High molecular weight polystyrene in inks and coatings

Abstract

To provide depolymerized polystyrene resins derived from polystyrene source resins.SOLUTION: The depolymerized polystyrene resins undergo a depolymerization in which chemical bonds are cleaved to produce depolymerized polystyrene resins of lower molecular weight. The polystyrene resins may be modified by chemical reaction with monomers, polymers, and oligomers, such as acrylates thereof. Also described are ink and coating compositions that include the depolymerized and modified polystyrene resins.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 292,906, filed February 9, 2016, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to polystyrene resins obtained by depolymerizing raw polystyrene resins. Depolymerization can occur through the action of free radical initiators, catalysts, exposure to radiation, and other means. The depolymerized polystyrene can be reacted with other components, such as monomers, oligomers, or polymers. This disclosure also relates to processes for producing depolymerized and / or modified polystyrene resins, and further relates to ink and coating compositions containing the same. The compatibility and stability of ink or coating compositions containing depolymerized and / or modified polystyrene resins are similar to those of commercially available ink and coating compositions. The depolymerized and / or modified polystyrene resins can also be used as components in other compositions, such as adhesives. The raw polystyrene resin can be, for example, virgin polystyrene resin, scrap polystyrene resin, recycled polystyrene resin, and / or regenerated polystyrene resin. [Background technology]

[0003] Reducing the amount of plastic material disposed of in landfills is an important environmental consideration. One approach has been to use post-consumer and post-industrial recycled plastic materials in newly manufactured plastic products. For certain plastic materials, this is relatively easy. However, recycling polystyrene is difficult. Polystyrene is a widely used thermoplastic resin with a hardness, hydrophobicity, and chemical composition that makes it essentially non-degradable under normal conditions. Foamed forms of polystyrene, often referred to as Styrofoam®, pose particularly serious problems for marine life and natural ecosystems due to their buoyancy, stability, and durability. Among the environmental problems they pose is the appearance of floating debris, which is often consumed by marine organisms.

[0004] Polystyrene packaging products do not degrade under normal conditions, making polystyrene a significant waste material problem. Recycling could alleviate environmental concerns. Developing methods to utilize post-consumer and post-industrial recycled polystyrene would be of clear benefit.

[0005] US Patent Application Publication No. 2014 / 004267 relates to radiation curable compositions incorporating an inactive resin described as a polystyrene resin having a number average molecular weight of 100 to 5000 Daltons.

[0006] U.S. Patent No. 4,007,311 relates to adhesives made by grafting acrylate monomers onto block copolymers of polystyrene-polybutadiene-polystyrene and polystyrene-polyisoprene-polystyrene, which have molecular weights of about 25,000 to 250,000 daltons, preferably about 50,000 to 150,000 daltons.

[0007] JP 2003 / 002914 A relates to an overprint varnish emulsion containing a styrene polymer having a molecular weight of 1500 to 2900 Daltons. The polymer is formulated from a crosslinkable monomer and / or crosslinkable oligomer and a photoinitiator. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US Patent Application Publication No. 2014 / 004267 [Patent Document 2] U.S. Patent No. 4,007,311 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003 / 002914 Summary of the Invention [Problem to be solved by the invention]

[0009] The present disclosure relates to polystyrene resins obtained by depolymerizing raw polystyrene resins. [Means for solving the problem]

[0010] The present disclosure describes depolymerized polystyrene resins having a number average molecular weight greater than 5,000 Daltons that are obtained from a raw polystyrene resin. The depolymerized polystyrene can be obtained from a polystyrene raw resin having a number average molecular weight (Mn) of, for example, 40,000 Daltons or greater, e.g., by cleavage of C—C bonds to produce depolymerized polystyrene of lower molecular weight.

[0011] In another aspect, this disclosure describes an inventive process for preparing a depolymerized polystyrene resin having a number average molecular weight greater than 5,000 daltons, the process comprising (a) introducing radical sites onto a relatively high molecular weight polystyrene raw resin by cleaving bonds in the polystyrene raw resin to produce a relatively low molecular weight depolymerized polystyrene resin. In a further inventive process embodiment, the depolymerized polystyrene resin of (a) is reacted with (b) a monomer or oligomer having a polar and / or polar-charged group at the radical site of the depolymerized polystyrene resin. In a further inventive process embodiment, the depolymerized polystyrene resin of (a) is reacted with (c) a polymer having polar functional groups to introduce functional groups.

[0012] For example, when component (c) such as a polystyrene raw resin and a polyacrylate polymer derived from recycled polystyrene materials is heated in, for example, ink oil, the materials are not soluble and / or miscible. However, the applicant has found that when a free radical initiator is added to the above system and reaction conditions are achieved, a polymerization reaction occurs that produces a stable, homogeneous copolymer solution / dispersion. Thus, a copolymer system can be produced.

[0013] Furthermore, for example, if the starting polystyrene resin is depolymerized in (a) to create reactive sites on the polystyrene polymer, these sites can react with functional groups provided, for example, by unsaturated monomers, to produce graft copolymer structures. These can also be produced in (c), where a copolymer of polystyrene polymer or polyacrylate polymer, or a combination thereof, can be placed in solution with the starting polystyrene resin. By adding a free radical initiator and achieving reaction conditions, radicals can be generated on the polymer chain. Another possible outcome of the absence of reactive species provided by the monomers, oligomers, or polymers in (b) and (c) is that the reactive sites on the polymer chains can recombine, resulting in the formation of copolymers through the combination of macromolecules.

[0014] Reaction of the depolymerized styrene resin with other functional groups described in (b) and (c) above, which may be functional groups of monomers, oligomers, and polymers, produces modified polystyrene resins. The depolymerized and / or modified polystyrene resins described herein exhibit improved compatibility and stability in ink or coating compositions compared to high molecular weight polystyrene resins. For example, depolymerized polystyrene resins according to the present disclosure have been shown to have good stability in ink and coating compositions. Furthermore, modified polystyrene resins, such as the depolymerized polystyrene resins of (b) and / or (c), also exhibit improved compatibility and stability in ink or coating compositions.

[0015] Radical sites can be introduced into the raw polystyrene resin by exposing it to the bond-cleaving action of initiators, catalysts, ionizing radiation, plasma sources, and other means. Ionizing radiation can be introduced by electron beams. Plasma can be generated by corona discharge.

[0016] When modifying depolymerized polystyrene resin, the polar and / or polar-charged functional groups used for modification can be derived from, for example, monomers, oligomers, and polymers. Such monomers, oligomers, and polymers can be, for example, (meth)acrylates, styrene, (meth)acrylic acid, esters of (meth)acrylic acid, polymers, copolymers thereof, terpolymers thereof, and combinations thereof. The styrene monomers, oligomers, and / or polymers used to modify the depolymerized polystyrene structure can differ from the starting polystyrene resin in one or more properties, resulting in a modified polystyrene resin with different quality(s) from the original starting polystyrene resin. For example, the modified material, such as a different polystyrene resin material, can differ from the starting polystyrene material in the degree of branching, or the length of the branched chains, that the material possesses.

