Plastic products

Abstract

The present invention relates to a plastic article formed of a plastic material having a colour forming compound incorporated therein. The present invention further relates to a method of producing said plastic article using the colour forming compound, as well as a method of forming a mark or image on a plastic article.

Description

[Technical field]

[0001] The present invention relates to the incorporation of color forming compounds into plastic articles and to plastic articles having color forming compounds incorporated therein. [Background technology]

[0002] The use of laser-responsive compositions containing color-forming compounds in coating compositions to produce human-readable and / or machine-readable images and to display variable information on a substrate is known. Typically, such laser-responsive compositions are applied to a substrate via a coating composition, and then the image(s) can be formed by applying suitable laser-applied radiation to the composition. The radiation acts on the color-forming compounds of the composition to display or change color in the areas of the composition to which the radiation is applied, thus forming the image(s).

[0003] In many different industries, the laser-reactive composition is applied as a coating composition to the outside of a substrate to provide variable information. For example, the laser-reactive coating composition has been used to provide variable information on a label or film attached to a plastic product, such as a plastic packaging. The laser-reactive coating composition is applied to the outside of the label. These labels are usually made of a plastic different from the plastic packaging, or even of a non-plastic material, such as paper, and constitute a separate article from the plastic packaging itself. This is clearly demonstrated by the wrap-around film labels or adhesive plastic labels used on plastic bottles for beverages. Traditionally, when such plastic packaging is disposed of, the disposal processes for the packaging and the label are different and incompatible. For separate articles (packaging and label), two different recycling processes are required, and one or the other of the articles is not recyclable, or in some cases, the two articles are combined after the label is applied to the packaging and cannot or are difficult to separate, and therefore a suitable recycling process cannot or is difficult to achieve. From a sustainability perspective, this is far from ideal.

[0004] It is therefore desirable to provide a sustainable solution to the above problems that allows for the efficient formation of clear, recognizable human-readable and / or machine-readable image(s) for providing variable information on plastic products, e.g., plastic packaging, while helping to reduce waste and streamlining waste disposal and recycling operations. Summary of the Invention

[0005] According to a first aspect of the present invention there is provided a plastic article formed from a plastic material having a colour forming compound incorporated therein, the plastic article being a plastic preform or a plastic package.

[0006] According to a second aspect of the present invention there is provided a plastic product formed of a plastic material having a colour forming compound incorporated therein, the plastic product being produced by contacting the colour forming compound with the plastic material to form a plastic material having the colour forming compound incorporated therein, and forming the plastic material having the colour forming compound incorporated therein into the plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0007] According to a third aspect of the present invention there is provided a plastic product formed from a plastic material having a colour forming compound incorporated therein, the plastic product being produced by forming the plastic material having the colour forming compound incorporated therein into the plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0008] According to a fourth aspect of the present invention there is provided a method of producing a plastic product formed of a plastic material having a colour forming compound incorporated therein, the method comprising the steps of contacting the colour forming compound with the plastic material to form a plastic material having the colour forming compound incorporated therein, and forming the plastic material having the colour forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0009] According to a fifth aspect of the present invention there is provided a method of producing a plastic product formed of a plastic material having a colour forming compound incorporated therein, the method comprising forming the plastic material having the colour forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0010] According to a sixth aspect of the present invention there is provided the use of a colour forming compound in the production of a plastic material having the colour forming compound incorporated therein, or in the production of a plastic product having the colour forming compound incorporated therein, wherein the plastic product is a plastic preform or a plastic packaging body.

[0011] According to a seventh aspect of the present invention, (i) a color-forming compound; and (ii) Plastic materials A mixture comprising:

[0012] According to an eighth aspect of the present invention there is provided a plastic article displaying a mark or image, the plastic article being formed from a plastic material having a colour forming compound incorporated therein, the plastic article being a plastic preform or a plastic package.

[0013] According to a ninth aspect of the present invention there is provided a plastic product displaying a mark or image, said product being obtainable by applying radiation to a plastic product having a colour forming compound incorporated therein such that the mark or image is formed where the radiation is applied to the plastic product, and the plastic product is a plastic preform or a plastic packaging product.

[0014] According to a tenth aspect of the present invention there is provided a method of forming a mark or image on a plastic article, the method comprising the step of exposing the plastic article to radiation to form the mark or image where the radiation is applied, the plastic article being formed of a material having a colour forming compound incorporated therein, and the plastic article being a plastic preform or a plastic packaging body.

[0015] In accordance with a further aspect of the present invention there is provided the use of a colour forming compound in the formation of a mark or image on a plastic article formed of a plastic material having the colour forming compound incorporated therein, the plastic article being a plastic preform or a plastic packaging body.

[0016] According to a further aspect of the present invention there is provided a plastic material having a colour forming compound incorporated therein.

[0017] According to a further aspect of the invention there is provided a method of forming a plastic material having a colour forming compound incorporated therein, the method comprising the step of contacting a colour forming compound with the plastic material.

[0018] According to a further aspect of the invention, there is provided a method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed of a plastic material having a color forming compound incorporated therein, the method including the steps of contacting the color forming compound with the plastic material to form the plastic material having the color forming compound incorporated therein, and forming the plastic preform from the plastic material having the color forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle.

[0019] According to a further aspect of the invention, there is provided a method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed of a plastic material having a colour forming compound incorporated therein, the method comprising forming the plastic preform from the plastic material having the colour forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] It has been surprisingly and advantageously found that the incorporation of color-forming compounds into plastic products allows for the effective formation of distinct, recognizable human-readable and / or machine-readable mark(s) or image(s) by application of suitable radiation to the plastic product, preferably from a laser source(s), lamp or LED. Thus, the resulting imaged plastic product can display any required variable information as mark(s) or image(s) in and on the plastic product without the need for additional attachment of any substrate or material, such as a separate label or film. It is noted that it is known to form mark(s) or image(s) on plastic products through application of radiation, preferably using a laser source(s), lamp or LED. Formation of the mark or image can be achieved through techniques such as ablation, engraving or foaming of the plastic material used to form the plastic product. However, problems exist regarding the effectiveness of the formed mark(s) or image(s). The mark(s) or image(s) may lack opacity, and therefore they are not effective and clear. The present invention provides for the formation of effective mark(s) or image(s) and overcomes the problems detailed above, i.e., streamlining waste disposal operations and avoiding the need for separate recycling processes for the plastic product and any additionally attached substrates or materials. Only one recycling process is required for proper waste disposal of the plastic product. Furthermore, since the color-forming compounds are already incorporated into the plastic product of the present invention to generate variable information on the plastic product, there is no need to additionally apply any ink, coating, transfer, pigment or dye to the outside of the product, for example, by application techniques such as jetting, spraying, screening, or overprinting, aimed at providing variable information.

[0021] It is surprising and advantageous that the color forming compounds can be used to create the plastic products of the present invention. In general, the formation, manufacture or conversion of plastic products, as well as any antibacterial, antimicrobial or antiviral processes to which the formed plastic products may be exposed, require high temperature processing conditions. It is therefore highly surprising and advantageous that under such high temperature processing conditions, the color forming compounds do not form a color in the plastic products that would prevent the subsequent generation of an effective and recognizable mark or image by the color forming compounds themselves or via marking of the plastic products via techniques such as those discussed above, such as ablation, engraving or foaming. The formation of the mark or image on the plastic products of the present invention is achieved after applying a specific radiation to the plastic products after their formation. To date, such advantageous effects have not been achieved for previously used color forming compounds known in laser marking.

[0022] According to a first aspect of the present invention there is provided a plastic article formed from a plastic material having a colour forming compound incorporated therein.

[0023] All features of the first aspect of the invention, including all preferred and optional features detailed below, are applicable to all other aspects described herein. Similarly, all features of all other aspects described herein are applicable to the first aspect of the invention, including the preferred and optional features of each aspect.

[0024] The plastic material from which the plastic product of the present invention is formed may be any suitable plastic material. The plastic material may be selected from any suitable commercially available plastic material, which are well known to those skilled in the art.

[0025] The plastic material may comprise a polymer, a copolymer, or a combination thereof as a major component. The plastic material may be poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymers; poly(ethylene acrylate) copolymers; acrylic acid; polyvinyl butyral; polyolefins, such as polybutene, polyethylene, and polypropylene, including both low density (LDPE) and high density (HDPE) polyethylene; polyamides, such as ethylenediamine and hexamethylenediamine; nylon; polyesters, such as poly(lactic acid) (PLA), polyethylene terephthalate (PET), polyester resins, polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (GCM), and the like. poly(propylene glycol tungsten phosphates (PCTG), polyhydroxyalkanoates (PHAs), and poly(glycolic acid) (PGAs); polyurethanes; acrylic acid and styrene-acrylate copolymers; polystyrene (PS); polycaprolactone; polycarbonates; fluoropolymers; phenolic or phenol formaldehyde resins; epoxy resins; elastomers, such as nitrile butadiene rubber, styrene butadiene rubber; silicone rubber; polypyrrole; ABS (acrylonitrile butadiene styrene); acetal; recycled materials, such as polyethylene terephthalate (r-PET); or combinations thereof.

[0026] The plastic material may comprise one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G), preferably a blend of polyethylene terephthalate (PET) with one or more of polyethylene, polypropylene (PP), polycarbonate (PC), polystyrene (PS), poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymers, and ABS (acrylonitrile butadiene styrene). The plastic material may include one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G), preferably a blend of polyethylene terephthalate (PET) with one or more of epoxy resins, polyester resins, phenolic resins or phenol formaldehyde resins, and elastomers, such as nitrile butadiene rubber, styrene butadiene rubber.

[0027] The plastic material can include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene (PCTFE), cyclic olefin copolymer (COC), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), polycarbonate (PC), poly(lactic acid) (PLA), polyethylene terephthalate (PET), polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), low density polyethylene (LDPE) and polystyrene (PS), or combinations thereof.

[0028] Preferably, the plastic material comprises polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), recycled polyethylene terephthalate (r-PET), low density polyethylene (LDPE), polyethylene terephthalate glycol (PET-G), and polystyrene (PS), or combinations thereof. These plastic materials are recyclable, and thus, it will be appreciated by those skilled in the art that the plastic material can be any suitable recyclable plastic material.

[0029] More preferably, the plastic material comprises polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP), or a combination thereof. More preferably, the plastic material comprises polyethylene terephthalate (PET), high density polyethylene (HDPE), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low density polyethylene (LDPE), polypropylene (PP), or a combination thereof. More preferably, the plastic material comprises polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G). More preferably, the plastic material comprises polyethylene terephthalate (PET).

[0030] Examples of commercially available PET and r-PET include PET available from Songhan Plastic Technology Co., Ltd. under the designation "DAK Americas Laser+® B90A PET" and r-PET available from Far Eastern New Century Corporation under the designation "FENC® Topgreen rPCT."

[0031] The plastic material may further comprise one or more additives. Suitable additives include: pigments that give rise to the plastic material and thus the plastic product formed from the pigment to display color; waxes, e.g., microcrystalline waxes, fatty acid waxes; waxes) or oxidized Fischer-Tropsch waxes; UV absorbers; slip additives; lubricants; inhibitors; antioxidants; stabilizers; UV stabilizers; adhesion promoters; plasticizers; light or energy absorbers; surfactants; wetting agents; drying accelerators; colorants, e.g., pigments; flame retardants; antistatic agents; fillers; tinting agents; fluorescent agents; optical brighteners; oxidizing or reducing agents; stabilizers; light stabilizers, e.g., hindered amines; rheology modifiers, e.g., thickeners or thinners; matting agents; activated clays; anti-settling agents; anti-sagging agents; dispersing agents; surface modification additives; slip agents, e.g., stearates; leveling agents; fillers; humectants; adhesion promoters, acid or base scavengers; retarders; defoamers; antifoaming agents; biocides; antimicrobial agents; antiviral agents; antibacterial agents; antifungal agents; mildewcides; bactericides; disinfectants; and other suitable processing additives; or combinations thereof. Typically, one or more of the following, or a combination of the following, may be selected from those listed above and present in the plastic material: pigments; waxes; plasticizers; antioxidants; UV stabilizers; and fillers. It should be recognized that the additives required for the plastic material vary depending on the desired plastic product. Such requirements are well known to those skilled in the art. Typically, the additive or additives may be present in the plastic material in an amount of 0.01-35% by weight, e.g., 0.02-30% by weight, or 0.05-25% by weight, or 0.1-20% by weight. Here, "wt. %" refers to the weight of the additive or additives relative to the total weight of the plastic material, i.e., the polymer, copolymer, or combination thereof, and the additive or additives, if present.

[0032] It should be appreciated that if the plastic material does not include any additives, the plastic material may simply be formed of a polymer, copolymer, or combination as detailed above.

[0033] The plastic materials of the present invention are generally known in the art by their polymeric, copolymeric components, for example, the "PET" or "HDPE" plastic materials forming the "PET" or "HDPE" plastic bottles. Thus, as detailed herein, plastic materials containing polymeric, copolymeric components, for example, plastic materials containing HDPE, LDPE and / or PP, may be considered as HDPE, LDPE and / or PP plastic materials, which in turn result in HDPE, LDPE and / or PP plastic products.

[0034] In the context of the present invention, a plastic material is not an adhesive material. A plastic material is not a hot melt adhesive.

[0035] The plastic article of the present invention may be any suitable article formed from a plastic material.

[0036] The plastic products of the present invention are suitable for holding or storing contents, e.g., liquids or solids. The contents may be medicines, food and beverages, and non-consumable personal care and household products. The plastic products of the present invention may be empty or partially or completely filled with contents.

[0037] The plastic product of the present invention can be three-dimensional. The plastic product of the present invention can define a volume usable for holding or storing contents, e.g., liquids or solids. The contents can be medicines, food and beverages, or non-consumable personal care and household products. The plastic product of the present invention can define an interior volume usable for holding or storing contents. The plastic product of the present invention can have an exterior wall(s), e.g., an exterior wall that defines an interior volume usable for holding contents. It should be appreciated that the exterior wall(s) can define more than one interior volume (separate or connected) within the plastic product usable for holding contents.

[0038] The plastic product is a plastic preform or a plastic package. The plastic package includes a plastic lid and a plastic container, such as a plastic food container and / or a beverage container or a container of a pharmaceutical or non-consumable personal care and household product. Suitable examples of plastic containers include a plastic box, a plastic pouch, a plastic bottle, such as a plastic beverage bottle, which is typically used in the pharmaceutical industry and the tobacco or vaping industry, a plastic blister package, and a clamshell package, which is typically used in the food industry. In the context of the present invention, the plastic product may also be a multi-layer plastic product, such as a multi-layer plastic preform, a container, or a bottle having at least one layer formed of the plastic material detailed herein, and further including additional layer(s), such as a barrier layer or an additional protective layer. Such a multi-layer plastic product may be formed by a multi-shot technique, such as a multi-shot injection molding (usually for multi-layer plastic bottles), or by other methods, such as thermoforming, capping, and heat sealing in the formation of a blister package. It should be recognized that in the context of the present invention, the plastic product is a uniformly formed plastic product, i.e., a plastic product formed uniformly with the same plastic material(s). Plastic products include the plastic products described herein with additional plastic components associated therewith, for example, a plastic bottle may have a plastic lid associated therewith. Plastic products also include the plastic products described herein with additional non-plastic components associated therewith, for example, a blister package with a metal, aluminum foil or paper closure layer (with lid). Thus, the plastic products of the present invention include any plastic product, including its closure, pump, cap, spout, handle, lid or cover, formed of the plastic materials described herein.

[0039] The plastic products of the present invention can be used to store, hold, transport and dispense items such as medicines, food and beverages, and non-consumable personal care and household products.

[0040] Preferably, the plastic product is a plastic preform or a plastic container. Preferably, the plastic product is a plastic container. Preferably, the plastic product is a plastic box, a plastic pouch, a plastic bottle, a plastic blister package, or a plastic clamshell package. More preferably, the plastic product is a plastic box, a plastic pouch, or a plastic bottle. More preferably, the plastic product is a plastic bottle.

[0041] Preferably, in the context of the present invention, the plastic packaging does not include a plastic film or label, i.e. the plastic packaging refers to the plastic packaging other than the plastic film or label.

[0042] "Plastic preform" means a plastic article, usually a plastic bottle, that is an intermediate product in a production process for a plastic product. This is a term well known in the art. The plastic preform is then formed, usually by blow molding, into a plastic product, such as a plastic bottle.

