300, 9600, 10200, or 10600 nm (irradiated using a CO 2 laser).

[0121] The radiation may be applied to the laser image-forming composition by any suitable means. Suitable means include laser excitation via the application of radiation from a laser source to the laser image-forming composition. It should be understood by those skilled in the art that the radiation may be applied to the laser image-forming composition at these local positions to selectively promote the formation of an image at the local positions in the laser image-forming composition. These local positions may overlap with each other. It should also be understood by those skilled in the art that the radiation is applied to the laser image-forming composition for a suitable time required to promote the formation of the image. Generally, the time required to deliver sufficient radiation depends on the means and method of irradiation used. For example, in one embodiment, the radiation may be applied to the laser image-forming composition for less than 120 seconds (e.g., 30 to 110 seconds, or even 75 to 105 seconds), or less than 60 seconds, such as less than 20 seconds, or even less than 10 or 5 seconds.

[0122] When irradiated using a laser source, the amount of radiation applied depends on the time during which the radiation is applied, the output (in watts) of the means used to apply the radiation, and thus the fluence (the amount of energy delivered per unit area) delivered by the laser source, e.g., J / cm 2It should be understood that it may be controlled by the change of . It should be understood by those skilled in the art that this may affect the density of the formed image and the degree of contrast with the background of the image. For example, when a laser source is used to irradiate radiation, the fluence (the amount of energy delivered per unit area) may affect the density of the formed image. In the context of the present invention, the fluence depends on the output (in watts) of the means used to irradiate the radiation, which can be controlled by the scan speed of the laser or the speed of the moving stage, and the time during which the radiation is irradiated onto a specific local position of the substrate. These two variables may be changed to vary the fluence. When the fluence is small (e.g., smaller output and / or shorter irradiation time), the formed image has a smaller optical density, and when the fluence is large (e.g., larger output and / or longer irradiation time), the formed image has a larger density and a greater contrast with the background of the laser image-forming composition. In the context of the present invention, the fluence value may be in the range of 0.01 - 20 J / cm 2 , for example, 0.1 - 10 J / cm 2 , and further 0.5 - 5 J / cm 2 .

[0123] Preferably, the radiation is irradiated onto the laser image-forming composition at a local position of the laser image-forming composition to form a desired image. Basically, when the radiation is irradiated, black is formed in the part of the laser image-forming composition on the substrate irradiated with the radiation. Thus, an image with a contrast that can be read by humans and / or machines is generated. What enables the formation of the image is the oxyanion of a polyvalent metal that functions as an "image-forming compound" of the laser image-forming composition.

[0124] In a sixth aspect of the present invention, the use of the laser image-forming composition according to the present invention in offset lithography is provided.

[0125] In the use of the laser image-forming composition of the present invention in offset lithographic printing, the laser image-forming composition may have any of the properties which are preferred or any of the above with respect to the present invention.

[0126] In a seventh aspect of the present invention, there is provided the use of a laser image-forming composition according to the present invention in the formation of an image on a substrate.

[0127] In the use of the laser image-forming composition of the present invention in the formation of an image on a substrate, the laser image-forming composition may have any of the properties which are preferred or any of the above with respect to the present invention.

[0128] All of the properties contained herein may be combined in any of the above aspects and in any combination.

[0129] Chemical Definitions The term "alkyl" refers to a straight-chain or branched saturated alkyl group usually having from 1 to 20 carbon atoms, and optionally the alkyl group may contain some degree of unsaturation (partially unsaturated), i.e., it may contain one or more alkene / alkenyl moieties. The alkyl group may optionally be substituted with one or more functional groups.

[0130] All references to specific chemical compounds herein are to be construed as including the compounds themselves, and, where appropriate, their derivatives, hydrates, solvates, complexes, isomers and tautomers.

[0131] For a better understanding of the present invention and to show how the embodiments of the foregoing may be carried out, reference is made hereinafter, by way of example, to the following experimental data.

Examples

[0132] In each of the examples, the color of the laser image-forming composition is almost white or white at the time of formulation, at the time of application to the substrate, and prior to irradiation with any radiation thereon.