[0017] The depolymerized and / or modified polystyrene resins described herein have physical properties suitable for use in ink and coating compositions. For example, the depolymerized and / or modified polystyrene resins can be used as binders in such compositions. The properties of the depolymerized and / or modified polystyrene resins are substantially similar to the properties of binders currently used in such compositions.

[0018] The depolymerized polystyrene resins herein can be derived from polystyrene feedstocks that contain up to 100% post-consumer and / or post-industrial recycled polystyrene. Recycling of waste or scrap polystyrene, whether post-consumer or non-post-consumer, has become a global concern due to the environmental impact caused by this material and the increasing amounts it is produced.

[0019] In one embodiment, the raw polystyrene resin is obtained from polystyrene molded articles considered post-consumer scrap. In another embodiment, the raw polystyrene resin can be obtained from expanded polystyrene resin. The raw polystyrene resin can be selected from one or more of expanded polystyrene (EPS) made from expandable polystyrene containing a blowing agent, general purpose polystyrene (GPPS), high impact polystyrene (HIPS), rubber-modified polystyrene such as styrene-butadiene rubber, ABS (acrylonitrile-butadiene-styrene), and extruded expanded polystyrene (XPS). These polystyrenes can be obtained from waste materials generated in the production of the specific type of polystyrene used as raw material and / or in the production of polystyrene molded articles, or can be secured from industrial sources having a number average molecular weight of 40,000 daltons or greater.

[0020] In one aspect, the relatively low molecular weight depolymerized and / or modified polystyrene is obtained by depolymerizing a polystyrene raw resin material, which can be, for example, virgin, scrap, recycled, or reclaimed polystyrene raw resin material. Depolymerization can occur through the action of an initiator or catalyst in a solution or melt of the polystyrene. Depolymerization can occur by irradiating the polystyrene raw material, such as with radiation from an electron beam source, or by exposing the polystyrene raw resin to a plasma source. In either case, the resulting depolymerized and / or modified material can improve the compatibility and stability of the resulting low molecular weight polystyrene in ink and coating compositions.

[0021] The degree of depolymerization can be controlled, for example, by controlling the temperature of the depolymerization process and the amount of depolymerization agent used, such as the amount of initiator and catalyst. When depolymerization occurs by exposing the polystyrene raw resin to radiation and plasma, the conditions of these processes can be controlled to control depolymerization. The pressure at which depolymerization occurs can also be used to control depolymerization.

[0022] In one embodiment, process steps (a) and (b) may be combined into a single step, and thus the present invention further provides a process for preparing a modified polystyrene resin having a number average molecular weight (Mn) of at least 5,000 daltons, comprising: (a) introducing radical sites onto the polystyrene using a catalyst, initiator, or ionizing radiation in the presence of polar and / or polar charged functional groups; and (b) optionally, optionally, further reacting the polar functional polystyrene to introduce functional groups that enhance compatibility or that can be further reacted with another component.

[0023] In one embodiment, the depolymerized polystyrene resin is modified with reactive monomers, oligomers, and polymers that react with radicals introduced by the action of catalysts, initiators, and / or other depolymerization means. Such monomers include, for example, (meth)acrylic acid, (meth)acrylic acrylate, styrene, and the like.

[0024] The Mn of the depolymerized and / or modified polystyrene resins of the present disclosure is greater than 5,000 daltons. In another embodiment, the Mn of the depolymerized and / or modified polystyrene resins of the present disclosure can be greater than about 10,000 daltons, in yet another embodiment, greater than about 15,000 daltons, in yet another embodiment, greater than about 20,000 daltons, in yet another embodiment, greater than about 25,000 daltons, in yet another embodiment, greater than about 30,000 daltons, in yet another embodiment, greater than about 35,000 daltons, in yet another embodiment, greater than about 40,000 daltons, in yet another embodiment, greater than about 45,000 daltons, and in yet another embodiment, greater than about 50,000 daltons. These Mn values ​​include depolymerized polystyrene resins and modified depolymerized polystyrene resins.

[0025] These and other objects, advantages and features of the present invention will become apparent to those skilled in the art upon reading the details of the methods and formulations as more fully described below. DETAILED DESCRIPTION OF THE INVENTION

[0026] Detailed Description of the Invention It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of any subject matter claimed.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Unless otherwise stated, all patents, patent applications, published applications and publications, websites and other publications mentioned throughout this disclosure are incorporated by reference in their entirety for all purposes.

[0028] definition In this application, the use of the singular includes the plural unless specifically stated otherwise. As used herein, the singular forms "a," "an," and "the" in foreign language specifications are intended to include the plural as well, unless the context clearly dictates otherwise.

[0029] In this application, the use of "or" means "and / or" unless stated otherwise.

[0030] As used herein, the terms "comprise" and / or "comprising" specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, to the extent that the terms "include," "having," "has," "with," "composed," "comprised," or variations thereof, are used in the detailed description or claims, such terms are intended to be inclusive in a manner similar to the term "comprising."

[0031] As used herein, ranges and amounts can be expressed as "about" a particular value or range. "About" includes the exact amount. Thus, "about 5%" means "about 5%" and "5%." "About" means within typical experimental error for the application or intended purpose.

[0032] As used herein, the term "(meth)acrylate or (meth)acrylic acid" includes both acrylate and methacrylate compounds, and both acrylic acid and methacrylic acid.

[0033] As used herein, the term "monofunctional" means having one functional group.

[0034] As used herein, "multifunctional" means having two or more functional groups. A multifunctional monomer can have, for example, difunctional, trifunctional, tetrafunctional, or higher functional groups. The two or more functional groups can be the same or different.

[0035] As used herein, the term "monomer(s)" is intended to include both monomers and oligomers, or mixtures thereof.

[0036] As used herein, the terms "(meth)acrylic resin," "acrylic polymer," and "acrylic resin" are used interchangeably. These terms encompass acrylic and methacrylic polymers, copolymers, and resins.

[0037] As used herein, the term "polymer(s)" includes copolymers unless otherwise indicated.

[0038] As used herein, the terms "inks and coatings," "ink," "composition," and "fluid" are used interchangeably.

[0039] Throughout this specification, all parts and percentages are by weight (% by weight or % by mass, based on total weight) and all temperatures are in degrees Celsius (°C) unless otherwise indicated.

[0040] The present disclosure describes depolymerized and / or modified polystyrene resins having a number average molecular weight (Mn) of greater than 5,000 Daltons, processes for making same, and ink and coating compositions containing same.