[0043] The plastic materials forming the plastic articles of the present invention have color forming compounds incorporated therein which allow for the formation of distinct marks or images upon application of radiation to the plastic article in which the color forming compounds are incorporated. The marks or images can be formed through application of specific radiation to the plastic article after processing and manufacture of the plastic article, and it is surprising and advantageous that the high temperature conditions of processing and manufacture do not result in color formation which would prevent the formation of a distinct and usable mark or image.

[0044] The color-forming compound may be selected from the following: inorganic hydrates; potassium bicarbonate; oxyanions of polyvalent metals or oxoacids, and / or hydrates thereof; kaolin; leuco dyes; diacetylenes; or combinations thereof. Preferably, the color-forming compound may be selected from the following: inorganic hydrates; potassium bicarbonate; oxyanions of polyvalent metals or oxoacids, and / or hydrates thereof; calcined kaolin; leuco dyes; diacetylenes; or combinations thereof. Preferably, the color-forming compound is selected from the following: inorganic hydrates; potassium bicarbonate; oxyanions of polyvalent metals or oxoacids, and / or hydrates thereof; calcined kaolin; and diacetylenes; or combinations thereof.

[0045] More preferably, the color forming compound is selected from the following: sodium molybdate dihydrate; ammonium pentaborate tetrahydrate; ammonium pentaborate octahydrate; potassium bicarbonate; ammonium octamolybdate; kaolin; leuco dyes; diacetylenes; or combinations thereof. More preferably, the color forming compound is selected from the following: sodium molybdate dihydrate; ammonium pentaborate tetrahydrate; ammonium pentaborate octahydrate; potassium bicarbonate; ammonium octamolybdate; calcined kaolin; leuco dyes; diacetylenes; or combinations thereof. More preferably, the color forming compound is selected from ammonium octamolybdate; calcined kaolin; and diacetylenes; or combinations thereof.

[0046] Without being bound by theory, when an inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, is selected as the color-forming compound, the inventors of the present invention believe that the inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, promotes the formation of color on the plastic product, and thus the formation of a mark or image, through dehydration (pyrolysis) to a dehydrated form after application of radiation to the plastic product, preferably from a laser source(s), lamp or LED. The inventors of the present invention believe that during dehydration, the off-gassing or outgassing ("foaming") of water vapor from the inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, creates microscopic pockets or bubbles within the plastic material of the plastic product, resulting in a change in refractive index, and thus causing the plastic product to display color after application of radiation to the plastic product. The present inventors believe that this effect enhances the color formation seen when radiation is applied to plastic products that do not have inorganic hydrates, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, incorporated therein. For ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, the present inventors also believe that the off-gassing or outgassing of ammonia enhances the "foaming" effect. The color formed by inorganic hydrates, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, is white or a shade thereof, and thus the mark or image formed is white or a shade thereof. When sodium molybdate dihydrate is selected as the color forming compound, the plastic material forming the plastic product preferably comprises polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G), more preferably polyethylene terephthalate (PET).

[0047] Without being bound by theory, when potassium bicarbonate is selected as the color forming compound, the inventors of the present invention believe that after application of radiation thereto, preferably from a laser source(s), lamp or LED, the potassium bicarbonate promotes the formation of color, and thus the formation of a mark or image, and through off-gassing or out-gassing of carbon dioxide creates fine pockets or bubbles in the plastic material of the plastic product, resulting in a change in refractive index, such that the plastic product displays color after application of radiation thereto. It may also be the case that some off-gassing or out-gassing of water vapor ("foaming") from the potassium bicarbonate is seen to create fine pockets or bubbles in the plastic material of the plastic product, resulting in a change in refractive index, such that the plastic product displays color after application of radiation thereto. The inventors of the present invention believe that this effect enhances the formation of color seen when radiation is applied to a plastic product that does not have potassium bicarbonate incorporated therein. The color formed by potassium bicarbonate is white or a shade thereof, and thus the mark or image formed is white or a shade thereof.

[0048] Without being bound by theory, when kaolin, discussed below, is selected as the color-forming compound, the kaolin may be provided in calcined or uncalcined form, i.e., calcined or uncalcined kaolin. The inventors of the present invention believe that the uncalcined kaolin can facilitate the formation of color, and thus the formation of a mark or image, through the loss of water retained within the layered silicate material after application of radiation to the layered silicate material, preferably from a laser source(s), lamp or LED. The inventors of the present invention believe that the off-gassing or out-gassing of water vapor ("foaming") from the layered structure of the uncalcined kaolin creates microscopic pockets or bubbles within the plastic material of the plastic product, resulting in a change in refractive index, such that the plastic product displays color after application of radiation to the plastic product. The inventors of the present invention believe that this effect enhances the formation of color seen when radiation is applied to a plastic product that does not have uncalcined kaolin incorporated therein. The color formed by the non-calcined kaolin may be white or a shade thereof, and the mark or image formed thereby may be white or a shade thereof. The inventors of the present invention believe that the calcined kaolin may facilitate the formation of color, and thus the mark or image, through the absorption of radiation by the calcined kaolin, preferably from a laser source(s), lamp or LED. The inventors of the present invention believe that this absorption of radiation then recrystallizes the localized plastic material surrounding the calcined kaolin to produce the color, and thus the mark or image. The color formed by the calcined kaolin may be white or a shade thereof, and the mark or image formed thereby may be white or a shade thereof. The color formed by the calcined kaolin may also be black, gray, brown, or a shade thereof, and the mark or image formed thereby may be black, gray, brown, or a shade thereof.The inventors of the present invention believe that this black, grey, brown colour is achieved through the absorption of higher levels of radiation by the calcined kaolin, preferably from a laser source(s), lamp or LED, which carbonises the localised, surrounding plastic material to promote the formation of a different colour than that formed at lower radiation fluences. When kaolin, either calcined or uncalcined kaolin, is selected as the colour forming compound, the plastic material forming the plastic product preferably comprises polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G), more preferably polyethylene terephthalate (PET).

[0049] Without being bound by theory, when the color forming compound is selected to be an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, the inventors of the present invention believe that the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, promotes the formation of color, and thus the formation of a mark or image, on the plastic article via thermal decomposition of the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof. Thus, in the context of the present invention, when the color forming compound is an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, it will be appreciated by those skilled in the art that the processing conditions used for the formation of the plastic article may be below the thermal decomposition temperature of the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, such that the color forming compound does not prematurely form color during the formation of the plastic article and inhibit the subsequent formation of a mark or image on the formed plastic article. Thermal decomposition of the polyvalent metal or oxyanion of an oxoacid and / or its hydrates occurs at 80-700°C, or 80-500°C, for example 100-500°C, for example 150-400°C, or even 200-300°C, or even around 250°C (decomposition temperature). The decomposition temperature of ammonium octamolybdate (AOM) is 275°C. Thus, when the polyvalent metal oxyanion of an oxoacid and / or its hydrates is selected as the color-forming compound, the plastic material used to form the plastic product can be selected, for example HDPE, LDPE and / or PP, so as to require a processing temperature lower than the decomposition temperature of the polyvalent metal or oxyanion of an oxoacid and / or its hydrate, i.e. the plastic material has a melting temperature lower than the decomposition temperature of the polyvalent metal or oxyanion of an oxoacid and / or its hydrate. When the color-forming compound is an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, preferably the plastic material used to form the plastic article is processed at a temperature below the thermal decomposition temperature (decomposition temperature) of the oxyanion of the polyvalent metal or oxoacid, and / or a hydrate thereof.When the color forming compound is an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, preferably the plastic material used to form the plastic product includes HDPE, LDPE, or PP, or a combination thereof. The color formed with the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, such as ammonium octamolybdate (AOM), can be black, dark gray, or gray, or a shade thereof, and the mark or image formed can be black, dark gray, or gray, or a shade thereof. It should be appreciated that if the processing of the plastic material used to form the plastic product is performed at a temperature higher than the thermal decomposition temperature of the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, the color forming compound will form a color during processing, and the plastic product as a whole will display a color. The same is true when the plastic material used to form the plastic product in which the oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof is incorporated is, for example, PET, r-PET, or PET-G. In some instances, this is preferred. Because the subsequent application of radiation to the plastic article having a "background" color, typically black, dark gray, or gray, via marking of the plastic article by techniques such as ablation, engraving, or foaming as discussed above, preferably using a laser source(s), lamp, or LED, achieves a distinct mark or image, typically a white mark or image, and thus the incorporation of the color-forming compound into the plastic article still achieves the formation of a distinct, recognizable mark or image. Preferably, when the color-forming compound is an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, the plastic material used to form the plastic article, and thus the plastic article, comprises HDPE, LDPE, and / or PP. More preferably, when the color-forming compound is an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof, e.g., ammonium octamolybdate (AOM), the plastic material comprises HDPE.

[0050] Without being bound by theory, when a diacetylene is selected as the color forming compound, the inventors of the present invention believe that the diacetylene promotes the formation of color, and thus the formation of a mark or image, on the plastic article via polymerization using different sources of radiation, as discussed in more detail below. The color formed by the diacetylene will depend on the diacetylene selected, but will typically be blue or red, or shades thereof, and the mark or image formed will typically be blue or red, or shades thereof.

[0051] Without being bound by theory, when a leuco dye is selected as the color forming compound, the inventors of the present invention believe that the leuco dye, through interaction with the acid generator, facilitates the formation of color, and thus the formation of a mark or image, on the plastic article. This is discussed in more detail below. The color formed by the leuco dye depends on the leuco dye selected. Leuco dyes that form a wide range of colors are widely available.

[0052] In the context of the present invention, the term "incorporated in" refers to the fact that the color forming compound is present and dispersed throughout within the plastic material or plastic material forming the plastic product. "Dispersed throughout" means that the color forming compound is distributed, preferably uniformly distributed, throughout the plastic material and thus the plastic product and is not present only in one part or area thereof, e.g., in the plastic product, merely in the part where the formation of a mark or image is desired.

[0053] Preferably, the color-forming compound is present in the plastic material, and thus in the plastic product, in solid form, and more preferably in particulate form, i.e., as particles of color-forming compound.Preferably, the color-forming compound is introduced in solid form as particles of color-forming compound into the plastic material during the formation of the plastic product.When the color-forming compound is an inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, kaolin, such as calcined kaolin, potassium bicarbonate, leuco dye, or polyvalent metal, or oxyanion of oxo acid, and / or its hydrate, preferably the color-forming compound is an inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, kaolin, such as calcined kaolin, potassium bicarbonate, or leuco dye.

[0054] Preferably, the plastic article of the present invention is formed from a plastic material having a colour forming compound incorporated therein and dispersed throughout. This is applicable to all aspects of the present invention which describe a plastic article.

[0055] As mentioned above, the color-forming compound can be selected from the following: inorganic hydrates, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate; potassium bicarbonate; oxyanions of polyvalent metals, or oxoacids, and / or hydrates thereof, such as ammonium octamolybdate (AOM); kaolins, such as calcined kaolin; leuco dyes; diacetylenes; or combinations thereof.

[0056] "Inorganic hydrate," as used herein, refers to a hydrate of an inorganic compound that has adsorbed or absorbed water and / or the associated water of hydration. Suitable inorganic hydrates include, but are not limited to: sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, and ammonium pentaborate octahydrate, or combinations thereof.

[0057] The color-forming compound may be an inorganic hydrate. Preferably, the inorganic hydrate may be selected from sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, and ammonium pentaborate octahydrate, or a combination thereof. Preferably, the inorganic hydrate is ammonium pentaborate tetrahydrate.

[0058] The color-forming compound may be sodium molybdate dihydrate. Sodium molybdate dihydrate (Na 2 MoO 4 2H 2 O) is designated by the CAS number 10102-40-6.

[0059] The color-forming compound may be ammonium pentaborate tetrahydrate. Ammonium pentaborate tetrahydrate ((NH 4 ) B 5 O 8 4H 2 O) is represented by CAS number 12046-04-7.

[0060] The color-forming compound may be ammonium pentaborate octahydrate. Ammonium pentaborate octahydrate ((NH 4 ) 2 B 10 O 16 8H 2 O) is represented by CAS number 12046-03-6.

[0061] The color-forming compound may be potassium bicarbonate. Potassium bicarbonate (KHCO 3 ) is designated by the CAS number 298-14-6.

[0062] The color-forming compound may be kaolin. Kaolin is an aluminum silicate clay mineral that is composed of alumina (AlO 6 ) octahedron, one of which is connected to the other octahedral sheet via an oxygen atom. 4) . Kaolin may be provided in calcined or uncalcined form, i.e., calcined kaolin or uncalcined (hydrated) kaolin. Calcined kaolin is designated CAS 92704-41-1. Uncalcined kaolin is designated CAS 1332-58-7. Calcined kaolin is subjected to a calcination process (heating / roasting / burning, usually at temperatures above 900°C) to remove the crystal-bound water. In the present invention, when kaolin is selected as the color-forming compound, calcined kaolin is preferably utilized.

[0063] The color-forming compound may be an oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof. The oxyanion of a polyvalent metal or oxoacid, and / or a hydrate thereof may be any suitable oxyanion (anion component) of a polyvalent metal present in combination with its cationic counterpart. The use of oxyanions of polyvalent metals in compositions is disclosed in U.S. Pat. No. 7,485,403, the contents of which are incorporated herein by reference. The anion component may be an inorganic metal oxyanion compound, such as molybdate, including dimolybdate, trimolybdate, hexamolybdate, heptamolybdate, octamolybdate and decamolybdate, tungstate, chromate, or a similar transition metal compound of inorganic metal oxyanion, which may also be in mixed oxidation states, with trace elements or any higher concentration ratio. Preferably, the associated cationic component is an alkali metal or alkaline earth metal or ammonium. One example of an oxyanion of a polyvalent metal is sodium molybdate. The preferred oxyanion of the polyvalent metal is an ammonium salt of an inorganic metal oxyanion compound, such as ammonium paratungstate (APT).Preferably, when the oxyanion of a polyvalent metal or oxoacid and / or its hydrate is selected as the color-forming compound, the oxyanion of the polyvalent metal or oxoacid and / or its hydrate is an ammonium salt of an oxyanion of a polyvalent metal, such as an ammonium salt of an oxyanion of molybdenum, more preferably ammonium octamolybdate (AOM).When the color-forming compound is AOM, the plastic material used to form the plastic product, and thus the plastic product, preferably comprises LDPE, HDPE and / or PP, preferably HDPE.

[0064] The color-forming compound may be a diacetylene, i.e. the compound contains a diacetylene moiety.

[0065] [ka] Includes.

[0066] Diacetylene compounds are well known to those skilled in the art as compounds capable of forming color. Upon exposure to radiation, diacetylene compounds usually polymerize and display color. Typical diacetylene compounds are disclosed for this purpose in WO2012 / 114121, the contents of which are incorporated herein by reference. Suitable examples are also taught in WO2009 / 093028, WO2010 / 001171, WO2010 / 029329, and WO2013 / 068729, the contents of which are incorporated herein by reference. Known methods of synthesis of diacetylene compounds include the formation of reactive acid chlorides and then adding amines or alcohols, or the formation of anhydrous mixtures and then reacting with amines or alcohols.

[0067] Diacetylenic compounds are usually capable of displaying multiple colors. Radiation, such as UV radiation, can usually be applied to affect the formation of a first color by the diacetylenic compound. Near infrared (NIR) or infrared (IR) radiation can then be applied to effect the formation of a second color by the diacetylenic compound. Thus, a mark or image can be formed on the product that displays the first color, the second color, or both the first and second colors.

[0068] It will be appreciated by those skilled in the art that, prior to the formation of the first color, certain diacetylenic compounds (e.g., diacetylenic compounds of formulas (I) and (II)) may need to be preferentially "activated" (i.e., rendered capable of forming color) prior to exposure to radiation (e.g., UV radiation) that affects the formation of the first color of the diacetylenic compound. This allows the diacetylenic compound to be capable of forming color. "Activation" is the process that allows the diacetylenic compound to form color, i.e., change from an unactivated form (not capable of forming color) to an activated form (capable of forming color). If required, activation can be accelerated by exposing the diacetylenic compound to an activation temperature. It will be appreciated by those skilled in the art that this activation may be performed prior to exposure to radiation to form the first color, or alternatively, the diacetylenic compound may be activated during this exposure. Preferably, activation is performed prior to exposure to a stimulus that effects the formation of the first color. If activation is performed prior to exposure to radiation to form the first color, the activation temperature is a temperature between ambient temperature (10-35°C) and the decomposition temperature of the diacetylenic compound. The activation temperature may be 40-150°C. Preferably, the activation temperature is 60-140°C, for example, 70-140°C. In the context of the present invention, without being bound by theory, the inventors of the present invention believe that the diacetylenic compound is exposed to the activation temperature during processing and manufacturing of the plastic product of the present invention or during application of radiation to form the first initial color.