[0133] In each of the examples, using a Brookfield DV2T Viscometer with a No. 7 spindle (RV spindle set), the printing viscosity of the laser image-forming composition was measured at 22 °C at a suitable speed selected from 2, 10, 12, 20, 40, 60, and 100 rpm. The oligomer and monomer viscosities were measured at 25 °C. As shown in the examples, the oligomer and monomer viscosities are the viscosities provided for commercially available products or were measured using a Brookfield DV2T Viscometer with a No. 7 spindle (RV spindle set) at a suitable speed selected from 2, 10, 12, 20, 40, 60, and 100 rpm).

[0134] In each of the examples, after application to the substrate and before irradiation with radiation, the laser image-forming composition was cured with UV light using a mercury lamp with an output of 160 W / cm.

[0135] In each of the examples, CO 2 laser (Videojet VJ-3320 or SHC60) with a wavelength of 10.6 microns (10600 nm) was used to irradiate infrared rays. CO 2 laser had the following settings: 12.9 J / s (output); 176 ms (time); and 2.2704 J / cm 2 (fluence).

[0136] [Example 1] The composition was prepared according to Table 1. All amounts are in weight percentages (wt%).

[0137]

Table 1

[0138] The viscosity of Genomer 4312 was 60 Pa·s (60,000 cP), and the viscosity of Laromer TPGDA was 0.018 Pa·s (18 cP).

[0139] The composition was pulverized by passing it through an Exakt 50 unit (three-roll mill) five times to produce a laser image-forming composition according to the present invention.

[0140] The printing viscosity of the laser image-forming composition was measured to be 103.6 Pa·s (103,600 cP).

[0141] A single layer of the laser image-forming composition was printed onto cardboard by offset lithographic printing up to a coating weight of 1.5 gsm.

[0142] Next, the laser image-forming composition was irradiated with infrared rays at local positions, and as a result, black was formed at the local positions, promoting the formation of an image.

[0143] [Example 2] A composition was prepared according to Table 2. All amounts are in weight percentages (wt%).

[0144]

Table 2

[0145] The viscosity of Genomer 3414 was 4.5 Pa·s (4,500 cP).

[0146] The composition was pulverized by passing it through an Exakt 50 unit (three-roll mill) five times to produce a laser image-forming composition according to the present invention.

[0147] The printing viscosity of the laser image-forming composition was measured to be 60 Pa·s (60,000 cP).

[0148] A single layer of the laser image-forming composition was printed onto cardboard by offset lithographic printing up to a coating weight of 1.5 gsm.

[0149] Next, the laser image-forming composition was irradiated with infrared rays at local positions, and as a result, black was formed at the local positions, promoting the formation of an image.

[0150] [Example 3] The composition was prepared according to Table 3. All amounts are in weight percentages (wt%).

[0151]

Table 3

[0152] The viscosity of Genomer 3480 was 3.2 Pa·s (3,200 cP).

[0153] The composition was pulverized by passing it through an Exakt 50 unit (3-roll mill) 5 times to produce a laser image-forming composition according to the present invention.

[0154] The printing viscosity of the laser image-forming composition was measured to be 152 Pa·s (152,000 cP).

[0155] A single layer of the laser image-forming composition was printed on a cardboard sheet by offset lithographic printing up to a coating weight of 1.5 gsm.

[0156] Next, the laser image-forming composition was irradiated with infrared rays at a local position, and as a result, black was formed at the local position to promote the formation of an image.

[0157] [Example 4] The composition was prepared according to Table 4. All amounts are in weight percentages (wt%).

[0158]

Table 4

[0159] The viscosity of Genomer 5271 was 1.2 Pa·s (1,200 cP).

[0160] The composition was pulverized by passing it through an Exakt 50 unit (three-roll mill) five times to produce a laser image-forming composition according to the present invention.

[0161] The printing viscosity of the laser image-forming composition was measured to be 155 Pa·s (155,000 cP).

[0162] A single layer of the laser image-forming composition was printed onto a cardboard by offset lithographic printing up to a coating weight of 1.5 gsm.

[0163] Next, the laser image-forming composition was irradiated with infrared rays at a local position, and as a result, black was formed at the local position to promote the formation of an image.

[0164] [Example 5] A composition was prepared according to Table 5. All amounts are in weight percentages (wt%).

[0165]

Table 5

[0166] The viscosity of Genomer 2263 was measured to be 500 Pa·s (500,000 cP), and the viscosity of Miramer M320 was 0.11 Pa·s (110 cP).

[0167] The composition was pulverized by passing it through an Exakt 50 unit (three-roll mill) five times to produce a laser image-forming composition according to the present invention.