[0041] The process involves (a) introducing radical sites into a relatively high molecular weight polystyrene raw resin by cleaving bonds in the polystyrene raw resin to produce a relatively low molecular weight depolymerized polystyrene resin. In a further embodiment of the process, the depolymerized polystyrene resin of (a) reacts with polar and / or polar charged groups provided by a monomer or oligomer at the radical sites of the depolymerized polystyrene resin. In a further embodiment of the process, the depolymerized polystyrene resin of (a) is (c) reacting with polar functional groups provided by the polymer to introduce functional groups therein. The depolymerization of polystyrene can include depolymerization by exposing the raw polystyrene resin to ionizing radiation in the presence of a catalyst, initiator, or second component (b) and / or (c), where a chemical reaction occurs between the second component to form the radicalized / depolymerized polystyrene resin and the modified polystyrene resin. The second component (b) and / or (c) can be a monomer, oligomer, or polymer, or a combination thereof.

[0042] In providing the depolymerized polystyrene resin, C—C bonds in the raw polystyrene resin material can be cleaved by the action of an initiator, catalyst, irradiation, plasma, etc. The resulting depolymerized polystyrene resin can be modified with radical sites formed such that the bonds are cleaved to attach polar and / or polar charged functional groups to the depolymerized polystyrene material.

[0043] Depolymerized and / or modified polystyrene resins can be included in ink and coating compositions. For example, they can be used as binders in such compositions. The modified polystyrene resins have physical properties substantially similar to those of binders used in prior art ink and coating compositions. The depolymerized and / or modified polystyrene resins described herein can be obtained from up to 100% post-consumer and / or post-industrial recycled polystyrene, such as high-impact polystyrene containing a nominal amount of styrene-butadiene rubber (SBR) in the polystyrene backbone. Recycling of waste polystyrene, either post-consumer or non-post-consumer, is a global concern due to its environmental impact and the increasing amount of these materials produced by society.

[0044] In one embodiment, polystyrene can be obtained from polymerized styrene monomer (virgin polystyrene), but is preferably obtained from waste or scrap materials generated in the polystyrene manufacturing process and waste materials (pre-consumer scrap) generated in polystyrene manufacturing. Advantageously, polystyrene is obtained from polystyrene moldings (post-consumer scrap). Polystyrene may be expanded polystyrene (EPS), which is made from expandable polystyrene containing a blowing agent. Polystyrene may be general purpose polystyrene (GPPS) or rubber-modified high impact polystyrene (HIPS). Polystyrene may be ABS, which is acrylonitrile, butadiene, and styrene. Polystyrene may be expanded polystyrene, an example of which is extruded expanded polystyrene (XPS). Polystyrene may be expanded polystyrene (EPS).

[0045] The starting polystyrene resin has a number average molecular weight greater than about 40,000 daltons. More preferably, the starting polystyrene resin has a molecular weight greater than about 50,000 daltons. Even more preferably, the starting polystyrene resin has a molecular weight greater than about 75,000 daltons. Even more preferably, the starting polystyrene resin has a molecular weight greater than about 100,000 daltons. Even more preferably, the starting polystyrene resin has a molecular weight greater than about 120,000 daltons.

[0046] Depolymerization of the raw polystyrene resin, cleavage of C-C bonds, and introduction of radicals at the cleavage sites can be achieved by introducing an initiator to the polystyrene raw resin under depolymerization conditions, such as bond-cleavage conditions. For example, the raw polystyrene resin may be dissolved in a suitable solvent in the presence of the initiator, or a melt of the raw polystyrene resin may be generated in the presence of the initiator. In either case, the temperature of the solution or melt can be raised and maintained at about 170°C or higher, preferably about 180°C or higher, and more preferably about 190°C or higher. Under these conditions, the initiator present in the melt or solution depolymerizes the polystyrene raw resin, such as by cleaving chemical bonds. The bonds may be homolytically cleaved, generating depolymerized moieties from the raw polystyrene resin. The degree of depolymerization of the raw polystyrene resin may be controlled by controlling the temperature, the amount of initiator and catalyst used, and the pressure at which the process is carried out.

[0047] Upon depolymerization, the polystyrene resin may have vinylic, saturated and / or oxy-substituted ends.

[0048] When the depolymerized polystyrene resin is modified by reaction with a monomer, oligomer, or polymer, the modification reaction may be carried out in stages, for example, by adding the monomer, oligomer, or polymer to the reaction vessel after depolymerization has occurred. Alternatively, the depolymerization may be carried out in one step, for example, by introducing the raw polystyrene resin, initiator (for example), solvent, monomer, oligomer, or polymer into the vessel and then raising the temperature to initiate the depolymerization and modification reaction.

[0049] Suitable initiators include, for example, organic peroxides, such as peroxides including alkyl and aryl hydroperoxides, persulfates, perborates, percarbonates, azo compounds, and the like. Suitable azo compounds that are initiators include both conventional azo compounds and non-nitrile azo compounds, such as azobis(isobutyronitrile) and 2,2'-azobis-(2-methylbutyronitrile). Commercially available initiator materials include those available under the Luperox® trade name. Luperox® is a trade name for a group of organic alkyl or aryl peroxides, hydroperoxides, and percarbonates.

[0050] It is also possible to carry out the depolymerization and / or modification reactions (e.g., reactions (b) and (c)) under the influence of a catalyst, in which case the catalyst is introduced to the starting polystyrene resin and / or monomers, oligomers, and polymers of (b) and (c) under reaction conditions (the same as or similar to these free radical initiator reaction conditions).

[0051] In another embodiment, irradiation of polystyrene, such as irradiation with an electron beam source, can be used to generate radicals in the polystyrene. Electron beam scission (e.g., cleavage) occurs when the formed radicals do not recombine with each other but instead react with oxygen and / or undergo hydrogen abstraction to form end groups. The end result of electron beam scission of the polymer is a reduction in polymer molecular weight and the introduction of oxygen groups. Exposing raw polystyrene resin to radiation (such as an electron beam radiation source) is another method of depolymerizing the raw polystyrene resin. In one embodiment, the electron beam energy must be about 8 MeV.

[0052] In yet another aspect, polystyrene is exposed to a plasma, such as that generated by a corona discharge plasma source. During exposure to the plasma, oxygen is incorporated into the polystyrene structure by insertion or chain degradation, e.g., chemical bond cleavage, thereby forming functional groups that can react with other components, such as monomers, oligomers, and acrylates, in further reactions.

[0053] The depolymerization reaction, in which bond cleavage results in a reduction in molecular weight, may be the only modification of the polystyrene raw resin, or it may be followed by further modification in which the depolymerized polystyrene resin is substituted with polar and / or polar-charged functional groups. Such groups may be provided by monomers, oligomers, and polymers, such as acrylate monomers, oligomers, and polymers. The reaction between the radical sites of the depolymerized polystyrene resin and the functional groups of such monomers, oligomers, and polymers produces polymer structures exhibiting relatively low molecular weights, e.g., number-average molecular weights greater than 5,000 daltons. In other embodiments, the number average molecular weight is greater than about 10,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 15,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 20,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 25,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 30,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 35,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 40,000 daltons; in still other embodiments, the number average molecular weight may be greater than about 45,000 daltons; and in still other embodiments, the number average molecular weight may be greater than about 50,000 daltons.