[0069] When the color-forming compound of the present invention is a diacetylene, it has the following formula (I):

[0070] [ka] [In the formula, x is 2 to 12, preferably 2 to 10, and L is a compound represented by the formula:

[0071] [ka] and amides having the formula:

[0072] [ka] and preferably L is selected from esters having the formula

[0073] [ka] and Q is an amide having the formula 1~20 Alkyl groups and C 3~18 cycloalkyl groups, preferably Q is selected from cyclopropyl and -(CH 2 ) y -CH 3 A linear alkyl chain, y is selected from 1 to 20, preferably 5 to 19, more preferably 5 to 17, T is hydrogen, C 1~20 Alkyl groups, and -(CH 2 ) x -LQ, where x, L and Q are as defined above, preferably T is selected from hydrogen, -(CH 2 ) y -(CH 3 ) a straight alkyl chain, where y is as defined above, and -(CH 2 ) x -LQ, where x, L and Q are as defined above.

[0074] The diacetylene compounds of formula (I) may be either symmetrical or asymmetrical, i.e., T is -(CH 2 ) x -LQ, where the values ​​of x, L and Q are the same on the other side of the diacetylene moiety (symmetrical), or T is hydrogen, C 1~20 Alkyl group or -(CH 2 ) x -LQ, where it will be appreciated by those skilled in the art that the values ​​of x, L and Q are not the same on either side of the diacetylene moiety (asymmetric). Preferably, T is -(CH 2 ) x-LQ, where the values ​​of x, L and Q are the same on both sides of the diacetylene moiety, and thus the diacetylene compound of formula (I) is symmetrical.

[0075] In the present invention, when diacetylene is selected as the color-forming compound, the color-forming compound is preferably represented by the following formula (II):

[0076] [ka] [In the formula, x is 2 to 12, preferably 2 to 10; Q is cyclopropyl or -(CH 2 ) y (CH 3 ) a straight alkyl chain, wherein y is selected from 1 to 20, preferably 5 to 19, and more preferably 5 to 17. Examples of suitable diacetylene compounds include, but are not limited to, N1,N22-dioctadecyldocosa-10,12-diynediamide, N1,N22-dihexadecyldocosa-10-12-diynediamide, N1,N22-ditetradecyldocosa-10,12-diynediamide, N1,N22-didodecyldocosa-10,12-diynediamide, N1,N22-didecyldocosa-10,12-diynediamide, N1,N22-dioctyldocosa-10,12-diynediamide, N1,N22-dihexyldocosa-10,12-diynediamide, N1,N22-dicyclopropyldocosa-10,12-diynediamide. When diacetylene is selected as the color-forming compound, the diacetylene is more preferably selected from N1,N22-dioctadecyldocosa-10,12-diynediamide, N1,N22-dihexadecyldocosa-10,12-diynediamide, N1,N22-ditetradecyldocosa-10,12-diynediamide, N1,N22-didodecyldocosa-10,12-diynediamide, and N1,N22-dicyclopropyldocosa-10,12-diynediamide, more preferably N1,N22-didodecyldocosa-10,12-diynediamide.

[0077] It is surprising and advantageous that diacetylenes can be utilized as color-forming compounds in the present invention.It is surprising that the high temperature processing conditions for forming the plastic product in which the leuco dye is incorporated do not cause the leuco dye to form or decompose.Furthermore, it is surprising that after the formation of the plastic product in which the leuco dye is incorporated, the leuco dye does not form color due to ambient light, but only forms color when the plastic product is applied with specific radiation, preferably with laser source(s), lamp or LED.

[0078] The color-forming compound may be a leuco dye. Leuco dyes are well known to those skilled in the art as compounds capable of forming color. Examples of suitable leuco dyes are contained in WO 2015 / 015200 and WO 2013 / 068729, the contents of which are incorporated herein by reference. Examples of suitable leuco dyes include, but are not limited to: spirooxazines, naphthopyrans, phthalides, fluorans, triarylmethanes, benzoxazines, quinazolines, spiropyrans, quinones, tetrazolium salts, thiazines, phenazines and oxazines, some of which are disclosed in WO 2006 / 108745, the contents of which are incorporated herein by reference.

[0079] Suitable sources of leuco dyes include, but are not limited to, Yamada Chemical Company Limited, Chameleon Speciality Chemicals Limited, and Connect Chemicals.

[0080] In the present invention, when a leuco dye is selected as the color-forming compound, the leuco dye can be selected from the following: 2-anilino-3-diethylamino-6-methylfluoran, 2-anilino-6-dibutylamino-3-methylfluoran, 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]phthalide, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, 6'-(diethylamino)phenylphthalide, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] ... N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]-benzeneamine, and 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-2'-carboxylic acid ethyl ester, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one, 2'-(dibenzylamino)-6'-(diethylamino)fluoran, N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]-benzeneamine, and 6'-(diethylamino) )-2'-[(dimethylphenyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 2'-anilino-6'-[ethyl(p-tolyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one (CAS number 59129-79-2), 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] (CAS number 67707-04-4), 6'-(diethylamino)-3-oxo- Spiro[isobenzofuran-1(3H),9'-(9H)xanthene]-2' carboxylic acid ethyl ester (CAS number 154306-60-2), and 2'-(dibenzylamino)-6'-(diethylamino)fluoran (CAS number 34372-72-0), 2'-anilino-6'-(dibutylamino)-3'-methyl-3H-spiro[2-benzofuran-1,9'-xanthene]-3-one (CAS number 89331-94-2), 6'-(diethylamino)-3'-methyl-2'-(phenylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one (CAS number 29512-49-0), 2-anilino-6'-[ethyl(p-toyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one (CAS number 59129-79-2), Blue 3-CVL 6-(dimethylamino)-3,3-bis-[4-(dimethylamino)phenyl)phthalide (CAS number 1522-42-7), Blue 4 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] (CAS number 67707-04-4), Red-5 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide (CAS number 50292-95-0), Orange-6 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-2'-carboxylic acid ethyl ester (CAS number 154306-60-2), Blue-8 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furo[3,4-b]pyri Din-5(7H)-one (CAS number 87563-89-1), Green-9 2'-(dibenzylamino)-6'-(diethylamino)fluoran (CAS number 34372-72-0), Yellow-10 N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]-benzenamine (CAS number 144190-25-0), Black-15 6'-(diethylamino)-2'-[(dimethylphenyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]- 3-one (CAS number 36431-22-8), keto acid-14-(N,N-diethylamino)-2-hydroxy-2'-carboxybenzophenone (CAS number 5809-23-4), keto acid-24-(N,N-dibutylamino)-2-hydroxy-2'-carboxybenzophenone (CAS number 54574-82-2), 2-anilino-3-diethylamino-6-methylfluoran, 2-anilino-6-dibutylamino-3-methylfluoran, 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]phthalide, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline], 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-2'-carboxylic acid ethyl ester, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one, 2'-(dibenzylamino)-6'-(diethylamino)fluoran, N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl 6'-(diethylamino)-2'-[(dimethylphenyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] (CAS number 67707-04-4), 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-(9H)xanthene]-2' carboxylic acid ethyl ester (CAS number 154306-60-2), and 2'-(dibenzylamino)-6'-(diethylamino)fluoran (CAS number 34372-72-0).

[0081] In the present invention, when a leuco dye is selected as the color-forming compound, the leuco dye is preferably 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]phthalide, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one, 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, N,N-Dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]-benzenamine, 6'-(diethylamino)-2'-[(dimethylphenyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 2'-anilino-6'-[ethyl(p-tolyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3 -one (CAS number 59129-79-2), 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] (CAS number 67707-04-4), 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-(9H)xanthene]-2'carboxylic acid ethyl ester (CAS number 154306-60-2), 2'-anilino-6'-(dibutylamino)-3 It can be selected from 6'-methyl-3H-spiro[2-benzofuran-1,9'-xanthene]-3-one (CAS number 89331-94-2), 6'-(diethylamino)-3'-methyl-2'-(phenylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one (CAS number 29512-49-0) and 2'-(dibenzylamino)-6'-(diethylamino)fluoran (CAS number 34372-72-0). More preferably, when a leuco dye is selected as the color-forming compound, the leuco dye is Blue 3-CVL 6-(dimethylamino)-3,3-bis-[4-(dimethylamino)phenyl)phthalide (CAS number 1522-42-7).

[0082] When the color forming compound is a leuco dye, the plastic material or plastic product in which the color forming compound is incorporated also incorporates an acid generator. Without being bound by theory, the inventors of the present invention believe that the acid generator and the leuco dye interact to achieve color formation. The acid generator is present in the composition to promote a change in pH upon application of radiation through the generation of an acid. This acid generation promotes color formation by the leuco dye. By "acid" is meant any molecular entity or chemical species capable of donating a hydrogen (proton) or forming a covalent bond with an electron pair. Suitable acid generators include any suitable commercially available or chemically synthesizable acid generator. Suitable acid generators include, but are not limited to, ammonium sulfate. Preferably, the acid generator is ammonium sulfate. It will be understood by those skilled in the art that the choice of acid generator will depend on the particular leuco dye utilized.

[0083] It is surprising and advantageous that leuco dyes can act as color forming compounds in the present invention. As mentioned above, color formation occurs for the leuco dye through interaction with the acid generator. Typically, when subjected to high temperature conditions, e.g., high temperature processing and manufacturing conditions utilized in forming the plastic articles of the present invention, both the leuco dye and the known acid generator enter the same phase (melt) and react to form color. However, in the context of the present invention, premature color formation by the leuco dye can be avoided through the selection of leuco dyes and acid generators with different melting temperatures, as well as by selecting the processing temperature for the formation of the plastic article (which typically depends on the melting temperature of the plastic material) to be lower than at least one of the melting temperatures of the leuco dye and acid generator. Typically, the leuco dye can have a melting temperature of 80-220°C, e.g., 100-220°C, or even 160-210°C. Typically, the acid generator can have a melting / decomposition temperature of 100-270°C, e.g., 110-250°C. Preferably, avoidance of premature color formation by the leuco dye is facilitated through the use of ammonium sulfate as a thermal acid generator. Ammonium sulfate has a thermal decomposition / melting temperature of around 235° C. Therefore, during high temperature processing conditions, the ammonium sulfate does not melt / thermally decompose and thus the acid generator is not present in the same phase as the leuco dye. This occurs only upon application of certain radiation, thus allowing the leuco dye to form color and form a mark or image.

[0084] The plastic product or plastic material may contain 0.2-30 wt. % of the acid generator, where "wt. %" means the weight of the acid generator relative to the total weight of the acid generator, color forming compound and plastic product or material, including any additive(s) incorporated into the plastic material / plastic material used to form the plastic product, and, if present, any carrier or other component of a "liquid concentrate or masterbatch" or any component of a solid masterbatch used to introduce particles of the color forming compound into the plastic material / plastic material used to form the plastic product, and, if present, any NIR absorber.

[0085] As discussed below, the color-forming compound, and if present, the acid generator and / or NIR absorber (discussed below), can be introduced into the plastic material to form the plastic product of the present invention with a liquid concentrate or masterbatch or a solid masterbatch. In such an example, it is recognized that the plastic product formed from said plastic material can further include a carrier or other additional ingredients used to form the liquid concentrate or masterbatch or solid masterbatch, as discussed in more detail below. The use of liquid concentrates or masterbatches or solid masterbatches to introduce ingredients such as additives into plastic materials is well known in the art, for example, for colorants.

[0086] After formation of the plastic article, the color forming compound can be present in the plastic article of the present invention in any suitable amount. It should be appreciated that this amount is the amount of color forming compound present in the plastic article of the present invention prior to the application of radiation to the plastic article. Similarly, the color forming compound can be used in any amount in forming the plastic article of the present invention. Preferably, the color forming compound is present in the plastic article in an amount of less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. By "% by weight" herein is meant the weight of the color forming compound relative to the total weight of the plastic article. The plastic article includes the color-forming compound; and the plastic material from which the plastic article is formed, including any additive(s) incorporated within the plastic material (discussed in more detail herein); and, if present, any NIR absorber and / or acid generator; or any carrier or other component of a "liquid concentrate or masterbatch" or "solid masterbatch" used to introduce the color-forming compound into the plastic material (discussed in more detail herein).

[0087] Advantageously, less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as less than 0.1-4% by weight, such as less than 4% by weight, such as less than 0.1-3% by weight, or less than 2% by weight, such as less than 0.1-1% by weight, of the color forming compound may be used in forming the plastic article of the present invention, and the color forming compound may be present in the plastic article in an amount of less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as less than 0.1-4% by weight, such as less than 4% by weight, such as less than 0.1-3% by weight, or less than 2% by weight, such as less than 0.1-1% by weight, such that a clear, recognizable mark or image may be effectively formed. The incorporation of the color forming compound in such an amount for effective mark or image formation is advantageous, since it is not believed that this amount will negatively affect the recyclability of the plastic article of the present invention and their performance as packaging for a wide variety of dry and wet items. In addition, the amounts do not negatively impact requirements for direct contact with plastic products, such as standards for direct contact with food, and thus it is believed that these amounts can meet the standards required during the storage, transportation and distribution of a wide variety of consumable products.

[0088] The amount of color-forming compound present in the plastic article can be calculated by the amount of color-forming compound used to form the plastic article, which in turn can be the amount of color-forming compound in the plastic material in which the color-forming compound is incorporated that is used to form the plastic article.

[0089] Thus, the amount of color forming compound in a plastic product can be quantified by the amount of color forming compound used to form the plastic product. This may be the amount of color forming compound present in the plastic material used to form the plastic product (the plastic material in which the color forming compound is incorporated). Thus, the plastic material used to form the plastic product can have less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. In other words, the color forming compound can be present in the plastic material in which the color forming compound is incorporated that is used to form the plastic product in an amount of less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. By "wt %" herein is meant the weight of the color forming compound relative to the total weight of the color forming compound and the plastic material, including any additive(s) incorporated therein, and, if present, any carriers or other components of the "liquid concentrate or masterbatch" or "solid masterbatch" used to introduce the particles of the color forming compound into the plastic material, and any NIR absorbers and / or acid generators.

[0090] Without being bound by theory, when sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate are selected as the color-forming compound, the inventors of the present invention believe that the plastic product of the present invention may contain trace amounts of sodium molybdate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, respectively, in dehydrated form after production. This may be prior to radiation application using laser source(s), lamps or LEDs. Sodium molybdate in dehydrated form may be sodium molybdate monohydrate (Na 2 MoO 4 .H2 O) and anhydrous sodium molybdate (Na 2 MoO 4 ;CAS No. 7631-95-0). Dehydrated forms of ammonium pentaborate tetrahydrate include anhydrous ammonium pentaborate (CAS No. 12007-89-5) and diammonium decaborate (ammonium borate). Dehydrated forms of ammonium pentaborate tetrahydrate include anhydrous ammonium pentaborate tetrahydrate, ammonium pentaborate (CAS No. 12007-89-5) and diammonium decaborate (ammonium borate).

[0091] The inventors of the present invention consider that the color-forming compound is preferably present in the plastic product in solid form, more preferably in particulate form, i.e. as particles of the color-forming compound. Preferably, the plastic product of the present invention is formed of a plastic material in which the color-forming compound is incorporated, and the color-forming compound is present in solid form. More preferably, the plastic product of the present invention is formed of a plastic material in which the particles of the color-forming compound are incorporated. For example, when the color-forming compound is an inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, kaolin, such as calcined kaolin, potassium bicarbonate, leuco dye, or an oxyanion of a polyvalent metal, or an oxo acid, and / or a hydrate thereof, the same is preferably true when the color-forming compound is an inorganic hydrate, such as sodium molybdate dihydrate or ammonium pentaborate tetrahydrate or ammonium pentaborate octahydrate, kaolin, such as calcined kaolin, potassium bicarbonate, or a leuco dye.