[0168] The printing viscosity of the laser image-forming composition was measured to be 85.76 Pa·s (85,760 cP).

[0169] A single layer of the laser image-forming composition was printed onto a cardboard by offset lithographic printing up to a coating weight of 1.5 gsm.

[0170] Next, the infrared rays were irradiated onto the laser image-forming composition at a local position, and as a result, black was formed at the local position, promoting the formation of the image.

[0171] [Example 6] The composition was prepared according to Table 6. All amounts are in weight percentages (wt%).

[0172] [Table 6]

[0173] The viscosity of Genomer 2263 was measured to be 500 Pa·s (500,000 cP), and the viscosity of Laromer TPGDA was 0.018 Pa·s (18 cP).

[0174] The composition was ground by passing it through a Buehler SDT-800 (three-roll mill) twice to produce a laser image-forming composition according to the present invention.

[0175] The printing viscosity of the laser image-forming composition was measured to be 115 Pa·s (115,000 cP).

[0176] A single layer of the laser image-forming composition was printed onto a cardboard sheet by offset lithographic printing up to a coating weight of 1.5 gsm.

[0177] Next, the infrared rays were irradiated onto the laser image-forming composition at a local position, and as a result, black was formed at the local position, promoting the formation of the image.

[0178] [Example 7] The composition was prepared according to Table 7. All amounts are in weight percentages (wt%).

[0179] [Table 7]

[0180] The viscosity of Genomer 2281 was measured to be 264 Pa·s (264,000 cP), and the viscosity of Laromer TPGDA was 0.018 Pa·s (18 cP).

[0181] The composition was ground by passing it through an Exakt 50 unit (three-roll mill) five times to produce a laser image-forming composition according to the present invention.

[0182] The printing viscosity of the laser image-forming composition was measured to be 59.2 Pa·s (59,200 cP).

[0183] A single layer of the laser image-forming composition was printed onto a carton board by offset lithographic printing up to a coating weight of 1.5 gsm.

[0184] Next, the laser image-forming composition was irradiated with infrared rays at a local position, and as a result, black was formed at the local position to promote the formation of an image.

[0185] Particle size and surface area analysis for Examples 1 to 7 In accordance with ISO 13320:2009, the D 50 , D 10 and D 90 particle size distribution values and surface area were calculated for Examples 1 to 7. The results are shown in Table 8.

[0186]

Table 8

[0187] Optical density black (ODB) measurement for Examples 1 to 7 Using an X-Rite SpectroEye spectrophotometer, the absolute ODB and background ODB were measured.

[0188] The absolute and background ODB values for each of Examples 1 to 7 are shown in Table 9. The ΔODB values (ODB value - background ODB) for each of Examples 1 to 7 are also shown in Table 9.

[0189]

Table 9

[0190] In the laser image-forming composition of the present invention, a ΔODB value of 0.6 or more is desirable. Such a ΔODB value indicates the formation of an image with high optical density, i.e., high contrast. The image is human and / or machine-readable.