[0054] In one embodiment of the present disclosure, polymerizable monomers, oligomers, and polymers that can react with depolymerized polystyrene include acrylic and methacrylic monomers that have only one (co)polymerizable double bond in the molecule. Such acrylic and methacrylic monomers include those that have a functional group capable of crosslinking, such as a hydroxyl group or a carboxyl group, as well as those that do not have such a functional group.

[0055] Examples of usable (meth)acrylic monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, and dodecyl (meth)acrylate; (meth)acrylic acid esters such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol ester (meth)acrylate; and (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and methylphenyl (meth)acrylate. These monomers may be used alone or in combination of two or more thereof. Preferably, alkyl acrylates are used, particularly preferably n-butyl acrylate or acrylic acid or lauryl methacrylate or n-butyl methacrylate.

[0056] The ink and coating compositions may also contain one or more colorants in the form of dyes or pigments dispersed therein. Suitable pigments include conventional organic or inorganic pigments. Representative pigments include, for example, Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 63, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 106, Pigment Yellow 111, Pigment Yellow 122, Pigment Yellow 124, Pigment Yellow 126, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 130, Pigment Yellow 131, Pigment Yellow 132, Pigment Yellow 133, Pigment Yellow 134, Pigment Yellow 135, Pigment Yellow 136, Pigment Yellow 137, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 140, Pigment Yellow 141, Pigment Yellow 142, Pigment Yellow 143, Pigment Yellow 144, Pigment Yellow 145, Pigment Yellow 146, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 149, Pigment Yellow 149, Pigment Yellow 149, Pigment Yellow 141, Pigment Yellow 142, Pigment Yellow 143, Pigment Yellow 144, Pigment Yellow 145, Pigment Yellow 146, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 149, Pigment Yellow 149, Pigment Yellow -114, Pigment Yellow 121, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 136, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 188, Pigment Yellow 194, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 34, Pigment Orange 36, Pigment Orange 61, Pigment Orange Orange 62, Pigment Orange 64, Pigment Red 2, Pigment Red 9, Pigment Red 14, Pigment Red 17, Pigment Red 22, Pigment Red 23, Pigment Red 37, Pigment Red 38, Pigment Red 41, Pigment Red 42, Pigment Red 48:2, Pigment Red 53:1, Pigment Red 57:1, Pigment Red 81:1, Pigment Red 112, Pigment Red 122, Pigment Red 170 , Pigment Red 184, Pigment Red 210, Pigment Red 238, Pigment Red 266, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 61, Pigment Green 7, Pigment Green 36, Pigment Violet 1, Pigment Violet 19, Pigment Violet 23 and Pigment Black 7.

[0057] Dyes suitable for use as colorants include, but are not limited to, azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, and combinations thereof. Other organic and inorganic pigments and dyes, as well as combinations to achieve the desired color, can also be used. The primer, ink, or coating composition can be any known color, such as black, white, red, orange, yellow, green, blue, indigo, violet, and all shades and combinations therebetween.

[0058] The ink and coating compositions described herein may contain from about 1 to about 90% by weight of the resin, preferably from about 2 to about 60% by weight of the resin, more preferably from about 5 to about 50% by weight of the resin, and even more preferably from about 10 to about 40% by weight of the resin of depolymerized and / or modified polystyrene resin, these amounts being based on the total weight of the ink and coating composition.

[0059] The ink and coating compositions can be cured to dry the film by methods using actinic radiation, such as solvent evaporation, air oxidation, and curing with an actinic light source such as ultraviolet light, which can be provided by electron beam energy, high voltage mercury bulbs, medium voltage mercury bulbs, xenon bulbs, carbon arc lamps, metal halide bulbs, UV-LED lamps, semiconductor lasers, UV lasers such as excimer lasers, sunlight, etc. Curing occurs primarily through unsaturated groups having mono-, di-, tri-, or higher functionality, called energy-curable monomers.

[0060] Examples of such monomers include, but are not limited to, the monofunctional ethylenically unsaturated monomers listed below and their combinations. The term "ethoxylated" refers to a chain-extended compound using ethylene oxide, "propoxylated" refers to a chain-extended compound using propylene oxide, and "alkoxylated" refers to a chain-extended compound using either ethylene oxide or propylene oxide, or both. Equivalent methacrylate compounds can also be used, but those skilled in the art will understand that methacrylate compounds have lower reactivity than their equivalent acrylate counterparts.

[0061] Isobutyl acrylate; cyclohexyl acrylate; isooctyl acrylate; n-octyl acrylate; isodecyl acrylate; isononyl acrylate; octyl / decyl acrylate; lauryl acrylate; 2-propylheptyl acrylate; tridecyl acrylate; hexadecyl acrylate; stearyl acrylate; isostearyl acrylate; behenyl acrylate; tetrahydrofurfuryl acrylate; 4-t.Butylcyclohexyl acrylate;3,3,5-Trimethylcyclohexane acrylate;Isobornyl acrylate;Dicyclopentyl acrylate;Dihydrodicyclopentadienyl acrylate;Dicyclopentenyloxyethyl acrylate;Dicyclopentanyl acrylate;Benzyl acrylate;Phenoxyethyl acrylate;2-Hydroxy-3-phenoxypropyl acrylate;Alkoxylated nonylphenol acrylate;Cumylphenoxyethyl acrylate;Cyclic trimethylolpropane formal acrylate;2(2-Ethoxyethoxy)ethyl acrylate;Polyethylene glycol monoacrylate;Polypropylene glycol monoacrylate;Caprolactone acrylate;Ethoxylated methoxypolyethylene glycol acrylate;Methoxytriethylene glycol acrylate;Trimethylolpropane Propylene glycol monomethyl ether acrylate;Diethylene glycol butyl ether acrylate;Alkoxylated tetrahydrofurfuryl acrylate;Ethoxylated ethylhexyl acrylate;Alkoxylated phenol acrylate;Ethoxylated phenol acrylate;Ethoxylated nonylphenol acrylate;Propoxylated nonylphenol acylate;Polyethylene glycol o-phenylphenyl ether acrylate;Ethoxylated p-cumylphenol acrylate;Ethoxylated nonylphenol acrylate;Alkoxylated lauryl acrylate;Ethoxylated tristyrylphenol acrylate;N-(Acryloyloxyethyl)hexahydrophthalimide;N-Butyl 1,2(acryloyloxy)ethyl carbamate;Acryloyloxyethyl hydrogen succinate oxyethyl hydrogen succinate); octoxypolyethylene glycol acrylate; octafluoropentyl acrylate; 2-isocyanatoethylacrylate; acetoacetoxyethyl acrylate; 2-methoxyethyl acrylate; dimethylaminoethyl acrylate; 2-carboxyethyl acrylate; and 4-hydroxybutyl acrylate.