[0092] The plastic product of the present invention or the plastic material used to form the plastic product may further incorporate a NIR absorber therein. Preferably, when used, the NIR absorber is present in solid form in the plastic material and thus in the plastic product. The NIR absorber may be present in particulate form as particles of NIR absorber. The NIR absorber is introduced in solid form as particles of NIR absorber into the plastic material during the formation of the plastic product. Alternatively, when used, the NIR absorber and color-forming compound, and if required, the acid generator, can be present in particulate form as combined particles of the NIR absorber and color-forming compound and, if present, the acid generator. By "combined particles" is meant that, rather than a particulate mixture of particles of NIR absorber and particles of color-forming compound (and, if required, particles of acid generator) being present in the plastic material or plastic product, the NIR absorber and color-forming compound and, if present, the acid generator are integrated together in individual particles.

[0093] Preferably, when the colour forming compound is a leuco dye as detailed herein, the colour forming compound, acid generator and NIR absorber are present as combined particles in the plastic material or plastic article.

[0094] The NIR absorber may be any suitable compound capable of absorbing near infrared or infrared radiation, preferably near infrared radiation. More than one NIR absorber may be present. It is to be appreciated that, if present, the NIR absorber enhances the absorption by the plastic article of near infrared or infrared radiation, preferably near infrared radiation, applied to the plastic article. Suitable examples of NIR absorbers include, but are not limited to, inorganic copper salts, such as copper(II) hydroxyphosphate; organic NIR dyes and pigments, such as N,N,N',N'-tetrakis(4-dibutylaminophenyl)-p-benzoquinone bis(iminium hexafluoro-antimonate); non-stoichiometric, reduced or doped inorganic compounds, such as reduced indium tin oxide, reduced zinc oxide, reduced tungsten oxide, reduced and doped tungsten oxide, such as inorganic compounds of the formula MxWyOz, where M is 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 at least one element selected from the group consisting of 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 satisfying 0.001≦x / y≦1; and 2.2≦z / y≦3.0), 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 sulfonate (PEDOT); and combinations thereof. The NIR absorber may be an inorganic copper salt, such as hydroxy copper (II) phosphate.

[0095] The NIR absorber can be any suitable D 50 It can have a particle size distribution value. 50 The particle size distribution is the mean or average value of the particle size distribution, i.e. the particle diameter at 50% in the cumulative distribution. Preferably, the D 50The particle size distribution value is 5 μm or less. More preferably, the D 50 The particle size distribution is 0.5 to 3 μm, and most preferably 1 to 2 μm. 50 Particle size distribution is measured using a Malvern Mastersizer according to ISO standard 13320:2009.

[0096] When present, the NIR absorber may be an inorganic copper salt, such as copper(II) hydroxyphosphate; and non-stoichiometric, reduced or doped inorganic compounds, such as reduced indium tin oxide, reduced zinc oxide, reduced tungsten oxide, reduced and doped tungsten oxide, such as inorganic compounds of the formula MxWyOz, where M is 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, I and ammonium, W is tungsten and O is oxygen, satisfying 0.001≦x / y≦1; and 2.2≦z / y≦3.0), reduced antimony tin oxide, or doped metal oxides, such as aluminum doped zinc oxide (AZO) and fluorine doped tin oxide (FTO).

[0097] The plastic product or plastic material may comprise 0.01-20 wt.% of the NIR absorber, e.g., 0.01-15 wt.%, or 0.01-10 wt.%, or 0.01-5 wt.%, e.g., 0.01-3 wt.% of the NIR absorber, where "wt.%" means the weight of the NIR absorber relative to the total weight of the NIR absorber, the color forming compound and the plastic product or material, including any additive(s) incorporated in the plastic material / plastic material used to form the plastic product, and any carrier or other component of a "liquid concentrate or masterbatch" or "solid masterbatch" used to introduce particles of the color forming compound into the plastic material / plastic material used to form the plastic product, if present, and any acid generator, if present.

[0098] The plastic product of the present invention may be transparent, translucent or opaque. It should be appreciated that this is different from when a mark or image is formed. The plastic product may have haze and / or opacity. This may be specific to the plastic material utilized to form the plastic product. Preferably, the plastic product of the present invention has a small amount of haze and / or opacity. If the plastic material used to form the plastic product, and thus the plastic product, is not transparent, the plastic product may be translucent or opaque. It should be appreciated that any haze and / or opacity may result from the type of plastic material used to form the plastic product of the present invention.

[0099] The plastic products of the present invention may be colored or colorless. If colored, it should be recognized that this is the color of the "background" of the plastic product, i.e., the color of the plastic product itself is not the color of the mark or image. Any suitable method can be used to provide a colored plastic product, i.e., a plastic product having a "background" color. For example, the plastic material used to form the plastic product can have a distinctive color, or shade thereof, which is displayed by the resulting plastic product. Alternatively, for example, if a NIR absorber is present in the plastic material and thus the plastic product, the color of the NIR absorber can be displayed by the plastic product. In addition, as discussed below, the "background" color can be introduced into the plastic product during the compounding of the plastic product using a colored masterbatch or colored ingredients to form a solid masterbatch or liquid concentrate or masterbatch. Still further, the interior of the plastic product can also be dyed to impart a "colored" background to the plastic product prior to the application of radiation to the plastic product to form the mark or image, as exemplified herein.

[0100] "Color", as used herein in relation to both the color-forming compounds and the "background" color of the plastic product, includes all colors, shades, tints and hues of the visible light color spectrum, i.e., red, orange, yellow, blue, green and violet, in addition to the colors, shades, tints and hues of black, brown, white, turquoise, purple, pink, cyan, magenta and all mixtures thereof. All first, second, third, fourth and fifth colors are encompassed. In the context of the present invention, the term can also be used to describe different shades of each color of the visible light color spectrum, in addition to black, brown, white, e.g., off-white, turquoise, purple, pink, cyan and magenta. Furthermore, in the context of the present invention, when the plastic product is a multi-layer plastic product, it may be advantageous to color additional layers, e.g., barrier layers.

[0101] In order to make the mark or image recognizable and distinct against the plastic article, the plastic article may be colorless, may have a "background" color different from the mark or image being formed, or may have a "background" color the same color as the mark or image but less opaque, thereby forming a contrasting, distinct and recognizable image.

[0102] To incorporate the color forming compound into a plastic article, the color forming compound is introduced into the plastic material used to form the plastic article prior to production of the plastic article, as well as any NIR absorbers and / or acid generators, if present.

[0103] According to a second aspect of the present invention there is provided a plastic product formed of a plastic material having a colour forming compound incorporated therein, the plastic product being produced by contacting the colour forming compound with the plastic material to form a plastic material having the colour forming compound incorporated therein, and forming the plastic material having the colour forming compound incorporated therein into the plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0104] According to a third aspect of the present invention there is provided a plastic product formed from a plastic material having a colour forming compound incorporated therein, the plastic product being produced by forming the plastic material having the colour forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic packaging body.

[0105] According to a fourth aspect of the present invention there is provided a method of producing a plastic article formed of a plastic material having a colour forming compound incorporated therein, the method comprising the steps of contacting the colour forming compound with the plastic material to form a plastic material having the colour forming compound incorporated therein, and forming the plastic material having particles of the colour forming compound incorporated therein into the plastic article.

[0106] According to a fifth aspect of the present invention there is provided a method of producing a plastic article formed from a plastic material having a colour forming compound incorporated therein, the method comprising forming the plastic material having the colour forming compound incorporated therein into a plastic article.

[0107] According to a sixth aspect of the present invention there is provided the use of a colour forming compound in the production of a plastic material having the colour forming compound incorporated therein, or in the production of a plastic article having the colour forming compound incorporated therein.

[0108] According to a seventh aspect of the present invention, (i) a color-forming compound; and (ii) Plastic materials A mixture comprising:

[0109] All features of the second to seventh aspects of the invention detailed above, including all preferred and optional features detailed below, are applicable to all other aspects described herein. Similarly, all features of all other aspects described herein are applicable to the second to seventh aspects of the invention detailed above, including the preferred and optional features of each aspect.

[0110] The colour forming compounds used to produce the plastic article according to the present invention may be in particulate form, which may have any particle size suitable for incorporation into the plastic material used to form the plastic article.

[0111] The color-forming compound utilized in the second to seventh aspects of the present invention can be present in the form of a powder, as particles of the color-forming compound.

[0112] The particles of the color-forming compound may have a volume-weighted average particle diameter D[4,3] of 0.1 to 40 μm, for example, 0.5 to 20 μm. Preferably, the particles of the color-forming compound have a volume-weighted average particle diameter D[4,3] of 1 to 15 μm, for example, 1 to 10 μm, or 1 to 7 μm. Most preferably, the particles of the color-forming compound have a volume-weighted average particle diameter D[4,3] of 3 to 7 μm.

[0113] Such volume weighted average particle size D[4,3] allows for uniform incorporation of the color forming compound into the final plastic article, which promotes efficient formation of a mark or image on the plastic article of the present invention.

[0114] Particles of the color-forming compound having such a volume weighted average particle size D[4,3] can be produced by any suitable method. If required, the color-forming compound can be dry ground or milled to form a fine powder of particles of the color-forming compound having the volume weighted average particle size D[4,3] detailed above. Apparatus suitable for such grinding or milling are well known to those skilled in the art and include, for example, the "opposed jet mill" apparatus used by British Rema.

[0115] Methods for measuring the volume weighted mean particle size D[4,3] are well known to those skilled in the art and include measurements using a Malvern Mastersizer™ particle size analyzer manufactured by Malvern Instruments under ISO standard ISO 13320:2020.

[0116] The particles of the color-forming compound may have an area-weighted average particle size D[3,2] of 0.5 to 4.0 μm, preferably 1.0 to 4.0 μm, or more preferably 1.6 to 4.0 μm.

[0117] Methods for measuring the area weighted mean particle size D[3,2] are well known to those skilled in the art and include measurements using a Malvern Mastersizer™ particle size analyzer manufactured by Malvern Instruments under ISO standard ISO 13320:2020.

[0118] Without being bound by theory, the inventors of the present invention expect that when the color-forming compound is present in the plastic product of the present invention in solid form, preferably in particulate form, i.e. as particles of color-forming compound, the particles of color-forming compound present in the plastic product may also have the volume weighted average particle size D[4,3], surface area and / or area weighted average particle size D[3,2] discussed above, even if no additional grinding or milling is performed during the production of the plastic product using particles of color-forming compound having the above volume weighted average particle size D[4,3], surface area and / or area weighted average particle size D[3,2].

[0119] The plastic material that can be utilized to generate the plastic product is as described above in connection with the first aspect of the invention. As discussed above, it is to be appreciated that the plastic material can further comprise additives. These additives may already be part of the plastic material utilized to generate the plastic product (e.g., incorporated into the plastic material, e.g., incorporated into plastic pellets) or may be introduced into the plastic material during the generation of the plastic product.

[0120] In forming the plastic product of the present invention, the color-forming compound and, if present, the NIR absorber and / or acid generator are contacted with the plastic material. The color-forming compound and, if present, the NIR absorber and / or acid generator are thus introduced into the plastic material. A plastic material is produced having the color-forming compound and, if present, the NIR absorber and / or acid generator incorporated therein. The color-forming compound is preferably in the form of particles of the color-forming compound. The same is true for the NIR absorber and / or acid generator, if utilized. The plastic material may be melted upon contacting the color-forming compound and, if present, the NIR absorber and / or acid generator with the plastic material. Preferably, the plastic material is melted upon contacting the color-forming compound and, if present, the NIR absorber and / or acid generator with the plastic material.

[0121] The term "molten" in relation to a plastic material means that the plastic material is capable of flowing. To be in the molten state, the plastic material is heated at or above its melting (melting) temperature so that it can be processed and manufactured into a plastic product. Typically, the plastic material is heated to a temperature in the range of 50-350°C, e.g., 100-300°C, i.e., the processing temperature. It will be appreciated that this temperature will vary depending on the plastic material used and its melting temperature, as well as the type of plastic product being formed. For example, PET has a melting temperature of 260°C, whereas HDPE is around 130°C.

[0122] Preferably, the plastic material may be in any form, such as a powder, pellets, prills or granules, prior to utilization in the process described herein to form the plastic product of the present invention. The molten plastic material may be obtained via heating of the plastic powder, pellets, prills or granules.

[0123] The color-forming compound and, if present, the NIR absorber and / or the acid generator can be contacted with the plastic material in several different ways.For example, the color-forming compound and, if present, the NIR absorber and / or the acid generator particles (as dry powder), or the combination particles of the color-forming compound and the NIR absorber and, if present, the acid generator (as dry powder), can be contacted and combined with the plastic material (preferably in the form of plastic powder, pellet, prill or granule), and then the mixture is heated, so that the plastic material melts and the color-forming compound and, if present, the NIR absorber and / or the acid generator are formed in the plastic material.Alternatively, the color-forming compound and, if present, the NIR absorber and / or the acid generator particles (as dry powder), or the combination particles of the color-forming compound and the NIR absorber and, if present, the acid generator (as dry powder) can be contacted and combined with the molten plastic material. Preferably, the particles of the color-forming compound and, if present, the NIR absorber and / or the acid generator, or the combined particles of the color-forming compound and the NIR absorber and, if present, the acid generator, can be contacted and combined with the molten plastic material. In either case, the resulting combination of the molten plastic material with the color-forming compound and, if present, the NIR absorber and / or the acid generator incorporated through the molten plastic material can be optionally cooled and granulated or pelletized to form a "solid masterbatch". This can be done using a twin-screw extruder compounding device. The "solid masterbatch" can then be heated to a molten state and used to form a plastic product, or can be optionally contacted with additional plastic material and then heated, thus completely molten, and used to form a plastic product. It should be recognized that the plastic material used to form the "solid masterbatch" can be the same or different from that used to form the plastic product.Typically, the plastic material used to form the "solid masterbatch" may be different from that used to form the plastic product if the plastic product is a PET plastic product. If the plastic material used to form the "solid masterbatch" is different from that used to form the plastic product, it is clear to one skilled in the art that the plastic material is a plastic material that is compatible with the plastic material used to form the product. For example, for a PET product, the plastic material used to form the solid masterbatch may be PET-G or based thereon, and PET-G is a plastic material that is compatible with PET. "Compatible," as used herein in connection with a solid masterbatch, means that the plastic material of the solid masterbatch fully integrates into or forms part of the polymer matrix of the plastic material used to form the plastic product.

[0124] It should also be appreciated that the solid masterbatch may optionally include other additional components. The other additional components of the solid masterbatch may include one or more additives, such as plasticizers and / or flow additives. The solid masterbatch may also be colored by using a colored masterbatch in the formulation of the solid masterbatch to provide color to the solid masterbatch. The colored masterbatch used is one that is compatible with the plastic material used to form the plastic product. It should also be appreciated that any additional components are compatible with the plastic material used to form the plastic product.

[0125] Alternatively, the particles of the color-forming compound and, if present, the NIR absorber and / or the acid generator (as a dry powder), or the combined particles of the color-forming compound and the NIR absorber and, if present, the acid generator (as a dry powder), may be incorporated into a "liquid concentrate or master batch", which is then contacted with, preferably poured into, the molten plastic material. Preferably, the particles of the color-forming compound and, if present, the NIR absorber and / or the acid generator, or the combined particles of the color-forming compound and the NIR absorber and, if present, the acid generator, are incorporated into a "liquid concentrate or master batch", which is then contacted with, preferably poured into, the molten plastic material. By "liquid concentrate or master batch" is meant a liquid composition comprising particles of the color-forming compound and, if present, the NIR absorber and / or the acid generator suspended in a carrier. Typically, the particles of the color-forming compound and, if present, the NIR absorber and / or the acid generator (as dry powder), or the combined particles of the color-forming compound, the NIR absorber, and, if present, the acid generator, are mixed in the carrier at room temperature. Typically, the carrier is lipophilic. Typically, the carrier is water-insoluble and therefore hydrophobic. The carrier may be a non-aqueous carrier, an oil-based carrier, including a biological oil-based carrier, a mineral oil-based carrier, or a petroleum-based carrier. The carrier may include a mixture or combination of petroleum hydrocarbons, mineral oil, organic solvent-based medium, liquid polymers, such as polybutene, liquid monomers, such as liquid acrylic monomers, liquid oligomers, or hydrocarbons. The carrier, and thus the liquid composition, is compatible with the plastic material used to form the plastic product. "Compatible," as used herein in connection with the liquid masterbatch, means that the liquid masterbatch fully integrates into or forms part of the polymer matrix of the plastic material used to form the plastic product. It should be recognized that the liquid composition may optionally include other additional ingredients. Other additional components of the liquid composition may include one or more additives, such as thermal stabilizers, antioxidants, surfactants, and / or dispersants.A color component may be included to promote a "background" color. The "liquid concentrate or masterbatch" may be a commercially available product. Such products are well known to those skilled in the art. It should be recognized that in some cases, further milling or grinding of the color forming compound and, if present, the NIR absorber and / or acid generator particles may occur during the formation of the "liquid concentrate or masterbatch."