[0191] Therefore, it can be seen from the ΔODB values for Examples 1 to 7 that the laser image-forming composition of the present invention promotes the formation of high-contrast images. The present invention includes the following embodiments. [Claim 1] (a) A polyvalent metal oxyanion and (b) an oligomer A laser image-forming composition comprising: wherein the polyvalent metal oxyanion 50 contains particles having a D particle size distribution of 10 μm or less. [Claim 2] The particles of the polyvalent metal oxyanion 50 have a D particle size distribution of 7 μm or less, preferably 5 μm or less, preferably 4.5 μm or less, preferably 4 μm or less, preferably 3.5 μm or less, preferably 3 μm or less, preferably 2.5 μm or less, preferably 2.4 μm or less. The laser image-forming composition according to claim 1. [Claim 3] The particles of the polyvalent metal oxyanion 90 have a D particle size distribution of 25 μm or less, preferably 20 μm or less, preferably 15 μm or less, preferably 10 μm or less, preferably 9.5 μm or less, preferably 9 μm or less, preferably 8.5 μm or less, preferably 8 μm or less. The laser image-forming composition according to claim 1 or 2. [Claim 4] The particles of the polyvalent metal oxyanion 10 have a D particle size distribution of 4 μm or less, preferably 3 μm or less, preferably 2.5 μm or less, preferably 2 μm or less, preferably 1.5 μm or less, preferably 1 μm or less. The laser image-forming composition according to any one of claims 1 to 3. [Claim 5] The particles of the polyvalent metal oxyanion have a surface area of 950 m 2 / kg or more, preferably 1200 m 2 / kg or more, preferably 1500 m 2 / kg or more, preferably 2000 m 2 / kg or more, preferably 2500 m 2 / kg or more, preferably 3000 m 2 / kg or more, preferably 3700 m 2 / kg, preferably 4000 m 2 / kg or more. The laser image-forming composition according to any one of claims 1 to 4. [Claim 6] The polyvalent metal oxyanion is an ammonium salt of a polyvalent metal oxyanion. The laser image-forming composition according to any one of claims 1 to 5. [Claim 7] The polyvalent metal oxyanion is an ammonium salt of a molybdenum oxyanion. The laser image-forming composition according to claim 6. [Claim 8] The polyvalent metal oxyanion is ammonium octamolybdate (AOM). The laser image-forming composition according to claim 6 or 7. [Claim 9] The laser image-forming composition according to any one of claims 1 to 8, wherein the oligomer is a radiation-curable oligomer, preferably a UV-curable oligomer. [Claim 10] The laser image-forming composition according to any one of claims 1 to 9, wherein the oligomer is difunctional, trifunctional or tetrafunctional, or an oligomer having a higher functionality. [Claim 11] The laser image-forming composition according to claim 10, wherein the oligomer is difunctional, trifunctional or tetrafunctional. [Claim 12] The laser image-forming composition according to claim 10 or 11, wherein the oligomer is difunctional or trifunctional. [Claim 13] The laser image-forming composition according to any one of claims 10 to 12, wherein the oligomer is difunctional. [Claim 14] The oligomer is an epoxy oligomer containing a modified epoxy oligomer; an epoxy (meth)acrylate oligomer containing a modified epoxy (meth)acrylate oligomer; a urethane oligomer; a silane or silicon oligomer; an alkyl (meth)acrylate oligomer, a polyether (meth)acrylate oligomer, a polyester (meth)acrylate oligomer, an acid-functional (meth)acrylate oligomer, a (meth)acrylate oligomer containing an amine (meth)acrylate oligomer; a polyester urethane acrylate oligomer; and a urethane (meth)acrylate oligomer, or a combination thereof. The laser image-forming composition according to any one of claims 1 to 13. [Claim 15] The oligomer is selected from an epoxy oligomer, a modified epoxy oligomer, a urethane oligomer, a polyether (meth)acrylate oligomer, a polyester (meth)acrylate oligomer, an epoxy (meth)acrylate oligomer, a modified epoxy (meth)acrylate oligomer, a polyester urethane (meth)acrylate oligomer and an amine (meth)acrylate oligomer, or a combination thereof. The laser image-forming composition according to claim 14. [Claim 16] The laser image-forming composition according to claim 14 or 15, wherein the oligomer is selected from polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester urethane (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or a combination thereof. [Claim 17] The laser image-forming composition according to claim 14, 15 or 16, wherein the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or a combination thereof. [Claim 18] The laser image-forming