[0062] Examples of suitable polyfunctional ethylenically unsaturated monomers that can be used in the ink and coating compositions include, but are not limited to, the polyfunctional compounds listed below (and combinations thereof). The term "ethoxylated" refers to compounds chain-extended with ethylene oxide, "propoxylated" refers to compounds chain-extended with propylene oxide, and "alkoxylated" refers to compounds chain-extended with either ethylene oxide or propylene oxide, or both. Equivalent methacrylate compounds can also be used, although those skilled in the art will understand that methacrylate compounds have lower reactivity than their equivalent acrylate counterparts.

[0063] 1,3-Butylene glycol diacrylate;1,4-Butanediol diacrylate;Neopentyl glycol diacrylate;Ethoxylated neopentyl glycol diacrylate;Propoxylated neopentyl glycol diacrylate;2-Methyl-1,3-propanediyl ethoxyacrylate;2-Methyl-1,3-propanediol diacrylate;Ethoxylated 2-methyl-1,3-propanediol diacrylate;3-Methyl 1,5-pentanediol diacrylate;2-Butyl-2-ethyl-1,3-propanediol diacrylate acrylate;1,6-Hexanediol diacrylate;Alkoxylated hexanediol diacrylate;Ethoxylated hexanediol diacrylate;Propoxylated hexanediol diacrylate;1,9-Nonanediol diacrylate;1,10-Decanediol diacrylate;Ethoxylated hexanediol diacrylate;Alkoxylated hexanediol diacrylate;Diethylene glycol diacrylate;Triethylene glycol diacrylate;Tetraethylene glycol diacrylate;Polyethylene glycol diacrylate;Propoxylated ethylene glycol diacrylate;Dipropylene glycol diacrylate;Tripropylene glycol diacrylate;Poly(tetramethylene glycol) diacrylate;Cyclohexanedimethanol diacrylate;Ethoxylated cyclohexanedimethanol diacrylate;Alkoxylated cyclohexanedimethanol diacrylate;Polybutadiene diacrylate;Hydroxypivalyl hydroxypivalate diacrylate;Tricyclodecane dimethanol diacrylate;1 ,4-Butanediylbis[oxy(2-hydroxy-3,1-propanediyl)]diacrylate;Ethoxylated bisphenol A diacrylate;Propoxylated bisphenol A diacrylate;Propoxylated ethoxylated bisphenol A diacrylate;Ethoxylated bisphenol F diacrylate;2-(2-Vinyloxyethoxy)ethyl acrylate;Ethoxylated glycerol triacrylate;Glycerol propoxylate triacrylate;Pentaerythritol triacrylate;Trimethylolpropane triacrylate;Caprolactone-modified trimethylolpropane triacrylate;Ethoxylated trimethylolpropane triacrylate;Propoxylated trimethylolpropane triacrylate;Tris(2-hydroxyethyl)isocyanurate triacrylate;ε-caprolactone-modified tris(2-hydroxyethyl)isocyanurate triacrylate;Melamine acrylate oligomer;Pentaerythritol tetraacrylate;Ethoxylated pentaerythritol tetraacrylate;Ditrimethylolpropane tetraacrylate;Dipentaerythritol pentaacrylate;Dipentaerythritol hexaacrylate;Ethoxylated dipentaerythritol hexaacrylate.

[0064] Other functional monomers that can be partially used in these formulations include cyclic lactams such as N-vinylcaprolactam, N-vinyloxazolidinone, and N-vinylpyrrolidone, as well as acryloylmorpholine, diacetone acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-octylacrylamide, Nt-octylacrylamide, N-dodecylacrylamide, N-benzylacrylamide, N-(hydroxymethyl)acrylamide, N-isobutoxymethylacrylamide, N-butoxymethylacrylamide, N-isopropyl ... and secondary or tertiary acrylamides such as N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-propylacrylamide, N,N-dibutylacrylamide, N,N-dihexylacrylamide, N,N-dimethylaminomethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminohexylacrylamide, N,N-diethylaminomethylacrylamide, N,N-diethylaminoethylacrylamide, N,N-diethylaminopropylacrylamide, N,N-dimethylaminohexylacrylamide, and N,N'-methylenebisacrylamide.

[0065] UV curable inks and coatings typically contain photoinitiators such as benzophenones, benzil ketals, dialkoxyacetophenones, hydroxyalkyl-acetophenones, aminoalkylphenones, acylphosphine oxides and thioxanthones such as benzophenone, methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)-benzophenone, 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy- Examples of suitable initiators include 2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinopropan-2-one, diphenylacylphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, or mixtures thereof. Electron beam curable inks and coatings do not require photoinitiators.

[0066] Ink and coating compositions may further contain additives to modify flow, adjust surface tension, control gloss, control pigment wetting, and adjust the abrasion resistance of the cured coating or printed ink. These are just a few of the types of additives that may be included in the compositions. Such additives include surfactants, waxes, shelf-life stabilizers, and combinations thereof.

[0067] The additives can function as leveling agents, shelf-life stabilizers, wetting agents, slip agents, flow agents, dispersants, and degassing agents. Preferred additives include fluorocarbon surfactants, silicones, and organic polymer surfactants. Examples include the commercially available Tegorad® product line (Tego Chemie, Essen, Germany) and the commercially available Solsperse® product line (Lubrizol Company).

[0068] The ink and coating compositions may further include extenders such as clay, talc, calcium carbonate, magnesium carbonate or silica to adjust water absorption, mist and color strength.

[0069] The inks and coatings can be applied using a variety of printing methods including, but not limited to, lithography, flexography, gravure, screen printing, and digital printing.

[0070] Ink and coating compositions are resistant to 2500 s at 25°C. -1 and a viscosity of about 4 Pa·sec to about 20 Pa·sec, preferably 5 Pa·sec to about 10 Pa·sec, at a shear rate of 2.5 s at 25°C. -1 and at these same conditions, a tack of about 5 (g-meter) to about 20 (g-meter) tack units, preferably 5 (g-meter) to about 10 (g-meter) tack units in a Thwing-Albert incommeter at 1200 rpm and 90°F.

[0071] Another aspect of the present invention describes an article, and a method for forming the same, in which an article, such as a substrate layer, is coated with an ink or coating composition comprising the modified polystyrene described herein. The ink and coating composition or ink can be applied to the article by printing methods such as inkjet, flexographic, gravure, screen, and lithographic printing. After application to the article, curing occurs.