[0126] The use of "solid masterbatches" or "liquid concentrates or masterbatches" in the formation of plastic materials and plastic products is known in the art. For example, it is known to utilize such masterbatches to overcome manufacturing problems that arise when introducing additives into polymers or copolymers used in the formation of plastic materials and plastic products. A typical method to overcome these problems includes using a concentrate of the required additive(s) in a carrier. See, for example, Plastics Additives Handbook (Hans Zweifel, Hanser, Munich, 6. Edition, 2009).

[0127] When a "solid masterbatch" or "liquid concentrate or masterbatch" is utilized, the masterbatch may comprise 5-90% by weight of the color forming compound, such as 9-90% by weight, such as 25-90% by weight, such as 25-80% by weight, or 50-75% by weight, such as 40-70% by weight of the color forming compound. Weight percent refers to the weight of the color forming compound relative to the total weight of the "solid masterbatch" or "liquid concentrate or masterbatch", i.e. the weight of the color forming compound relative to the total weight of the color forming compound, NIR absorber and / or acid generator, if present, carrier, and any other components of the "liquid concentrate or masterbatch", or the weight of the color forming compound relative to the total weight of the plastic material of the "solid masterbatch", including the color forming compound, NIR absorber and / or acid generator, if present, and any other components, if present.

[0128] When a "solid masterbatch" or "liquid concentrate or masterbatch" is utilized, the masterbatch may comprise 0.4 to 20 wt. %, e.g., 0.5 to 10 wt. % of the NIR absorber. Wt. % refers to the weight of the NIR absorber relative to the total weight of the "solid masterbatch" or "liquid concentrate or masterbatch", i.e., the weight of the NIR absorber relative to the total weight of the color forming compound, NIR absorber and acid generator, if present, carrier, and any other components of the "liquid concentrate or masterbatch", or the weight of the color forming compound relative to the total weight of the plastic material of the "solid masterbatch" including the color forming compound, NIR absorber, and acid generator, if present, and any other components, if present.

[0129] When a "solid masterbatch" or "liquid concentrate or masterbatch" is utilized, the masterbatch may comprise 2% to 90% by weight of acid generator, preferably 2 to 60% by weight, e.g., 2 to 55% by weight of acid generator. Weight percent refers to the weight of NIR absorber relative to the total weight of the "solid masterbatch" or "liquid concentrate or masterbatch", i.e., the weight of NIR absorber relative to the total weight of the color forming compound, NIR absorber and acid generator, if present, carrier, and any other components of the "liquid concentrate or masterbatch", or the weight of sodium, color forming compound relative to the total weight of the plastic material of the "solid masterbatch" including the color forming compound, NIR absorber, and acid generator, if present, and any other components, if present.

[0130] It should be appreciated that the use of "solid masterbatches" or "liquid concentrates or masterbatches" to introduce ingredients, such as additives, into plastic materials is well known in the art.

[0131] When a "solid masterbatch" or "liquid concentrate or masterbatch" is utilized, the masterbatch containing the color forming compound can be used in an amount of less than 20% by weight, e.g., less than 12% by weight, or less than 6% by weight, e.g., less than 4% by weight, or less than 2% by weight, relative to the plastic material. The "weight percent" is the weight of the masterbatch relative to the total weight of the masterbatch (including any carrier or other components, if present, or NIR absorber and / or acid generator, if present) and the plastic material. The plastic material includes any additive(s) incorporated therein. Thus, the plastic material can be used in an amount of 80% by weight or more, e.g., 88% by weight or more.

[0132] The colour forming compound is introduced into the plastic material by contacting it, i.e. the colour forming compound is used in the process according to the second to sixth aspects of the invention in an amount of preferably less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. "% by weight" refers to the weight of colour forming compound and, if present, NIR absorber and / or acid generator, and colour forming compound relative to the total weight of the plastic material. This plastic material includes any additive(s) incorporated into the plastic material, and, if present, any carrier or other component of a "liquid concentrate or masterbatch" or any component of a "solid masterbatch" (used to introduce the colour forming compound and, if present, NIR absorber and / or acid generator into the plastic material).

[0133] It should be appreciated that in the context of the seventh aspect of the invention, the plastic material is preferably molten. It should therefore be appreciated that the color-forming compound, and if present, the NIR absorber and / or acid generator, can be incorporated into the plastic material at the time the plastic material is melted. The color-forming compound may be present as particles of the color-forming compound. Preferably, the color-forming compound is present as particles of the color-forming compound. It should also be appreciated that the color-forming compound, and if present, the NIR absorber and / or acid generator, may be present in the mixture as part of a "liquid concentrate or masterbatch" or "solid masterbatch" as discussed herein. It should instead be appreciated that for the mixture of the seventh aspect of the invention, the color-forming compound may be present as particles of the color-forming compound, for example as a dry powder, and the plastic material is present as a powder, pellets, granules or prills.

[0134] The colour forming compound is preferably present in the mixture according to the seventh aspect of the invention in an amount of less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. "% by weight" refers to the weight of colour forming compound relative to the total weight of the mixture, i.e. colour forming compound and, if present, NIR absorber and / or acid generator, and plastic material. This plastic material includes any additive(s) incorporated in the plastic material, and, if present, any carrier or other component of a "liquid concentrate or masterbatch" or any component of a "solid masterbatch" (used to introduce the colour forming compound and, if present, NIR absorber and / or acid generator into the plastic material). Preferably, the plastic material of the seventh aspect of the invention is molten. Preferably, the plastic material of the seventh aspect of the invention is molten and the colour forming compound is a particle of the colour forming compound.

[0135] Thus, the present invention further relates to a plastic material, preferably a molten plastic material, having a colour forming compound incorporated therein.

[0136] The present invention also relates to a method of forming a plastic material having a colour forming compound incorporated therein, the method comprising the step of contacting a colour forming compound with the plastic material.

[0137] All features of these further aspects of the invention, including all preferred and optional features detailed below, are applicable to all other aspects described herein Similarly, all features of all other aspects described herein are applicable to these further aspects of the invention, including the preferred and optional features of each aspect.

[0138] Typically, the color-forming compound may be present in the plastic material in an amount of less than 15% by weight, such as less than 12% by weight, such as less than 10% by weight, such as less than 5% by weight, such as 0.1-4% by weight, such as less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, such as 0.1-1% by weight. Here, "% by weight" refers to the weight of the color-forming compound, and, if present, the NIR absorber and / or acid generator, and the color-forming compound relative to the total weight of the plastic material. This plastic material includes any additive(s) incorporated therein, and, if present, any carrier or other component of a "liquid concentrate or masterbatch" or any component of a solid masterbatch (used to introduce the color-forming compound, and, if present, the NIR absorber and / or acid generator into the plastic material).

[0139] The colour forming compound, and, if present, the NIR absorber and / or acid generator, are contacted with a plastic material and incorporated into the plastic material to form the plastic article of the present invention.

[0140] It should be appreciated that the color-forming compound and, if present, the NIR absorber and / or acid generator can be contacted with and incorporated into the plastic material in the same process required for the formation of the plastic product of the present invention. This may be in the same equipment or machine. For example, if the plastic product is formed by injection molding, the color-forming compound and, if present, the NIR absorber and / or acid generator can be contacted with and incorporated into the plastic material in an equipment or machine in a first step, for example melt blended and then injected into a mold. Alternatively, the color-forming compound and, if present, the NIR absorber and / or acid generator can be contacted with the plastic material before processing to form the plastic product of the present invention.

[0141] It should further be appreciated that the plastic material itself may be compounded in the same equipment or machine in which the formation of the plastic product of the present invention takes place. Such methods are well known in the art. For example, the plastic material may be compounded in a first step via the addition of additives. This may be before, during, or after contact with the color-forming compound and, if present, the NIR absorber and / or acid generator. The additives may be introduced as solids, as solids dissolved in a liquid, or as liquids, including in liquid or solid concentrates or masterbatches. Alternatively, the additives may be introduced into the plastic material prior to its addition to the equipment or machine in which the formation of the plastic product of the present invention takes place. Such methods are well known in the art.

[0142] Typically, the plastic materials having the color forming compounds incorporated therein are formed into plastic articles by thermal processing. These processes for forming the plastic articles of the present invention typically include high temperature processing conditions. Typical conditions for thermal processing include temperatures in the range of 50-350°C, e.g., 100-300°C, and pressures of 1000 kPa to 4000 kPa. As discussed above, it should be recognized that the particular temperatures used during processing will depend on the plastic material utilized and its melting (melting) temperature, as well as the type of plastic article being formed.

[0143] Suitable processes for forming the plastic products of the present invention are well known to those skilled in the art. These include thermal processing methods such as extrusion, extrusion blow molding, 3D printing, compression molding, rotational molding, thermoforming, injection molding, and blow molding, or combinations thereof. Suitable equipment for these thermal processing methods is well known to those skilled in the art.

[0144] When the plastic product being produced is a plastic preform, the plastic preform is typically produced by injection molding. Typical conditions for injection molding include temperatures of 200-300° C. Suitable equipment for accomplishing such injection molding includes Aaburg injection molding systems.

[0145] If the plastic product produced is a plastic bottle, and known techniques for producing plastic bottles, such as blow molding, are used, another manner in which the plastic bottle may be produced is by injection molding to form a plastic preform, and subsequently blow molding the plastic preform to form a plastic bottle. Typical conditions of injection molding and suitable equipment are as described above. Typical conditions for blow molding include temperatures of 100-200°C, such as temperatures of 100-150°C, and pressures of 1000-4000 kPa. Suitable equipment for accomplishing such blow molding includes blow molding equipment available from Parker Plastic Machinery.

[0146] It will be appreciated that in the production of plastic bottles via plastic preforms, the production of the plastic preform and the subsequent plastic bottles may occur on the same machine or equipment, usually in a continuous process, or each step (the formation of the plastic preform, and the subsequent formation of the plastic bottle from the plastic preform) may occur separately, usually on separate equipment. Suitable equipment for accomplishing the one or two step process includes equipment available from Parker Plastic Machinery.

[0147] Thus, according to a further aspect of the invention, there is provided a method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed of a plastic material having a colour forming compound incorporated therein, the method comprising the steps of contacting the colour forming compound with the plastic material to form the plastic material having the colour forming compound incorporated therein, and forming the plastic preform from the plastic material having the colour forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle. Preferably, the plastic bottle is formed

[0148] According to a further aspect of the invention there is provided a method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed from a plastic material having a colour forming compound incorporated therein, the method comprising forming the plastic preform from the plastic material having the colour forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle. Preferably a plastic bottle is formed.

[0149] All features of these further aspects of the invention detailed above are applicable to all other aspects described herein, including all preferred and optional features detailed below. Similarly, all features of all other aspects described herein are applicable to these further aspects of the invention detailed above, including the preferred and optional features of each aspect.

[0150] In the present invention, it is surprising and advantageous that a distinct and recognizable mark or image can be formed on a plastic article after exposure of the color forming compound to the high temperature processing and manufacturing conditions required during the formation of the plastic article. It is surprising that the color forming compound does not form a color upon exposure to the high temperature processing and manufacturing conditions that would prevent the subsequent formation of the mark(s) or image(s) by application of certain radiation to the plastic article.

[0151] The incorporation of color forming compounds into the plastic article of the present invention facilitates the display of a mark(s) or image(s) by the plastic article.

[0152] Thus, according to an eighth aspect of the present invention there is provided a plastic article displaying a mark or image, wherein the plastic article is formed from a plastic material having a colour forming compound incorporated therein, and the plastic article is a plastic preform or a plastic package.

[0153] According to a ninth aspect of the present invention there is provided a plastic product displaying a mark or image, said product being obtainable by applying radiation to a plastic product having a colour forming compound incorporated therein such that the mark or image is formed where the radiation is applied to the plastic product, and wherein the plastic product is a plastic preform or a plastic packaging product.

[0154] According to a tenth aspect of the present invention there is provided a method of forming a mark or image on a plastic article, the method comprising the step of exposing the plastic article to radiation to form the mark or image where the radiation is applied, the plastic article being formed of a material having a colour forming compound incorporated therein, and the plastic article being a plastic preform or a plastic packaging body.

[0155] According to a further aspect of the present invention there is provided the use of a colour forming compound in the formation of a mark or image on a plastic article formed from a plastic material having the colour forming compound incorporated therein.

[0156] All features of the eighth to tenth and further aspects of the invention detailed above are applicable to all other aspects described herein, including all preferred and optional features detailed below. Similarly, all features of all other aspects described herein are applicable to the eighth to tenth and further aspects of the invention detailed above, including the preferred and optional features of each aspect.

[0157] It will be appreciated that plastic products according to the first, second and third aspects of the invention may be utilised to form plastic products displaying images according to the eighth and ninth aspects of the invention.

[0158] The marks or images formed by the application of radiation to the plastic articles of the present invention are clearly visible to the human eye and / or machine readable.

[0159] It should be appreciated that in the context of the present invention, the mark or image may be formed on the surface of the plastic article or may be incorporated into the plastic article by color forming compounds incorporated within the plastic article.

[0160] The mark(s) or image(s) of the present invention formed by the application of radiation to a plastic article is particularly distinct, recognizable and clearly visible to the human eye.

[0161] Radiation can be applied to a plastic article to selectively promote the formation of color at defined locations to form a desired image, i.e., to form variable information. The application of radiation is controlled and specific. A human-readable and / or machine-readable image is formed, usually in only one portion or area of ​​the plastic article.

[0162] As discussed above, in the context of the present invention, it will be appreciated that the color of the mark or image formed by the application of radiation will contrast with the portion or portions of the plastic article to which no radiation has been applied.

[0163] The term "mark or image" as used herein includes, but is not limited to, logos, marks, such as text and words, graphics, diagrams, pictures, symbols, codes, such as linear barcodes, 2D Datamatrix, QR codes, Digimarc codes, and text, such as alphanumeric and symbol-based. In the context of the present invention, it is recognized that it is the manipulation of color-forming compounds that facilitates the formation of a mark or image on and within a plastic product. The images formed are human-readable and / or machine-readable and can be used for coding and marking, tagging, tracking and tracing, and later customization or personalization purposes. The marks or images formed are typically marks or images used to display variable information.

[0164] In the context of the present invention, radiation is applied to the plastic product after its formation. This application can occur immediately after formation (once the plastic product has cooled to ambient temperature) or at a later time, for example after storage or transportation. Radiation can be applied to the plastic product when it is empty, or alternatively when it is filled or partially filled with contents.

[0165] As used herein, "radiation" and like 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) radiation, beta (β) radiation, neutron radiation and plasma. The wavelength bands in the different regions of the electromagnetic spectrum are known to those of skill in the art.

[0166] The radiation may be selected from ultraviolet (UV) radiation having a wavelength of 10-400 nm, visible radiation having a wavelength of 400-700 nm, infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700-1600 nm. Preferably, the radiation is selected from UV radiation having a wavelength of 10-400 nm, IR radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700-1600 nm. More preferably, the radiation is selected from UV radiation having a wavelength of 250-370 or 405 nm, infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO2). 2 Laser radiation), infrared radiation having a wavelength between 700 nm and 1 mm, and near infrared (NIR) radiation having a wavelength between 700 and 1600 nm. More preferably, the radiation is infrared (IR) radiation (CO) having a wavelength between 9300, 9600, 10200 or 10600 nm. 2Laser radiation), infrared radiation having a wavelength of 700 nm to 1 mm, and near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example 950 to 1100 nm. More preferably, the radiation is infrared (IR) radiation (CO) having a wavelength of 10600 nm. 2 laser) and near-infrared (NIR) radiation having a wavelength of 700 to 1600, e.g., 950 to 1100 nm.

[0167] It will be appreciated by those skilled in the art that the radiation selected is required to cause the color-forming compounds to form a clear, discernible image.

[0168] When the color-forming compound is sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, ammonium pentaborate octahydrate, or potassium bicarbonate, the radiation is preferably infrared (IR) radiation having a wavelength of 700 nm to 1 mm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 (applied using a laser).