composition according to any one of claims 14 to 17, wherein the oligomer is selected from epoxy (meth)acrylate oligomers, modified epoxy (meth)acrylate oligomers, and amine (meth)acrylate oligomers, or a combination thereof. [Claim 19] The laser image-forming composition according to any one of claims 14 to 18, wherein the oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or a combination thereof. [Claim 20] The laser image-forming composition according to any one of claims 14 to 19, wherein the oligomer is an epoxy (meth)acrylate oligomer. [Claim 21] The laser image-forming composition according to any one of claims 1 to 20, wherein the oligomer has a viscosity of 200 Pa·s or less, preferably 160 Pa·s or less, preferably 100 Pa·s or less, more preferably 80 Pa·s or less. [Claim 22] The laser image-forming composition according to any one of claims 1 to 21, wherein the oligomer has a viscosity of 1 to 200 Pa·s, preferably 1 to 160 Pa·s. [Claim 23] The laser image-forming composition according to claim 22, wherein the oligomer has a viscosity of 1 to 100 Pa·s, preferably 1 to 80 Pa·s. [Claim 24] The oligomer is a laser image-forming composition according to any one of claims 1 to 21, having a viscosity of 3 to 200 Pa·s, preferably 3 to 160 Pa·s. [Claim 25] The oligomer is a laser image-forming composition according to claim 24, having a viscosity of 3 to 100 Pa·s, preferably 3 to 80 Pa·s. [Claim 26] The laser image-forming composition according to any one of claims 1 to 25, further comprising a monomer. [Claim 27] The laser image-forming composition according to claim 26, wherein the monomer is a monofunctional, difunctional, trifunctional or tetrafunctional monomer, or a monomer having a higher functionality. [Claim 28] The laser image-forming composition according to claim 26 or 27, wherein the monomer is a difunctional, trifunctional or tetrafunctional monomer, or a monomer having a higher functionality. [Claim 29] The laser image-forming composition according to claim 26, 27 or 28, wherein the monomer is a difunctional or trifunctional monomer. [Claim 30] The laser image-forming composition according to any one of claims 26 to 29, wherein the monomer is a difunctional monomer. [Claim 31] The monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and is a laser image-forming composition according to any one of claims 26 to 30. [Claim 32] The monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and is a laser image-forming composition according to any one of claims 26 to 31. [Claim 33] The monomer is tripropylene glycol diacrylate (TPGDA), and is a laser image-forming composition according to any one of claims 26 to 32. [Claim 34] The oligomer has a viscosity of 50 Pa·s or more, preferably 100 Pa·s or more, or 200 Pa·s or more, more preferably 1,000 Pa·s or more, and is the laser image-forming composition according to any one of claims 26 to 33. [Claim 35] The monomer has a viscosity of 1.8 Pa·s or less, preferably 0.8 Pa·s or less, and is the laser image-forming composition according to any one of claims 26 to 34. [Claim 36] The monomer has a viscosity of 0.1 Pa·s or less, preferably 0.05 Pa·s or less, preferably 0.02 Pa·s or less, and is the laser image-forming composition according to claim 35. [Claim 37] The monomer has a viscosity of 0.01 to 1.8 Pa·s, preferably 0.01 to 0.8 Pa·s, and is the laser image-forming composition according to any one of claims 26 to 34. [Claim 38] The monomer has a viscosity of 0.01 to 0.1 Pa·s, preferably 0.01 to 0.05 Pa·s, more preferably 0.01 to 0.02 Pa·s, and is the laser image-forming composition according to claim 37. [Claim 39] The monomer has a viscosity of 0.015 to 1.8 Pa·s, preferably 0.015 to 0.8 Pa·s, preferably 0.015 to 0.1 Pa·s, and is the laser image-forming composition according to any one of claims 26 to 34. [Claim 40] The monomer has a viscosity of 0.015 to 0.05 Pa·s, preferably 0.015 to 0.02 Pa·s, and is the laser image-forming composition according to claim 39. [Claim 41] The oligomer is selected from epoxy (meth)acrylate oligomer, modified epoxy (meth)acrylate oligomer, and amine (meth)acrylate oligomer, or a combination thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and is the laser image-forming composition according to any one of claims 26 to 40. [Claim 42] The oligomer is selected from epoxy (meth) acrylate oligomers, modified epoxy (meth) acrylate oligomers, or combinations thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), the laser image-forming composition according to claim 41. [Claim 43] The oligomer is selected from epoxy (meth) acrylate oligomers, modified epoxy (meth) acrylate