[0072] The article may be composed of any typical substrate, such as paper, polymer, plastic, metal, and composite. The substrate may be paper printing stock, such as that used in publications, or packaging material in the form of cardboard sheets or corrugated board. Suitable polymer and plastic materials that can be used as the substrate include polyolefins (e.g., polyethylene, polypropylene), polyesters (e.g., polyethylene terephthalate). Metallized materials, such as metal-coated foils (e.g., laminated aluminum foils) or metal-coated polyesters, can be used as the substrate.

[0073] The present invention is further illustrated by the following examples. [Example]

[0074] The following examples illustrate certain aspects of the present invention and are not intended, nor should they be construed, to limit its scope in any manner.

[0075] Test methods and definitions: Molecular weight determination method: The molecular weight and polydispersity values ​​are 300 × 7.8 mm outer diameter, particle size 5 μm, pore size 50 Å, 100 Å, 500 Å, 10 3 Å and 10 4Polydispersity was measured by gel permeation chromatography (GPC) in a suitable solvent using a Waters 515 HPLC pump (equipped with Waters Millennium chromatography software, version 3.0 or equivalent) with a Phenogel GPC5 column set at 0.05 Å and equipped with a Waters 2410 refractive index detector or equivalent. As used herein, "polydispersity" or "dispersity" is a measure of the broadness of a polymer's molecular weight distribution. It is calculated as Mw / Mn, where Mw is the weight average molecular weight of the polymer and Mn is the number average molecular weight of the polymer. A polymer with a polydispersity index of 1 means that all chain lengths in the polymer are equal.

[0076] How to determine UV curing: The degree of UV cure is assessed by thumb twist and solvent resistance tests using isopropanol (IPA) and / or methyl ethyl ketone (MEK). Such tests are well known in the art and are described, for example, in Test Methods for UV and EB Curable Systems (C. Lowe & P. ​​KT Oldring, SITA Technology, 1994, ISBN 0 947798 07 2) page 74. The coatings were cured using a 200 watt / inch UV lamp at 150 fpm.

[0077] Viscosity and yield stress measurement methods: Viscosity was measured using a falling rod Laray viscometer. Sample size (e.g., ink, coating composition) is about 2 grams to about 3.5 grams. Testing is performed at 25°C ± 1°C. Viscosity is measured using 2500 reciprocating sections (sec -1 ) shear rate. Yield stress is the kinematic viscosity in poise at a shear rate of 2.5 (inverse seconds). ASTM D4040 can be used to determine these values.

[0078] Tack measurement method: Tack was measured using a calibrated electronic incometer (Thwing-Albert Instrument Co.). The ink or coating as described is metered to 1 milliliter of fluid drawn into a syringe. The fluid is placed on the top rubber roller of the incometer. The incometer is turned on, the roller begins to rotate, and the reported tack value is the maximum value reached after 1 minute of operation. The incometer is operated at 90°F and 1200 rpm.

[0079] Mist measurement method: Mist is evaluated in different locations on the printing press, usually near the ink ducts and the printing plate. In this specification, mist-catching paper is attached to the backplate of an ink meter. A white piece of paper is placed a predetermined distance from the ink roller, and the press is run at a predetermined speed and temperature for a predetermined time. The ink mist transferred to the paper is then evaluated by visual comparison with a master example or by measurement with a densitometer. Very little ink on the paper means that the ink has very low mist and is less likely to contaminate the printing press and contaminate the press room with ink mist.

[0080] The visual assessment of misting is assigned a numerical grade: 1 indicates no misting (undetectable or minimal ink mist), 3 indicates acceptable misting (a small amount of ink mist on the paper), and 5 indicates severe misting (a large amount of ink mist on the paper).

[0081] Dry transfer measurement method Dry transfer refers to the amount of ink used to target a print density of 1.10 as measured with a densitometer. A Prufbau printability tester can be used for this test. A graduated pipette is used to apply the ink to a roller set at approximately 25°C. The heatset dryer is set at 395°C. The roller pressure is set at 700N. The printing unit speed is 3 meters / second. Printing is performed on the substrate. The dry transfer to achieve the specified print density is measured in cubic millimeters (mm 3 ) is shown.

[0082] Water absorption measurement method Water absorption provides information about the lithographic printing performance of the finished ink on the printing press. Water absorption is measured with a Duke Ink Water Emulsification tester. The test is performed on a specified amount of ink or coating sample (e.g., 50 g ± 0.1 g) with or without additional water or fountain solution (e.g., 50 mL ± 0.5 mL). Water absorption is expressed as a percentage of the water (and fountain solution, if applicable) decanted after the test is performed relative to the total amount of water / fountain solution present before the test is performed. Water absorption may also be evaluated at different time intervals. The fountain solution used for the test was Rycoline PrintEasy® 2050 at 5.5 ounces per gallon of water (4.3%-w / v basis).

[0083] How to measure printed optical density: This is the achieved optical density of the print using a densitometer.

[0084] How to measure gloss: Coatings were applied to uncoated BYK Renata paper or coated BYK Chart PA-2810 using a #3 Mayer rod or a two-roll 14bcm anilox hand proofer. Gloss is measured with a glossmeter at a 60° angle.

[0085] Example 1: Depolymerization and reaction with acrylic monomers A 1000 ml four-neck flask equipped with a mechanical stirrer, reflux condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 153.1 g of MagieN40 (solvent) and 199.6 g of polystyrene (Aldrich Mw 192000). The flask was heated to 190 °C with stirring using a heating mantle. 27.27 g of styrene, 20.63 g of lauryl methacrylate, 1.08 g of n-butyl methacrylate, and 1.03 g of acrylic acid were added dropwise over 2 hours via a funnel containing 12.47 g of MagieN40 and 12.47 g of Luperox DI (initiator). The flask was held at 150 °C for 2 hours, after which 13.24 g of MagieN40 and 13.24 g of Luperox DI were immediately added. The flask was held at 150°C for 2 hours, after which 45.94g of MagieN40 was immediately added and then the resin was discharged.

[0086] Example 1 shows that the depolymerization reaction and the modification reaction with the monomer can occur in a one-step process. The reaction occurs between the depolymerized polystyrene and the monomer at the radical sites of the depolymerized polystyrene. [Table 1]

[0087] This average molecular weight is much lower than typical industrial polystyrene (whether linear, expanded, extruded, or oriented), which is typically above 100,000 daltons.