[0169] When the colour forming compound is kaolin, for example calcined kaolin, the radiation is preferably UV radiation having a wavelength of 10 to 400 nm, for example 250 to 370 or 405 nm, infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, preferably infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 laser) and near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, more preferably infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2For calcined kaolin, the radiation is selected from UV radiation having a wavelength of 10 to 400 nm, e.g., 250 to 370 or 405 nm, or infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, e.g., infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 Application of near infrared (NIR) radiation having a wavelength of 700-1600 nm, e.g., NIR radiation having a wavelength of 950-1100 nm, promotes the formation of a black, gray, or brown mark or image, or shades thereof.

[0170] When the colour forming compound is kaolin, for example calcined kaolin, preferably the radiation is infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 The radiation is selected from near infrared (NIR) radiation having a wavelength of 700-1600 nm, or even 950-1100 nm, and the plastic product is formed of a plastic material including PET, r-PET, or PET-G.

[0171] When the color-forming compound is sodium molybdate dihydrate, preferably the radiation is infrared (IR) radiation having a wavelength of 700 nm to 1 mm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 Laser applied), and preferably the plastic product is formed of a plastic material including PET, r-PET or PET-G.

[0172] When the color-forming compound is a diacetylene, preferably the radiation is UV radiation having a wavelength of 10 to 400 nm, e.g., 250 to 370 or 405 nm. As discussed above, the UV radiation may be followed by infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, e.g., infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 The radiation may be near-infrared (NIR) radiation having a wavelength of 700-1600 nm, or even 950-1100 nm, as applied using a laser.

[0173] When the color-forming compound is a leuco dye, preferably the radiation is infrared (IR) radiation having a wavelength of 700 nm to 1 mm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 (applied using a laser).

[0174] As mentioned above, it should be appreciated that when a NIR absorber is also present in a plastic product or plastic material according to the invention, the NIR absorber aids in the absorption of NIR or IR radiation by the plastic product. Thus, when a NIR absorber is present in a plastic product, it absorbs infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example IR radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, or even near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, or even infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2Laser irradiation (applied using a laser) may be used conventionally or additionally to form a mark or image on the plastic article of the present invention. For example, sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, ammonium pentaborate octahydrate or potassium bicarbonate are color-forming compounds incorporated into the plastic article, and if a NIR absorber is also present, the radiation may be infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 Laser (applied using a laser) and near-infrared (NIR) radiation having a wavelength of 700 to 1600 nm, e.g., 950 to 1100 nm.

[0175] Radiation can be applied to the plastic article by any suitable means. Suitable means include application of radiation by laser source(s), lamps or LEDs. Preferably, radiation is applied from laser source(s). It will be understood by those skilled in the art that radiation can be applied to localized locations of an area or portion of the plastic article to selectively promote the formation of color, and thus the formation of a mark or image, at these localized locations. These localized locations may overlap with each other. It will also be understood by those skilled in the art that radiation is applied for an appropriate amount of time required to promote the formation of a mark or image. Typically, the time required to deliver sufficient radiation depends on the means and application method used to apply radiation. For example, in one embodiment, radiation can be applied for less than 30 seconds, for example, less than 20 seconds or less than 15 seconds, or even less than 10 or less than 5 seconds.

[0176] When applied using a laser source(s), the dose of radiation applied will depend on the time the radiation is applied, the power (wattage) of the means used to apply the radiation, and thus the fluence (amount of energy delivered per unit area) delivered by the laser source(s), e.g., J / cm. 2 It will be appreciated that the fluence can be controlled by modifying the fluence. It will be appreciated by those skilled in the art that this can affect the density / opacity, i.e., "effectiveness", of the mark or image formed. For example, if a laser source(s) is used to apply the radiation, the fluence (amount of energy delivered per unit area) can affect the density / opacity, i.e., "effectiveness", of the mark or image formed. In the context of the present invention, the fluence depends on the power (wattage) of the means used to apply the radiation, and the time that the radiation is applied to a particular location on the part of the plastic article, which power and time can be controlled by the scanning speed of the laser or the speed of the moving stage. These two variables can be modified to change the fluence. If the fluence is low (e.g., lower power and / or shorter exposure time), the mark or image formed will have a lower density / lower opacity, and if the fluence is high (e.g., higher power and / or longer exposure time), the mark or image formed will have a higher density / higher opacity. In the context of the present invention, fluence values ​​range from 0.01 to 100 J / cm 2 , e.g., 0.1 to 50 J / cm 2 , and even 0.5 to 25 J / cm 2 The range may be:

[0177] Without being bound by theory, the present inventors believe that when radiation is applied by a laser source(s), the concentrated energy of the radiation promotes the formation of the mark(s) or image(s).

[0178] In the present invention, the opacity or "effectiveness" of a mark or image, other than being visually discernible, i.e., human-readable and / or machine-readable, can be demonstrated by measuring the opacity value. This is particularly relevant when the color of the mark or image formed is white or a shade thereof. As used herein, opacity is a measure of the impenetrability of a plastic product to light, in this example, visible light. Opacity is expressed as a percentage from transparent (0%) to opaque (100%). The percentage is a measure of the amount of light that does not pass through the plastic product, i.e., at 0% opacity, 0% of the light does not pass through the plastic product, so the plastic product is completely transparent, and at 100% opacity, 100% of the light does not pass through the plastic product, so the plastic product is completely opaque. In the context of the present invention, the opacity values ​​of the areas of the plastic product to which radiation has been applied (mark or image) and the areas of the plastic product to which radiation has not been applied (background) can be measured to demonstrate the effective formation of a recognizable human-readable and / or machine-readable mark or image. In the context of the present invention, it will be appreciated by those skilled in the art that the opacity of the mark or image is usually greater than the opacity of the background, thus forming a recognizable human-readable and / or machine-readable mark or image. The greater the difference between the opacity value of the mark or image and the opacity value of the background, the more distinct and recognizable the mark or image will be. The background of the plastic product, i.e., the part(s) of the plastic product to which radiation has not been applied, may have an opacity of 20% or less, such as 15% or less, preferably 10% or less, or even 5% or less. Furthermore, the area of ​​the plastic product location to which radiation has been applied and the mark or image formed thereon may have an opacity of 40% or more, such as 45% or more, preferably 50% or more, or even 60% or more, such as 70% or more. It will be appreciated that the higher the opacity value of the mark image, the more distinct and recognizable the mark or image will be formed.Thus, a high opacity value represents a valid mark or image formation. Alternatively, if the opacity of the background and the mark or image are not contrasted sufficiently, a clear and recognizable mark or image may still be formed if the background and the mark or image are contrasting in color. In the context of the present invention, opacity measurements may be made in accordance with ASTM standard ASTM D589-97 using the opacity function of a Techkon SpectroDens spectrophotometer, where the marked or imaged (mark or image) and unmarked or unimaged (background) areas of the plastic article may be measured relative to black and white standards, respectively. It should be appreciated that for such measurements, a section of the plastic article must usually be cut out.

[0179] In the present invention, besides being visually discernible, i.e. human-readable and / or machine-readable, the density of the mark or image can be demonstrated by measuring the ODB, ODC, ODM and ODY values. This measurement is particularly useful when the mark or image formed is black, red, magenta, cyan or yellow, or shades thereof. In the context of the present invention, the mark or image is a contrasting image. By "contrasting image" is meant that the mark or image formed is clear and easily recognizable. Preferably, the mark or image formed has an ODB, ODC, ODM or ODY absolute value of 0.5 or more, such as 0.7 or more, or even 0.8 or more, such as 0.9 or more, or even 1.0 or more. An ODB, ODC, ODM or ODY absolute value of 0.5 or more results in a clear and easily recognizable contrasting image. The ODB (optical density black) absolute value measures the optical density of the black color of the mark or image. This is useful when the color of the mark or image formed is black, or shades thereof. ODM (Optical Density Magenta) Absolute measures the optical density of the magenta color of the image. This is useful when the color of the mark or image being formed is red or a shade thereof. ODC (Optical Density Cyan) Absolute measures the optical density of the cyan color of the image. This is useful when the color of the mark or image being formed is blue or a shade thereof. ODY (Optical Density Yellow) Absolute measures the optical density of the yellow color of the image. This is useful when the color of the mark or image being formed is red or a shade thereof. In the context of ODB, ODM, ODC and ODY values, the higher the value, the darker the color is formed. ODB, ODM, ODC and ODY Absolute values ​​quantify the optical density on a color scale from low to high, and measurements of ODB, ODM, ODC and ODY can be made using standard equipment densitometers and X-Rite eXact or SpectroEye or TechKon SpectroDens spectrophotometers.The measured optical density difference, ΔODB, ΔODM, ΔODC or ΔODY, between the mark or image (ODB, ODM, ODC or ODY absolute value) and the "background", i.e., the portion(s) of the plastic article that has not been exposed to radiation (background ODB, ODM, ODC or ODY) may also be measured.

[0180] In the present invention, besides being visually discernible, i.e. human-readable and / or machine-readable, the density of the mark or image can be determined by measuring the ΔE value using an X-Rite eXact or SpectroEye spectrophotometer. ΔE can be calculated from L*a*b* measurements (CIE L*a*b* color system, where L* stands for lightness, a* stands for red / green value, and b* stands for yellow / blue value). ΔE is a standard mathematical calculation that allows the quantification of the visual perception of the difference between two colors, i.e. between the mark or image and the "background". The calculation is given below:

[0181]

number

[0182] Preferably, radiation is applied to the plastic article at defined locations to form desired marks or images at those defined locations. Essentially, by application of radiation, preferably from a laser source(s), lamp or LED, color is formed in the areas of the plastic article where radiation was applied. A human-readable and / or machine-readable mark or image is thus produced. It is the color-forming compound that allows the mark or image to be formed on and in the plastic article.

[0183] All of the features contained herein can be combined with any of the above aspects in any combination.

[0184] All references herein to specific chemical compounds are intended to cover the compound itself, as well as, where appropriate, its derivatives, hydrates, solvates, complexes, isomers and tautomers.

[0185] For a better understanding of the present invention, and to show how this embodiment may be put into practice, reference is now made, by way of example, to the following experimental data. EXAMPLES

[0186] Sodium molybdate dihydrate (CAS number: 10102-40-6, EC number: 231-551-7) was purchased from ABSCO Limited, UK. Sodium molybdate dihydrate is a granular crystalline solid with a typical average particle size >149 μm (>100 mesh).

[0187] Ammonium pentaborate tetrahydrate (CAS number 12046-04-7) was purchased from Merck Sigma Aldrich Limited, UK. Ammonium pentaborate tetrahydrate is a crystalline solid in powder form.

[0188] Low density polyethylene (LDPE) pellets Exxon Mobil 600BA were purchased from Colourmaster Limited, UK.

[0189] Ammonium octamolybdate (AOM) (CAS number: 12411-64-2) was purchased. Ammonium octamolybdate has a D of 1 to 3 microns. 50 It is a solid in powder form having the following structure:

[0190] Calcined kaolin (CAS number: 92704-41-1) was purchased from Merck Sigma Aldrich Limited, UK. Calcined kaolin is a solid in powder form.

[0191] Polyethylene terephthalate (PET) powder PR12747 was purchased from Colourmaster Limited, UK.

[0192] Blue indium tin oxide (ITO) (CAS number: 1312-43-2 / 18282-10-5) was purchased from Keeling & Walker Limited, UK. ITO is a crystalline solid in powder form.

[0193] High density polyethylene (HDPE) pellets, Sibur Natural HD85612IM, were purchased from Colourmaster Limited, UK.

[0194] Polypropylene (PP) pellets, SABIC PP PHC31 00900, were purchased from Colourmaster Limited, UK.

[0195] Polyethylene terephthalate (PET) compatible liquid masterbatch was provided by Riverdale Global Limited, UK.

[0196] Polypropylene (PP) compatible liquid masterbatch provided by Riverdale Global Limited, UK

[0197] High density polyethylene (HDPE) compatible liquid masterbatch was provided by Riverdale Global Limited, UK.

[0198] Ammonium sulfate (CAS number 7783-20-2) was purchased from Merck Sigma Aldrich Limited, UK. Ammonium sulfate is a solid in powder form.

[0199] 6-Dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide (CAS number: 1552-42-7) is purchased from Sigma Aldrich. This leuco dye is a solid in powder form.

[0200] Canary Yellow OM1700 Masterbatch was purchased from Colourmaster Limited, UK.

[0201] Ultra Blue OM5179 Masterbatch was purchased from Colourmaster Limited, UK.

[0202] RIT Dye Daffodil Yellow 2118 was purchased from Dyeing for Change, UK.

[0203] [Example 1] General Method for Forming and Imaging Plastic Products Sodium molybdate dihydrate was milled using an "opposed jet mill" operated by British REMA to achieve particles, powder form, with a volume weighted mean particle size D[4,3] of 3-7 μm. The milled sodium molybdate dihydrate particles, in powder form, were incorporated into a carrier to form a "liquid concentrate or masterbatch". This "liquid concentrate or masterbatch" was contacted (injected) into and incorporated into molten polyethylene terephthalate (PET) as a plastic material, such that the sodium molybdate dihydrate particles were completely and uniformly dispersed throughout the polyethylene terephthalate (PET).

[0204] Molten polyethylene terephthalate (PET) having sodium molybdate dihydrate particles incorporated therein was injection molded to produce a bottle preform (plastic product of the present invention) made of polyethylene terephthalate (PET) having sodium molybdate dihydrate incorporated therein. The bottle preform was then blow molded to produce a plastic bottle. Thus, a plastic bottle (plastic product of the present invention) made of polyethylene terephthalate (PET) having sodium molybdate dihydrate incorporated therein was formed. Videojet VJ-3320 SHC-60 CO2 Using a laser with a wavelength of 10.6 μm and lens configurations of, for example, 64, 95 or 127 mm, infrared (IR) radiation was applied to defined locations on a portion of a plastic bottle to form a white image at those defined locations.

[0205] [Example 2] 500 g of ammonium pentaborate tetrahydrate was combined with 4,500 g of LDPE pellets and tumble blended to form a mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140° C. (zone 1), 200° C. (zone 5) and 190° C. (die) and the mixture was melt extruded to form a first masterbatch containing 10 wt. % ammonium pentaborate tetrahydrate. This first masterbatch was cooled using a chilled water bath and then pelletized using an Accrapal 750 / 3 Free-standing Strand Dry Cut Pelletizer. The pellets were collected and dried using a Drymaster device for several hours to form a solid masterbatch containing 10 wt. % ammonium pentaborate tetrahydrate.

[0206] Pellets of the solid masterbatch were loaded into the feed hopper of an Arburg Allrounder 420°C injection molding machine to produce plastic plaques having ammonium pentaborate tetrahydrate incorporated therein. The plastic plaques had an off-white haze / cloudiness characteristic of LDPE (background color). The present inventors believe that the formation of plastic plaques via injection molding substantially replicates the manufacturing and processing conditions required during the production of plastic articles according to the present invention.

[0207] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque, creating a clear and distinct white mark or image at the stereotactic location where the radiation was applied.

[0208] [Example 3] 500g of AOM was combined with 4,500g of LDPE pellets and tumble blended to form a mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140°C (zone 1), 200°C (zone 5) and 190°C (die) and the mixture was melt extruded to form a first masterbatch containing 10% by weight of AOM. A chilled water bath was used to cool the first masterbatch and then pelletized using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried using a Drymaster machine for several hours to form a solid masterbatch containing 10% by weight of ammonium octamolybdate.

[0209] [Example 3.1] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques with the AOM incorporated therein. The plastic plaques had an off-white haze / cloudiness characteristic of LDPE (the "background" color).

[0210] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a black mark or image.

[0211] [Example 3.2] 2 kg of the solid masterbatch containing 10 wt% AOM was processed with a 65:35 virgin HDPE:rHDPE mix of 24.7 kg of Marlex HHM 5502BN virgin HDPE and 13.3 kg of SIRENE HD E 80 PWP rHDPE (post-consumer recycled HDPE) to extrusion blow mold 500 mL tall Boston round (TBR) plastic bottles. The resulting plastic bottles contained 5 wt% of the solid masterbatch and 0.5 wt% AOM. The plastic bottles had an off-white haze / cloudiness typical of LDPE and HDPE (the "background" color).