oligomers, or combinations thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), the laser image-forming composition according to claim 41 or 42. [Claim 44] The oligomer is an epoxy (meth) acrylate oligomer, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), the laser image-forming composition according to any one of claims 41 to 43. [Claim 45] The oligomer is an epoxy (meth) acrylate oligomer, and the monomer is tripropylene glycol diacrylate (TPGDA), the laser image-forming composition according to any one of claims 41 to 44. [Claim 46] The oligomer is selected from a bifunctional or trifunctional epoxy (meth)acrylate oligomer, a modified epoxy (meth)acrylate oligomer, and an amine (meth)acrylate oligomer, or a combination thereof, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and the laser image-forming composition according to any one of claims 26 to 40. [Claim 47] The oligomer is selected from a bifunctional or trifunctional epoxy (meth)acrylate oligomer and a modified epoxy (meth)acrylate oligomer, or a combination thereof, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and the laser image-forming composition according to claim 46. [Claim 48] The oligomer is bifunctional, and the laser image-forming composition according to claim 46 or 47. [Claim 49] The oligomer is a bifunctional epoxy (meth)acrylate oligomer, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) 3 triacrylate (TMP(EO) 3 TA) and trimethylolpropane (EO) 9 triacrylate (TMP(EO) 9 TA), and the laser image-forming composition according to any one of claims 46, 47 or 48. [Claim 50] The oligomer is a bifunctional epoxy (meth)acrylate oligomer, and the monomer is tripropylene glycol diacrylate (TPGDA), and the laser image-forming composition according to any one of claims 46 to 49. [Claim 51] The printing viscosity of the laser image-forming composition is 10 to 600 Pa·s, preferably 55 to 500 Pa·s, more preferably 80 to 400 Pa·s, the laser image-forming composition according to any one of claims 1 to 50. [Claim 52] The printing viscosity is 100 to 400 Pa·s, preferably 100 to 300 Pa·s, the laser image-forming composition according to claim 51. [Claim 53] A substrate comprising the laser image-forming composition according to any one of claims 1 to 52. [Claim 54] The substrate according to claim 53, which is a non-metallic substrate. [Claim 55] The laser image-forming composition is applied to the substrate at a coating weight of 0.7 to 2 gsm, preferably 0.7 to 1.8 gsm, more preferably 0.7 to 1.7 gsm, the substrate according to claim 53 or 54. [Claim 56] The laser image-forming composition is applied to the substrate at a coating weight of 0.8 to 1.5 gsm, preferably 0.8 to 1.2 gsm, the substrate according to claim 55. [Claim 57] The substrate according to any one of claims 53 to 56, wherein the substrate comprises a single layer of the laser image-forming composition applied thereto. [Claim 58] A method of forming a substrate having the laser image-forming composition according to any one of claims 1 to 52 applied thereto, the method comprising the step of applying the laser image-forming composition to the substrate. [Claim 59] A method of forming an image on a substrate comprising the laser image-forming composition according to any one of claims 1 to 52 applied thereto, the method comprising the step of exposing the laser image-forming composition to radiation to form an image on the substrate. [Claim 60] A method of forming the laser image-forming composition according to any one of claims 1 to 52, the method comprising combining a polyvalent metal oxyanion and an oligomer. [Claim 61] (a) forming a composition comprising a polyvalent metal oxyanion and an oligomer, and (b) pulverizing the composition to obtain the laser image-forming composition comprising a polyvalent metal oxyanion and an oligomer, wherein the polyvalent metal oxyanion is D 50The step comprising particles having a particle size distribution of 10 μm or less. The method according to claim 60. [Claim 62] (a’) pulverizing a polyvalent metal oxyanion to obtain D 50 The step of obtaining particles having a particle size distribution of 10 μm or less, and (b’)D 50 The step of combining the oxyanion of the polyvalent metal containing particles having a particle size distribution of 10 μm or less with an oligomer The method according to claim 60, comprising: [Claim 63] Use of the laser image-forming composition according to any one of claims 1 to 52 in offset lithographic printing. [Claim 64] Use of the laser image-forming composition according to any one of claims 1 to 52 in forming an image on a substrate.