[0088] Coating 1, having the composition shown in Table 2, was prepared as follows. All amounts listed are in weight percent (wt%). 33.97 wt% of the resin produced in Example 1, 1.02 wt% of a blend of 95 wt% 1,6-HDDA and phenothiazine, 15.05 wt% HDDA, 33.99 wt% TPGDA, and 15.97 wt% TMPTA were heated to 125°C for 50 minutes and then cooled. A clear solution was present at room temperature. Then, 10.18 wt% benzophenone (photoinitiator), 5.19% Omnirad 481 (hydroxycyclohexyl phenyl ketone, photoinitiator), 19.86 wt% Ebecryl P115 synergist (an aminoacrylate used to synergize the free radical generation of Type II photoinitiators such as benzophenone), 2.89 wt% TegoRad 2300 (flow aid), 1.10 wt% Airex 920 (antifoaming agent), 10.98 wt% TPGDA, and 49.80 wt% TMPTA are mixed to form a clear solution at room temperature. The two parts are mixed at room temperature.

[0089] [Table 2]

[0090] Coating 1 and the commercial coatings identified in Table 3 below were applied to a test form of paper material (BYK Chart 2810). The coatings were applied by hand with a #3 Mayer rod and cured with a medium pressure Hg vapor UV lamp at 200 ft / min and 200 watts / inch (61 m / min and 80 W / cm).

[0091] [Table 3]

[0092] The commercial coating RCSFV0343453 is based on an epoxy oligomer containing bisphenol A (BPA). The inclusion of BPA in consumer products such as water bottles and food containers has become problematic due to health concerns posed by this material. Table 3 contains information demonstrating that it is possible to achieve the same properties in a coating without BPA with a coating containing Example 1. Coating 1 of the present invention exhibits gloss and resistance to removal comparable to commercial coatings that use bisphenol A.

[0093] Example 2: Grafting reaction between polystyrene and acrylic polymer (a) Preparation of acrylic polymer: A 1-L four-neck flask equipped with a mechanical stirrer, reflux condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 104.1 g of Magie N40. The flask was heated to 125°C with stirring using a heating mantle. 136.4 g of styrene, 103.2 g of lauryl methacrylate, 5.2 g of n-butyl methacrylate, and 5.2 g of acrylic acid were added dropwise via the dropping funnel over 4 hours, along with 40.0 g of Magie N40 and 1.2 g of Luperox P. The flask was held at 125°C for 2 hours, after which 3.4 g of Magie N40 and 0.7 g of Luperox P were immediately added. The flask was held at 125°C for 3 hours, after which 100.6 g of Magie N40 was immediately added, and the resin was then discharged at 90°C.

[0094] (b) A 250 mL four-neck flask equipped with a mechanical stirrer, reflux condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 20.0 g of polystyrene (MW 250,000 (from ACROS)) and 40.0 g of Example 2(a). The flask was heated to 170°C with stirring using a heating mantle. After the mixture was melted and homogenized, the flask was cooled to 150°C, and 18.4 g of Magie N40 and 1.6 g of Luperox DI were added dropwise via the dropping funnel over 2 hours. The flask was held at 150°C for 3 hours, after which the resin was discharged into a glass bottle at 140°C.

[0095] [Table 4]

[0096] Example 3: Grafting reaction between polystyrene and acrylic monomers A 250 mL four-neck flask equipped with a mechanical stirrer, reflux condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 199.68 g of polystyrene (MW 250,000 (ACROS)) and 153.24 g of Magie N40. The flask was heated to 170°C with stirring using a heating mantle. After the mixture was melted and homogenized, the flask was cooled to 150°C. 27.27 g of styrene, 20.60 g of lauryl methacrylate, 1.07 g of n-butyl methacrylate, and 1.03 g of acrylic acid were then added dropwise via the dropping funnel over 2 hours, along with 24.94 g of Magie N40 and 25.01 g of Luperox DI. The flask was held at 150°C for 1.5 hours, after which 0.76 g of Magie N40 and 0.8 g of Luperox DI were immediately added. The flask was held at 150°C for 3.5 hours, after which 12.0g of Magie N40 was immediately added and the resin was then ejected onto an aluminum sheet at 140°C.

[0097] [Table 5]

[0098] [Table 6]

[0099] Using a mixer at 3000 rpm, combine A&B and mix for 2 minutes, add C and mix for 5 minutes. Add D and mix for 2 minutes. Add E and mix for 30 seconds. Add F and mix for 30 seconds, then add I and mix for 5 minutes.

[0100] Table 7 shows the properties of the ink of Example 3 and the commercially available ink. Higher viscosity is preferred, and higher yield stress is preferred (especially at low tack). The ink of Example 3 has lower tack, viscosity, and yield, but surprisingly, the mist is comparable, indicating that this can be an ink composition with excellent printing properties, especially on low basis weight paper (which tends to peel and pill at high viscosity, high tack, and high yield stress).

[0101] [Table 7]

[0102] Example 4: Depolymerization A 1000 ml flask was charged with 500.00 g of polystyrene (Chemical Resources, Mn 41,300; Mw 112,000) and 500.00 g of toluene. The reaction was heated to 100°C. A mixture of 26.6 g of Luperox 26M50 (Arkema) and 25.0 g of toluene (Sigma) was added dropwise over 3 hours. The reaction was run for 1 hour, stopped, and the resin was discharged onto an aluminum sheet and air-dried. A clear, light gray solid was obtained. A 250 ml flask was charged with 85 g of TPGDA (Miwon), 15.0 g of resin, and 0.50 g of 4-methoxyphenol (MEHQ, Sigma), heated to 115°C for 3 hours, and filtered to obtain a single-phase system. The depolymerized polystyrene product of the present invention was made into a stable 15 wt% solids coating solution in TPGDA. This is Coating 4 in Table 11 below. In contrast, the stock polystyrene resin can be made into a coating solution with only 4 wt % resin in a solution of TPGDA.

[0103] [Table 8]

[0104] Example 5: Depolymerization and Grafting with Acrylic Monomers A 500 ml flask was charged with 50.00 g of polystyrene (Chemical Resources, Mn 41,300; Mw 112,000) and 60.00 g of toluene. The reaction was blanketed with nitrogen and heated to 100°C. 2.6 g of Luperox 26M50 (Arkema) and 10.0 g of toluene (Sigma) were added dropwise over 6 minutes. 1.1 g of acrylic acid (Acros), 2.66 g of Luperox 26M50, and 10 g of toluene were then added over 9 minutes. After the reaction had run for 3 hours, 1.65 g of MEHQ in 25 ml of toluene was added over 10 minutes. 283.30 g of tripropylene glycol diacrylate was added over 9 minutes, and the temperature was increased to 116°C to distill off the toluene.

[0105] [Table 9]

[0106] [Table 10]

[0107] [Table 11]

[0108] As shown in Table 11, coatings 4 and 5 exhibited excellent solvent resistance and exhibited resistance of over 500+ MEK rubs, far superior results compared to commercial coatings.