[0212] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic bottles to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic bottles to create a black mark or image. A Coherent 355nm UV laser was used to apply UV radiation to plastic bottles to create a black mark or image.

[0213] [Example 4] 500 g of calcined kaolin was combined with 4,500 g of PET powder and tumble blended to form a mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 150° C. (zone 1), 220° C. (zone 6) and 200° C. (die) and the mixture was melt extruded to form a first masterbatch containing 10 wt. % calcined kaolin. A chilled water bath was used to cool the first masterbatch and then pelletized using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried using a Drymaster machine for several hours to form a solid masterbatch containing 10 wt. % calcined kaolin.

[0214] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques with the calcined kaolin incorporated therein. The plastic plaques had an off-white haze / cloudiness (the "background" color).

[0215] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic plaques to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic plaques to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to plastic bottles to create a white mark or image.

[0216] [Example 5] A Nutribullet electromechanical high speed blender was used to blend 475 g of ammonium pentaborate tetrahydrate and 25 g of ITO to produce a powder mixture. 500 g of the mixture was combined with 4,500 g of LDPE pellets and tumble blended to form a solid mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140° C. (zone 1), 200° C. (zone 5), and 190° C. (die) and the mixture was melt extruded to form a first masterbatch containing 10 wt. % of the mixed ammonium pentaborate tetrahydrate and ITO (9.5 wt. % ammonium pentaborate tetrahydrate and 0.5 wt. % ITO). A chilled water bath was used to cool the first masterbatch and then pelletized into granules using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried for several hours using a Drymaster apparatus to form a solid masterbatch containing 10 wt % mixed ammonium pentaborate tetrahydrate and ITO.

[0217] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques with ammonium pentaborate tetrahydrate and ITO incorporated therein. The plastic plaques had an off-white haze / cloudiness typical of LDPE with a blue hue / tint from the NIR absorber (the "background" color).

[0218] Videojet VJ-3320 CO 2 Lasers were used to apply IR radiation to plastic plaques to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic plaques to create a white mark or image.

[0219] [Examples 6 and 7] Example 5 was repeated, except that the LDPE pellets were replaced by HDPE pellets (Example 6) and PP pellets (Example 7), respectively. A white mark or image was produced.

[0220] [Example 8] A Nutribullet electromechanical high speed blender was used to blend 475g of AOM and 25g of ITO to produce a powder mixture. A mixture of 500g of AOM and ITO was combined with 4,500g of LDPE pellets and tumble blended to form a solid mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140°C (zone 1), 200°C (zone 5) and 190°C (die) and the mixture was melt extruded to form a first masterbatch containing 10% by weight of mixed AOM and ITO (9.5% by weight AOM and 0.5% by weight ITO). A chilled water bath was used to cool the first masterbatch and then pelletized into granules using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried for several hours using a Drymaster apparatus to form a solid masterbatch containing 10 wt % mixed AOM and ITO.

[0221] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques with the AOM and ITO incorporated therein. The plastic plaques had an off-white haze / cloudiness typical of LDPE with a blue hue / tint from the NIR absorber (the "background" color).

[0222] Videojet VJ-3320 CO 2A laser was used to apply IR radiation to a plastic plaque to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a black mark or image.

[0223] [Examples 9 and 10] Example 8 was repeated, except that HDPE (Example 9) or PP (Example 10) was used instead of the LDPE pellets. A black mark or image was produced.

[0224] [Example 11] A Nutribullet electromechanical high speed blender was used to blend 11.875 kg of AOM and 625 g of ITO to produce a powder mixture. 12.5 kg of the mixed AOM and ITO were combined with 12.5 kg of LDPE pellets and tumble blended to form a mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140° C. (zone 1), 200° C. (zone 5), and 190° C. (die) and the mixture was melt extruded to form a first masterbatch containing 50 wt. % of the mixed AOM and ITO (47.5 wt. % AOM and 2.5 wt. % ITO). A chilled water bath was used to cool the first masterbatch and then pelletized into granules using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried for several hours using a Drymaster apparatus to form a solid masterbatch containing 50% by weight of mixed AOM and ITO.

[0225] 2 kg pellets of the solid masterbatch were processed with 24.7 kg of Marlex HHM 5502BN virgin HDPE and 13.3 kg of SIRENE HD E 80 PWP rHDPE (post-consumer recycled HDPE) in a 65:35 solid HDPE mix (virgin HDPE:rHDPE) to produce 500 mL tall Boston round (TBR) bottles by extrusion blow molding. The resulting plastic bottles contained 5 wt% solid masterbatch and 2.5 wt% AOM and ITO (2.375 wt% AOM and 0.125 wt% ITO). The plastic bottles had an off-white haze / cloudiness typical of LDPE and HDPE with a blue hue / tint from the NIR absorber (the "background" color).

[0226] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic bottles to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic bottles to create a black mark or image. A Coherent 355nm UV laser was used to apply UV radiation to plastic bottles to create a black mark or image.

[0227] [Example 12] A Nutribullet electromechanical high speed blender was used to blend 450g of calcined kaolin and 50g of ITO to produce a mixture. 500g of the mixed calcined kaolin and ITO were combined with 4,500g of PET powder and tumble blended to form a mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 150°C (zone 1), 220°C (zone 6) and 200°C (die) and the mixture was melt extruded to form a first masterbatch containing 10% by weight of the mixed calcined kaolin and ITO (9% by weight of calcined kaolin and 1% by weight of ITO). A chilled water bath was used to cool the first masterbatch and then pelletized using an Accrapak 750 / 3 Free-standing Strand Dry Cut Pelletiser. The pellets were collected and dried for several hours using a Drymaster apparatus to form a solid masterbatch containing 10% by weight of mixed calcined kaolin and ITO.

[0228] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques containing calcined kaolin and ITO. The plastic plaques had an off-white haze / cloudiness with a blue tint / tinge from the NIR absorber (the "background" color).

[0229] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic plaques to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic plaques to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to plastic plaques to create a white mark or image.

[0230] [Example 13] 7.2 kg of calcined kaolin and 800 g of ITO were blended using a Nutribullet electromechanical high speed blender to produce a powder mixture. 8 kg of the mixed calcined kaolin and ITO were combined with 12 kg of PET powder and the mixture was melt extruded to form a first masterbatch containing 40 wt% calcined kaolin. A chilled water bath was used to cool the first masterbatch and then pelletized. The pellets were collected and dried to form a solid masterbatch containing 40 wt% of the mixed calcined kaolin and ITO (36 wt% calcined kaolin and 4 wt% ITO).

[0231] 2 kg of the solid masterbatch was processed with 42.0 kg of virgin PET and 22.6 kg of rPET (post-consumer recycled PET) in a 65:35 PET mix (virgin PET:rPET) to produce 500 mL tall Boston round (TBR) bottles by extrusion blow molding. The resulting plastic bottles contained 3 wt% of the solid masterbatch and 1.2 wt% of mixed calcined kaolin and ITO (1.08 wt% calcined kaolin and 0.12 wt% ITO). The plastic bottles had an off-white haze / cloudiness with a blue hue / tint from the NIR absorber (the "background" color).

[0232] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic bottles to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic bottles to create a black mark or image. A Coherent 355nm UV laser was used to apply UV radiation to plastic bottles to create a white mark or image.

[0233] [Example 14] A Nutribullet electromechanical high speed blender was used to blend 475 g of AOM and 25 g of ITO to produce a powder mixture. 500 g of the mixed AOM and ITO was combined with 214 g of the PET compatible liquid masterbatch to form a liquid masterbatch containing 70 wt% AOM and ITO (66.5 wt% AOM and 3.5 wt% ITO).

[0234] The liquid masterbatch was taken from the pellets and metered into molten PET using a Boy 22S injection molding machine to produce plastic plaques. The plastic plaques contained 0.7 wt% liquid masterbatch and 0.49 wt% mixed AOM and ITO (0.4655 wt% AOM and 0.0245 wt% ITO). The plastic plaques had a black / gray color (the "background" color).

[0235] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a white mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a white mark or image.

[0236] [Example 15] A Nutribullet electromechanical high speed blender was used to blend 475 g of AOM and 25 g of ITO to produce a powder mixture. 500 g of the mixed AOM and ITO was combined with 214 g of the PP compatible liquid masterbatch to form a liquid masterbatch containing 70 wt% AOM (66.5 wt% AOM and 3.5 wt% ITO).

[0237] The liquid masterbatch was taken from the pellets and metered into molten PP using a Boy 22S injection molding machine to produce a plastic plaque. The plastic plaque contained 0.7 wt% liquid masterbatch and 0.49 wt% mixed AOM and ITO (0.4655 wt% AOM and 0.0245 wt% ITO). The plastic plaque had an off-white color (the "background" color).

[0238] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to the plastic plaque to form a dark gray mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to the plastic plaque to form a gray mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to the plastic plaque to form a gray mark or image.

[0239] [Example 16] 450 g of calcined kaolin and 50 g of ITO were blended using a Nutribullet electromechanical high speed blender to produce a powder mixture. 500 g of the mixed calcined kaolin and ITO were combined with 214 g of the PET compatible liquid masterbatch to form a liquid masterbatch containing 70 wt% calcined kaolin (63 wt% calcined kaolin and 7 wt% ITO).

[0240] The liquid masterbatch was taken from the pellets and metered into molten PET using a Boy 22S injection molding machine to produce plastic plaques. The plastic plaques contained 0.7 wt% liquid masterbatch and 0.49 wt% mixed calcined kaolin and ITO (0.441 wt% AOM and 0.049 wt% ITO). The plastic plaques were colorless.

[0241] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic plaques to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic plaques to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to plastic plaques to create a white mark or image.

[0242] [Example 17] 475 g of ammonium pentaborate tetrahydrate and 25 g of ITO were blended using a Nutribullet electromechanical high speed blender to produce a powder mixture. 500 g of the mixed ammonium pentaborate tetrahydrate and ITO was combined with 214 g of a HDPE compatible liquid masterbatch containing 70 wt% ammonium pentaborate tetrahydrate and ITO.

[0243] 500 g of the liquid masterbatch was milled with recycling using an electromechanical Eiger Torrance bead mill with 1.5 mm yttria zirconia ceramic beads.

[0244] The milled liquid masterbatch was taken and metered from the pellets into molten HDPE using a Boy 22S injection molding machine to produce plastic plaques that had the off-white haze / cloudiness typical of HDPE with a blue tint / tint from the NIR absorber (the "background" color).

[0245] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque, creating a white mark or image.

[0246] [Example 18] Sodium molybdate dihydrate was milled using an "opposed jet mill" operated by British REMA to achieve particles with a powder morphology with a volume weighted mean particle size D[4,3] of 3-7 μm. 15 g of sodium molybdate dihydrate was mixed with 50 g of LDPE pellets to form plastic plaques using a CR Clarke Manual injection molding machine at 190 °C. The plastic plaques had an off-white haze / turbidity characteristic of LDPE.

[0247] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque, creating a white mark or image.

[0248] [Example 19] 3 g of diacetylene (N1,N22-didodecyldocosa-10,12-diynediamide) was mixed with 60 g of LDPE pellets and formed into a plastic plaque using a CR Clarke Manual injection molding machine at 200°C.

[0249] Using a UV 254 nm lamp, UV radiation was applied to one portion of the plastic plaque (the remaining portion was blocked from the UV radiation) to produce a blue mark or image.

[0250] [Example 20] Combined AOM and ITO particles were formed as follows: 500 mL of deionized water, 500 g of AOM, and a magnetic stirrer bar were added to a 2 L jug. The jug was placed on a stirrer hot plate with the temperature set to 60° C. and the stirrer speed set to 500 rpm. Once up to temperature, 25% ammonia solution was added to 250 g. The white opaque dispersion became a pale solution (more ammonia solution can be added if necessary). Once complete solubilization occurred, the stirrer bar was removed and the solution was mixed at 3000 rpm using a Silverson high shear mixer, taking care not to pull the beaker into the head of the mixer. 25 g of ITO was added to the AOM solution and mixed for 5 minutes or until dispersed. The beaker was removed from the Silverson and the stirrer bar was added again. The beaker was then placed back on the stirrer hot plate set to 500 rpm with no heat. 500 g of ethanol was added to quench the ammonia, causing the solids to precipitate out. The stirrer bar was removed using pliers. The mixture was cooled in a freezer until it was below 5°C. Excess solvent was decanted and an additional 500mL ethanol was added, then mixed in the Silverson at 3000 rpm for 5 minutes. The mixture was gravity filtered and the filter paper containing the wet solids was removed, placed in a borosilicate tray and dried in a vacuum oven set at 60°C (solids should be dried until free of moisture and ammonia). During the drying process, the solids formed large agglomerates. These were crushed using a nutribullet until a fine powder was formed.

[0251] 500 g of the combined AOM:ITO particles were combined with 4500 g of LDPE pellets and tumble blended to form a powdered pellet mixture. The solid mixture was poured into a Brabender feed hopper and slowly metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140° C. (zone 1), 200° C. (zone 5), and 190° C. (die). The mixture was melt extruded to form a first masterbatch containing 10% by weight of the combined AOM and ITO. The first masterbatch was cooled using a chilled water bath and then pelletized using an Accrapak 750 / 3 Free-standing Strand dry cut Pelletiser. The pellets were collected and then dried using a Drymaster machine for several hours to form a solid masterbatch containing 10% by weight of the combined AOM and ITO.

[0252] Pellets of the solid masterbatch were taken and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques containing the combined AOM and ITO. The plastic plaques had an off-white haze / cloudiness with a blue tint / tint from the NIR absorber (the "background" color).

[0253] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a black mark or image.

[0254] [Example 21] Combination particles of leuco dye, acid generator and ITO were formed as follows: 150g of leuco dye (6-dimethylamino-3,3-bis(4-dimethylaminophenyl)phthalide) was added to 1500g of acetone with magnetic stirring at 500 RPM. A heating element was set up to reach 30-40°C. Once the temperature of the solution reached 30°C, the leuco dye was completely dissolved and changed from a cloudy solution to a completely clear solution. 15g of ITO (ground) was then added to the sample while stirring by vortex. The sample was then subjected to high shear from a medium sized silverson mixer for up to 15 minutes after which 555g (sub-batch 1) of the solution mix was decanted into a separate container for further processing. The remaining 1110g of the solution mixture was allowed to remain for an additional 15 minutes after which a further 555g (sub-batch 2) of the solution mixture was decanted for further processing. Similarly, the last portion of the solution mixture, 555g (sub-batch 3), was allowed to remain for an additional 15 minutes of mixing. Sub-batch 1 was thus subjected to 15 minutes of silverson mixing, sub-batch 2 to 30 minutes of silverson mixing, and sub-batch 3 to a total of up to 45 minutes of silverson mixing, after which all were further processed in the crystallization stage. Concurrently, 840g of pre-weighed deionized water was cooled to <10°C in a freezer for up to 15-20 minutes. These last three steps were repeated for sub-batches 2 and 3. The crystals appeared light blue in color due to the presence of ITO. 555g of the decanted solution mixture of sub-batch 1 was placed under magnetic stirring at 500+ RPM again while cooling to ≦10°C using an ice-water bath cooling jacket. Once the 555g of solution mixture of sub-batch 1 was sufficiently cooled or below 10°C, pre-chilled ≦10°C deionized water was slowly added to the vortex until all the water had been added. The resulting crashed mixture was then allowed to settle in a 5°C refrigerator for up to 1 hour. After refrigeration, each sample was loaded onto a Buchner filter and suctioned until semi-dry crystals were obtained. The crystals were then placed in a vacuum oven and left over a 3-day weekend period, subject to full vacuum and a temperature of 60° C. After drying, the crystals were isolated.