Claims

1. (a) an oxyanion of a polyvalent metal and (b) an oligomer A laser image-forming composition comprising: The oxyanion of the polyvalent metal is D ５０ A laser image-forming composition comprising particles having a particle size distribution of 10 μm or less, wherein the particles of the oxyanion of the polyvalent metal have a D10 particle size distribution of 4 μm or less, and the oligomer is selected from an epoxy (meth)acrylate oligomer, a modified epoxy (meth)acrylate oligomer, an amine (meth)acrylate oligomer, or a combination thereof.

2. The particles of the oxyanion of the polyvalent metal are D ５０ The laser image-forming composition according to claim 1, wherein the particle size distribution is 7 μm or less, preferably 5 μm or less, preferably 4.5 μm or less, preferably 4 μm or less, preferably 3.5 μm or less, preferably 3 μm or less, preferably 2.5 μm or less, preferably 2.4 μm or less.

3. The particles of the oxyanion of the polyvalent metal are D ９０ The laser image-forming composition according to claim 1 or 2, wherein the particle size distribution is 25 μm or less, preferably 20 μm or less, preferably 15 μm or less, preferably 10 μm or less, preferably 9.5 μm or less, preferably 9 μm or less, preferably 8.5 μm or less, preferably 8 μm or less.

4. The particles of the oxyanion of the polyvalent metal are D １０ The laser image-forming composition according to any one of claims 1 to 3, wherein the particle size distribution is 3 µm or less, preferably 2.5 µm or less, preferably 2 µm or less, preferably 1.5 µm or less, preferably 1 µm or less.

5. The particles of the oxyanion of the polyvalent metal have a surface area of 950 m ２ / kg or more, preferably 1200 m ２ / kg or more, preferably 1500 m ２ / kg or more, preferably 2000 m ２ / kg or more, preferably 2500 m ２ / kg or more, preferably 3000 m ２ / kg or more, preferably 3700 m ２ / kg, preferably 4000 m ２ / kg or more, and is the laser image-forming composition according to any one of claims 1 to 4.

6. The laser image-forming composition according to any one of claims 1 to 5, wherein the oxyanion of the polyvalent metal is an ammonium salt of the oxyanion of the polyvalent metal, or the oxyanion of the polyvalent metal is an ammonium salt of the oxyanion of molybdenum, or the oxyanion of the polyvalent metal is ammonium octamolybdate (AOM).

7. The laser image-forming composition according to any one of claims 1 to 6, wherein the oligomer is a radiation-curable oligomer or a UV-curable oligomer.

8. The laser image-forming composition according to any one of claims 1 to 7, wherein the oligomer is difunctional, trifunctional or tetrafunctional, or an oligomer having a higher functionality.

9. The laser image-forming composition according to claim 8, wherein the oligomer is difunctional, trifunctional or tetrafunctional.

10. The laser image-forming composition according to claim 8 or 9, wherein the oligomer is difunctional or trifunctional.

11. The laser image-forming composition according to any one of claims 8 to 10, wherein the oligomer is difunctional.

12. The oligomer is selected from epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or combinations thereof, or The laser image-forming composition according to any one of claims 1 to 11, wherein the oligomer is an epoxy (meth)acrylate oligomer.

13. The laser image-forming composition according to any one of claims 1 to 12, wherein the oligomer has a viscosity of 200 Pa·s or less, or 160 Pa·s or less, or 100 Pa·s or less, or 80 Pa·s or less.

14. The laser image-forming composition according to any one of claims 1 to 13, wherein the oligomer has a viscosity of 1 to 200 Pa·s, or 1 to 160 Pa·s, or 1 to 100 Pa·s, or 1 to 80 Pa·s.

15. The laser image-forming composition according to any one of claims 1 to 13, wherein the oligomer has a viscosity of 3 to 200 Pa·s, or 3 to 160 Pa·s, or 3 to 100 Pa·s, or 3 to 80 Pa·s.

16. The laser image-forming composition according to any one of claims 1 to 15, further comprising a monomer.

17. The laser image-forming composition according to claim 16, wherein the monomer is a monofunctional, difunctional, trifunctional or tetrafunctional monomer, or a monomer having a higher functionality.

18. The laser image-forming composition according to claim 16 or 17, wherein the monomer is a difunctional, trifunctional or tetrafunctional monomer, or a monomer having a higher functionality.

19. The laser image-forming composition according to claim 16, 17 or 18, wherein the monomer is a difunctional or trifunctional monomer.

20. The laser image-forming composition according to any one of claims 16 to 19, wherein the monomer is a difunctional monomer.

21. The monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The laser image-forming composition according to any one of claims 16 to 20, wherein the monomer is tripropylene glycol diacrylate (TPGDA).

22. The laser image-forming composition according to any one of claims 16 to 21, wherein the oligomer has a viscosity of 50 Pa·s or more, or 100 Pa·s or more, or 200 Pa·s or more, or 1,000 Pa·s or more.

23. The laser image-forming composition according to any one of claims 16 to 22, wherein the monomer has a viscosity of 1.8 Pa·s or less, or 0.8 Pa·s or less, or 0.1 Pa·s or less, or 0.05 Pa·s or less, or 0.02 Pa·s or less.

24. The laser image-forming composition according to any one of claims 16 to 22, wherein the monomer has a viscosity of 0.01 to 1.8 Pa·s, or 0.01 to 0.8 Pa·s, or 0.01 to 0.1 Pa·s, or 0.01 to 0.05 Pa·s, or 0.01 to 0.02 Pa·s.