[0109] Example 6: Grafting by Corona Discharge (Prophetic Example) Polystyrene pellets are exposed to a 15 kV voltage in a 60 Hz corona discharge treatment in air, thereby introducing peroxide onto the surface. The polystyrene is then copolymerized with an acrylic monomer (i.e., 2-hydroxyethyl methacrylate) in a solvent. The resulting polystyrene has improved hydrophilicity due to the increased concentration of hydroxyl and ester groups depending on the treatment time. One skilled in the art can then formulate aqueous-based inks and coatings containing the more hydrophilic polystyrene copolymer to be compatible with typical water-based acrylic resins based on styrenated acrylic.

[0110] Example 7: Electron Beam Irradiation and In-Situ Graft Polymerization with Monomer One hundred grams of polystyrene beads were sealed in a polyethylene bag with air. Electron beam irradiation was performed outside the polyethylene bag in 200 ppm oxygen at room temperature (25°C). The electron beam energy was 8 MeV at 20 mA electron beam current. The distance from the output electron beam source to the sample was 30 cm. The accelerator generated a stable electron beam of the same energy, and the samples were irradiated with different doses by irradiating for different times. Care was taken to ensure that the sample temperature did not vary significantly from room temperature. In situ graft polymerization of polyethylene glycol (PEG 1000) and (methyl vinyl ether / maleic anhydride), VEMA H or VEMA AN (Ashland) at various PEG to VEMA ratios resulted in a series of grafted polystyrenes compatible with inks and coatings.

[0111] Although the present invention has been described in detail, including preferred embodiments thereof, it will be understood that those skilled in the art, upon consideration of this disclosure, may make modifications and / or improvements to the invention which are within the scope and spirit of the invention.

Claims

1. a modified depolymerized polystyrene resin grafted with a monomer, oligomer, polymer, copolymer, and / or terpolymer selected from the group consisting of (meth)acrylic acid alkyl ester monomers, (meth)acrylic acid monomers, combinations thereof, and oligomers, polymers, copolymers, and terpolymers thereof, and combinations thereof; the modified depolymerized polystyrene resin has a number average molecular weight greater than 5,000 Daltons; Ink or coating composition.

2. The modified depolymerized polystyrene resin is obtained by modifying a raw material polystyrene resin selected from the group consisting of depolymerized scrap polystyrene resin produced in a polystyrene production process or a process for producing a polystyrene molded product; and / or depolymerized polystyrene foam; and / or depolymerized general-purpose polystyrene; and / or depolymerized extruded polystyrene foam; and / or depolymerized expanded polystyrene; 10. The ink or coating composition of claim 1, wherein the base polystyrene resin has a number average molecular weight greater than 5,000 Daltons.

3. 3. The ink or coating composition of claim 1 or 2, further comprising a colorant, said colorant being selected from the group consisting of organic pigments, inorganic pigments, organic dyes, inorganic dyes, and combinations thereof.

4. The ink or coating composition of any one of claims 1 to 3, further comprising an energy curable component and a photoinitiator.

5. 5. The ink or coating composition of any one of claims 1 to 4, wherein the modified depolymerized polystyrene resin is present in an amount of 1 to 90 wt%, based on the total weight of the composition.

6. Features include: a) 2500 s at 25 °C －１ a viscosity of 4 Pa·sec to 20 Pa·sec at a shear rate of; b) 2.5 s at 25°C －１ a flow value (yield value) of 40 Pa·sec to 200 Pa·sec at a shear rate of 100°C; The ink or coating composition of any one of claims 1 to 5, wherein the ink or coating composition has one or more of the following:

7. 7. The ink or coating composition of any one of claims 1 to 6, wherein the composition has a tack of from 5 Tack Units (g-meter) to 20 Tack Units (g-meter) at 1200 rpm, 90°F, in a Thwing-Albert incometer.

8. 8. The ink or coating composition of any one of claims 1 to 7, wherein the modified depolymerized polystyrene resin is also grafted with a styrene-containing monomer, oligomer, polymer, or copolymer.

9. The ink or coating composition of any one of claims 1 to 8, further comprising an energy curable component.

10. The ink or coating composition of any one of claims 1 to 9, further comprising an acrylated oligomer, an acrylic monomer, or a combination thereof.

11. The ink or coating composition of any one of claims 1 to 10, further comprising a secondary acrylamide, a tertiary acrylamide, or a cyclic lactam.

12. 1. An ink or coating composition comprising a modified depolymerized polystyrene resin, The modified depolymerized polystyrene resin comprises a depolymerized polystyrene resin having a number average molecular weight greater than 5,000 Daltons that has been modified with a monomer, oligomer, polymer, copolymer, and / or terpolymer selected from the group consisting of (meth)acrylic acid alkyl ester monomers, (meth)acrylic acid monomers, combinations thereof, and oligomers, polymers, copolymers, and terpolymers thereof, and combinations thereof; the depolymerized polystyrene resin is derived from a raw polystyrene resin having a number average molecular weight of 40,000 Daltons or greater; Ink or coating composition.

13. 13. A method for making the ink or coating composition of any one of claims 1 to 12, comprising a modified depolymerized polystyrene resin and an energy curable component, comprising: a) generating a depolymerized polystyrene resin derived from a raw polystyrene resin by cleaving chemical bonds in the raw polystyrene resin to generate the depolymerized polystyrene resin; and b) reacting the depolymerized polystyrene resin with a monomer, oligomer, or polymer, or combination thereof, comprising one or more selected from the group consisting of (meth)acrylic acid alkyl ester monomers, (meth)acrylic acid monomers, and oligomers, copolymers, and terpolymers thereof, and combinations thereof, to produce a modified depolymerized polystyrene resin. and performing the steps a) and b) in one step.

14. An ink or coating composition according to any one of claims 1 to 12, wherein the (meth)acrylic acid alkyl ester monomer is selected from n-butyl acrylate, n-butyl methacrylate, and lauryl methacrylate, and the (meth)acrylic acid monomer is acrylic acid.

15. a modified depolymerized polystyrene resin grafted with a monomer, oligomer, polymer, copolymer, and / or terpolymer selected from the group consisting of (meth)acrylic acid alkyl ester monomers, (meth)acrylic acid ester monomers, (meth)acrylic acid aryl ester monomers, (meth)acrylic acid monomers, combinations thereof, and oligomers, polymers, copolymers, and terpolymers thereof, and combinations thereof; the modified depolymerized polystyrene resin has a number average molecular weight greater than 5,000 Daltons; the (meth)acrylic acid ester monomer is a monomer selected from benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol ester (meth)acrylate; and The (meth)acrylic acid aryl ester monomer is a monomer selected from phenyl (meth)acrylate and methylphenyl (meth)acrylate. Ink or coating composition.

16. The ink or coating composition of claim 15, wherein the (meth)acrylic acid alkyl ester monomer is cyclohexyl (meth)acrylate.

17. The ink or coating composition of claim 16, wherein the (meth)acrylic acid aryl ester monomer is phenyl (meth)acrylate or methylphenyl (meth)acrylate.

Images