25. The laser image-forming composition according to any one of claims 16 to 22, wherein the monomer has a viscosity of 0.015 to 1.8 Pa·s, or 0.015 to 0.8 Pa·s, or 0.015 to 0.1 Pa·s, or 0.015 to 0.05 Pa·s, or 0.015 to 0.02 Pa·s.

26. The oligomer is selected from an epoxy (meth)acrylate oligomer, a modified epoxy (meth)acrylate oligomer, and an amine (meth)acrylate oligomer, or a combination thereof, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or the oligomer is selected from an epoxy (meth)acrylate oligomer and a modified epoxy (meth)acrylate oligomer, or a combination thereof, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), lauryl acrylate (LA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The oligomer is selected from epoxy (meth)acrylate oligomers, and modified epoxy (meth)acrylate oligomers, or combinations thereof, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The oligomer is an epoxy (meth) acrylate oligomer, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The laser image-forming composition according to any one of claims 16 to 25, wherein the oligomer is an epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA).

27. The oligomer is selected from a bifunctional or trifunctional epoxy (meth)acrylate oligomer, a modified epoxy (meth)acrylate oligomer, and an amine (meth)acrylate oligomer, or a combination thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The oligomer is selected from bifunctional or trifunctional epoxy (meth)acrylate oligomers and modified epoxy (meth)acrylate oligomers, or a combination thereof, and the monomer is tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or is selected from The oligomer is bifunctional, or The oligomer is a bifunctional epoxy (meth)acrylate oligomer, and the monomer is selected from tripropylene glycol diacrylate (TPGDA), glyceryl propoxytriacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane (EO) ３ triacrylate (TMP(EO) ３ TA) and trimethylolpropane (EO) ９ triacrylate (TMP(EO) ９ TA), or The laser image-forming composition according to any one of claims 16 to 25, wherein the oligomer is a bifunctional epoxy (meth) acrylate oligomer and the monomer is tripropylene glycol diacrylate (TPGDA).

28. The laser image-forming composition according to any one of claims 1 to 27, wherein the printing viscosity of the laser image-forming composition is 10 to 600 Pa·s, or 55 to 500 Pa·s, or 80 to 400 Pa·s, or 100 to 400 Pa·s, or 100 to 300 Pa·s.

29. A substrate comprising the laser image-forming composition according to any one of claims 1 to 28.

30. The substrate according to any one of claims 1 to 28, comprising a cured laser image-forming composition obtained by curing the laser image-forming composition.

31. The substrate according to claim 29 or 30, which is a non-metallic substrate.

32. The substrate according to any one of claims 29 to 31, wherein the laser image-forming composition is applied to the substrate to a coating weight of 0.7 to 2 gsm, or 0.7 to 1.8 gsm, or 0.7 to 1.7 gsm, or 0.8 to 1.5 gsm, or 0.8 to 1.2 gsm.

33. The substrate according to any one of claims 29 to 32, wherein the substrate comprises a single layer of the laser image-forming composition applied to the substrate.

34. A method of forming a substrate having the laser image-forming composition according to any one of claims 1 to 28 applied thereto, the method comprising the step of applying the laser image-forming composition to the substrate.

35. The method according to claim 34, wherein the laser image-forming composition is cured after being applied to the substrate.

36. A method of forming an image on a substrate comprising the laser image-forming composition according to any one of claims 1 to 28 applied thereto, the method comprising the step of exposing the laser image-forming composition to radiation to form an image on the substrate.

37. A method of forming the laser image-forming composition according to any one of claims 1 to 28, the method comprising combining a polyvalent metal oxyanion and an oligomer.

38. (a) forming a composition comprising a polyvalent metal oxyanion and an oligomer, and Step (b) of pulverizing the composition to obtain the laser image-forming composition containing the oxyanion and oligomer of the polyvalent metal, wherein the oxyanion of the polyvalent metal is D ５０ The step of including particles having a particle size distribution of 10 μm or less comprising, or (a') pulverizing an oxyanion of a polyvalent metal to obtain particles having a particle size distribution of 10 µm or less, and ５０ a step of obtaining particles having a particle size distribution of 10 µm or less, and (b') D ５０ The step of combining the oxyanion of the polyvalent metal containing particles with a particle size distribution of 10 μm or less with an oligomer comprising, the method according to claim 37.

39. Use of the laser image-forming composition according to any one of claims 1 to 28 in offset lithographic printing or in the formation of an image on a substrate.

Images