[0255] 300g of ammonium sulfate was added to 1000g of deionized water under magnetic stirring at 500 RPM and 30°C. Once the ammonium sulfate was completely dissolved, 200g of isolated crystals formed from the leuco dye and ITO were added to the solution, which was transferred en bloc to a medium-sized silverson mixer. The sample was then subjected to high shear from the medium-sized silverson mixer for up to 15 minutes, after which 500g (sub-batch 1) of the solution mixer was decanted into another container for further processing. The remaining 1000g of the solution mixture was allowed to stand for an additional 15 minutes, after which a further 500g (sub-batch 2) of the solution mixture was decanted for further processing. Similarly, the last portion of the 500g (sub-batch 3) solution mixture was left for further mixing for 15 minutes. Sub-batch 1 was thus subjected to 15 minutes of silverson mixing, sub-batch 2 to 30 minutes of silverson mixing, and sub-batch 3 to a total of 45 minutes of silverson mixing, after which all were further processed in the crystallization stage. While on the silverson mixer, foaming and rheological changes were evident, resulting in stagnant flow during shear. To address this, a small amount of ethanol, approximately 90-100g, was added to the total solution mixture on the vortex and contact surface, which reduced the surface tension sufficiently to allow the foaming agent to disperse without causing crystal crushing. Once flow returned to the total solution mixture, 500g (sub-batch 1) was decanted into another metal jug and placed back under magnetic stirring at 500+ RPM while being cooled to ≦10°C using an ice-water bath cooling jacket. Simultaneously, 1170g of pre-weighed ethanol was cooled to <10°C in a freezer for up to 15-20 minutes. Once the 500 g solution mixture of sub-batch 1 had cooled sufficiently to below 10° C., pre-chilled ≦10° C. ethanol was slowly added to the vortex and all the water was added. The resulting crashed mixture was then allowed to settle in a 5° C. refrigerator for up to 1 hour. These last three steps were repeated for sub-batches 2 and 3. After refrigeration, each sample was suctioned through a Buchner filter and continued until semi-dry crystals were obtained.The crystals appeared light blue due to the presence of ITO in the encapsulation core. The crystals were then placed in a vacuum oven and left for a period of two days, subject to full vacuum and a temperature of 40° C. with intermittent purging to remove excess moisture. After complete drying, the crystals were isolated.

[0256] 500 g of the combined acid generator:ITO:leuco dye particles were combined with 4500 g of LDPE pellets and tumble blended to form a powdered pellet mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. The mixture was melt extruded by setting the heating zones at temperatures of 140° C. (zone 1), 200° C. (zone 5), and 190° C. (die) to form a first masterbatch with 10% by weight of the combined acid generator, ITO, and leuco dye. The first masterbatch was cooled using a chilled water bath and then pelletized into granules using an Accrapak 750 / 3 Free-standing Strand dry cut Pelletiser. The pellets were collected and then dried using a Drymaster machine for several hours to form a solid masterbatch with 10% by weight of the combined acid generator, ITO, and leuco dye.

[0257] The solid masterbatch pellets were collected and loaded into the feed hopper of an Arburg Allrounder 420C injection molding machine to produce plastic plaques containing the combined acid generator, leuco dye and ITO. The plastic plaques had an off-white haze / cloudiness with a blue tint / tint from the NIR absorber (the "background" color).

[0258] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque to create a blue mark or image.A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a blue mark or image.

[0259] [Example 22] A Nutribullet electromechanical high speed blender was used to blend 11.875 kg of AOM and 625 g of ITO to produce a powder. 1680 g of the mixed AOM and ITO was combined with 3.12 kg of LDPE pellets and the mixture was melt extruded to form a first masterbatch containing 35 et.% AOM and ITO. The extruded filaments were pelletized and the pellets were collected. 4800 g of the first masterbatch was combined with 200 g of Canary Yellow OM1700 masterbatch pellets and tumble blended to form a pellet mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140°C (zone 1), 200°C (zone 5), and 190°C (die) and the mixture was melt extruded to produce a first masterbatch containing 4 wt% Canary Yellow and 35% mixed AOM and ITO. This initial masterbatch was cooled using a chilled water bath and then pelletized into granules using an Accrapak 750 / 3 Free-standing strand dry cut pelletiser. The pellets were collected and then dried for several hours using a Drymaster machine to form a solid masterbatch.

[0260] The solid masterbatch pellets were taken and loaded into the feed hopper of a bench-top, manually operated device, a CW Clarke 25 plastic injection molding machine, to produce plastic plaques containing the mixed AOM and ITO. The plastic plaques had a yellow "background" color.

[0261] Plaques were harvested and tested for laser imaging performance using a Coherent 355 nm UV laser, a Macsa F-9020 (continuous wave) Fibre laser, an IPG YLPN-30 (pulsed) Fibre laser and a Videojet VJ-3320 CO2 laser.

[0262] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to a plastic plaque to create a black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a black mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a black mark or image.

[0263] [Example 23] A Nutribullet electromechanical high speed blender was used to blend 11.875 kg of ammonium pentaborate dihydrate and 625 g of ITO to produce a powder. 1680 g of the mixed ammonium pentaborate tetrahydrate and ITO were combined with 3.12 kg of LDPE pellets and the mixture was melt extruded to form a first masterbatch containing 35 wt% mixed ammonium pentaborate and ITO. The first masterbatch was pelletized and the pellets were collected. 4800 g of the first masterbatch was combined with 200 g of Ultra Blue OM5179 masterbatch pellets and tumble blended to form a pellet mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140°C (zone 1), 200°C (zone 5), and 190°C (die) and the mixture was melt extruded to form a first masterbatch containing 4 wt% Ultra Blue and 35 wt% ammonium pentaborate tetrahydrate and ITO. A chilled water bath was used to cool the first masterbatch and then pelletized into granules using an Accrapak 750 / 3 free-standing strand dry cut pelletiser. The pellets were collected and then dried using a Drymaster machine for several hours to form a solid masterbatch.

[0264] The solid masterbatch pellets were taken and loaded into the feed hopper of a bench-top, manually operated device, a CW Clarke 25 plastic injection molding device, to produce plastic plaques containing the mixed ammonium pentaborate tetrahydrate and ITO. The plastic plaques had a blue "background" color.

[0265] Videojet VJ-3320 CO 2A laser was used to apply IR radiation to a plastic plaque to create a white mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to a plastic plaque to create a white mark or image. A Coherent 355 nm UV laser was used to apply UV radiation to a plastic plaque to create a white mark or image.

[0266] [Example 24] 500g of AOM was combined with 4500g of LDPE pellets and tumble blended to form a powdered pellet mixture. The solid mixture was poured into a Brabender feed hopper and gradually metered into the feed throat of a Rondol twin screw extruder using a feed screw. Heating zones were set at temperatures of 140°C (zone 1), 200°C (zone 5), and 190°C (die) and the mixture was melt extruded to obtain a first masterbatch containing 10% by weight AOM. The first masterbatch was cooled using a chilled water bath and then pelletized using an Accrapak 750 / 3 free-standing strand dry cut pelletiser. The pellets were collected and then dried using a Drymaster device for several hours to form a solid masterbatch containing 10% by weight AOM.

[0267] 2 kg of the solid masterbatch pellets were processed with 24.7 kg of Marlex HHM 5502BN virgin HDPE and 13.3 kg of SIRENE HD E 80 PWP rHDPE (post-consumer recycled HDPE) in a 65:35 HDPE mix (virgin HDPE:rHDPE mix) to produce 500 mL tall Boston round (TBR) plastic bottles using extrusion blow molding. The formed plastic bottles contained 5 wt% solid masterbatch and 0.5 wt% AOM.

[0268] A plastic bottle was taken and filled with a water-based synthetic (plastic) fiber dye mixture. 5 mL of the RIT dye Daffodil Yellow 2118 was mixed with 495 mL of water in a 500 mL tall Boston round (TBR) plastic bottle. The plastic bottle was heated to 91° C. in a water bath for 5 hours and allowed to cool to room temperature. The dye mixture was decanted from the bottle, and the bottle was washed and dried, leaving the plastic bottle with a yellow "background" color.

[0269] Videojet VJ-3320 CO 2 A laser was used to apply IR radiation to plastic bottles to create a dark grey / black mark or image. A Macsa F-9020 (continuous wave) Fiber Laser and an IPG YLPN-30 (pulsed) Fiber Laser were used to apply NIR radiation (both continuous and pulsed) to plastic bottles to create a dark grey / black mark or image. A Coherent 355nm UV laser was used to apply UV radiation to plastic bottles to create a dark grey mark or image.

[0270] Embodiment 1. A plastic article formed of a plastic material having a color forming compound incorporated therein, the plastic article being a plastic preform or a plastic package. 2. A plastic product formed of a plastic material having a color-forming compound incorporated therein, the plastic product being produced by contacting the color-forming compound with the plastic material to form a plastic material having the color-forming compound incorporated therein, and forming the plastic material having the color-forming compound incorporated therein into the plastic product, the plastic product being a plastic preform or a plastic package. 3. A plastic product formed of a plastic material having a color forming compound incorporated therein, the plastic product being produced by forming the plastic material having the color forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic package. 4. A plastic product displaying a mark or image, wherein the plastic product is formed of a plastic material having a color-producing compound incorporated therein, and the plastic product is a plastic preform or a plastic package. 5. A plastic product displaying a mark or image, said plastic product being obtainable by applying radiation to a plastic product having a color-forming compound incorporated therein such that the mark or image is formed where the radiation is applied to the plastic product, and the plastic product is a plastic preform or a plastic package. 6. A method of forming a mark or image on a plastic article, the method including the step of exposing the plastic article to radiation to form the mark or image where the radiation is applied, the plastic article being formed of a material having a color forming compound incorporated therein, and the plastic article being a plastic preform or a plastic package. 7. Use of particles of a color-forming compound in the formation of a mark or image on a plastic article formed of a plastic material having the color-forming compound incorporated therein, the plastic article being a plastic preform or a plastic packaging body. 8. A method for producing a plastic product formed of a plastic material having a color-forming compound incorporated therein, the method including the steps of contacting the color-forming compound with the plastic material to form a plastic material having the color-forming compound incorporated therein, and forming the plastic material having the color-forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic packaging body. 9. A method for producing a plastic product formed of a plastic material having a color-forming compound incorporated therein, the method including forming the plastic material having the color-forming compound incorporated therein into a plastic product, the plastic product being a plastic preform or a plastic package. 10. A method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed of a plastic material having a color forming compound incorporated therein, the method including contacting the color forming compound with the plastic material to form a plastic material having the color forming compound incorporated therein, and forming a plastic preform from the plastic material having the color forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle. 11. A method of producing a plastic preform, and optionally a plastic bottle, wherein the plastic preform or plastic bottle is formed of a plastic material having a color forming compound incorporated therein, the method comprising forming the plastic preform from the plastic material having the color forming compound incorporated therein, and optionally forming the plastic preform into a plastic bottle, preferably forming the plastic bottle. 12. The plastic product or method of any of embodiments 2, 3, or 8-11, wherein the plastic product, plastic preform, or plastic bottle is further exposed to radiation to form a mark or image. 13. The plastic product or method of any of embodiments 2, 3, or 8-12, wherein the plastic material is melted once the color-forming compound has been incorporated therein, or the plastic material having the color-forming compound incorporated therein is melted, preferably wherein the color-forming compound is present as particles of color-forming compound. 14. Use of a colour forming compound in the production of a plastic material having a colour forming compound incorporated therein or a plastic product having a colour forming compound incorporated therein, wherein the plastic product is a plastic preform or a plastic packaging body. 15. The plastic product, method or use according to any of embodiments 12 or 13, and embodiment 14, when dependent on embodiments 1 to 9, or embodiment 8 or 9, wherein the plastic product is a plastic preform or a plastic container, preferably a plastic container, such as a plastic box, a plastic pouch, a plastic bottle, a plastic blister package or a plastic clamshell package, more preferably a plastic pouch or a plastic bottle, most preferably a plastic bottle. 16. The plastic product, method or use according to any of the preceding embodiments, wherein the colour-forming compound is present in the plastic product, plastic preform or plastic bottle in particulate form as particles of the colour-forming compound. 17. The plastic product, method or use according to any of the preceding embodiments, wherein the colour-forming compound is present in the plastic product in an amount of less than 15% by weight, such as less than 12% by weight, for example less than 10% by weight, such as less than 5% by weight, for example 0.1-4% by weight, such as less than 4% by weight, for example 0.1-3% by weight, or less than 2% by weight, for example 0.1-1% by weight, or the plastic material used to form the plastic product contains less than 15% by weight, such as less than 12% by weight, for example less than 10% by weight, such as less than 5% by weight, for example 0.1-4% by weight, such as less than 4% by weight, for example 0.1-3% by weight, or less than 2% by weight, for example 0.1-1% by weight, of the colour-forming compound. 18. The plastic product, method or use according to any of embodiments 2, 8 and 10 and, when dependent thereon, any of embodiments 12, 13, 14, 15 or 16, wherein the color-forming compound is contacted with the plastic material in an amount of less than 15% by weight, such as less than 12% by weight, for example less than 10% by weight, for example less than 5% by weight, such as 0.1-4% by weight, for example less than 4% by weight, such as 0.1-3% by weight, or less than 2% by weight, for example 0.1-1% by weight, and optionally in the form of particles of the color-forming compound. 19. (i) a color-forming compound; and (ii) Plastic materials A mixture comprising: 20. A plastic material having a color-producing compound incorporated within it. 21. A plastic material according to embodiment 19 or 20, in which the colour-forming compound is present in an amount of less than 15% by weight, such as less than 12% by weight, for example less than 10% by weight, for example less than 5% by weight, for example 0.1 to 4% by weight, for example less than 4% by weight, for example 0.1 to 3% by weight, or less than 2% by weight, for example 0.1 to 1% by weight, optionally in the form of particles of colour-forming compound. 22. Plastic materials include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene (PCTFE), cyclic olefin copolymer (COC), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), polycarbonate (P C), poly(lactic acid) (PLA), polyethylene terephthalate (PET), polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), low density polyethylene (LDPE) or polystyrene (PS), or a combination thereof, preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), recycled polyethylene terephthalate More preferably, the polystyrene (PS) or polystyrene-modified polyethylene terephthalate (PS) may be polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP), or combinations thereof, more preferably, polyethylene terephthalate (PET), high density polyethylene (HDPE), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low density polyethylene (LDPE), polypropylene (PP), or combinations thereof, more preferably, polyethylene terephthalate (PET), high density polyethylene (HDPE), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low density polyethylene (LDPE), polypropylene (PP), or combinations thereof, more preferably, polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET) or polyethylene terephthalate glycol (PET-G), more preferably,22. The plastic product, method, use, mixture or plastic material according to any one of the preceding claims, wherein the plastic material comprises polyethylene terephthalate (PET). 23. The plastic product, method, use, mixture or plastic material according to any of embodiments 1 to 22, wherein the color-forming compound is present as particles of color-forming compound, and the particles of color-forming compound have a volume-weighted average particle size D[4,3] of 0.1 to 40 μm, preferably 0.5 to 20 μm, more preferably 1 to 15 μm, more preferably 1 to 10 μm, more preferably 1 to 7 μm, and most preferably 3 to 7 μm. 24. The plastic product or method according to any of embodiments 5, 6, 12 and, when dependent thereon, any of embodiments 13, 15, 16, 17, 18, 22 and 23, wherein the radiation is applied from a laser source(s), a lamp or an LED, preferably from a laser source(s). 25. The radiation is selected from ultraviolet (UV) radiation having a wavelength of 10-400 nm, visible light having a wavelength of 400-700 nm, infrared (IR) radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700-1600 nm, preferably the radiation is selected from UV radiation having a wavelength of 10-400 nm, IR radiation having a wavelength of 700 nm to 1 mm, including near infrared (NIR) radiation having a wavelength of 700-1600 nm, more preferably the radiation is selected from UV radiation having a wavelength of 250-370 or 405 nm, infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 laser), infrared radiation having a wavelength of 700 nm to 1 mm, and near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, more preferably the radiation is infrared (IR) radiation (CO) having a wavelength of 9300, 9600, 10200 or 10600 nm. 2laser), infrared radiation having a wavelength of 700 nm to 1 mm, and near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, e.g., 950 to 1100 nm, more preferably the radiation is infrared (IR) radiation (CO 2 The plastic product or method according to any of embodiments 5, 6, 12 and 24, and, when dependent thereon, any of embodiments 13, 15, 16, 17, 18, 22 and 23, wherein the radiation applied is near-infrared (NIR) radiation having a wavelength of 700 to 1600, e.g., 950 to 1100 nm. 26. The plastic product, method, use, mixture, or plastic material according to any one of the preceding embodiments, wherein the color-forming compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, oxyanions of polyvalent metals or oxoacids and / or hydrates thereof, diacetylenes and leuco dyes, or combinations thereof. 27. The plastic product, method, use, mixture or plastic material according to embodiment 26, wherein the color-forming compound is selected from sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, ammonium pentaborate octahydrate, potassium bicarbonate, kaolin, e.g. calcined kaolin, ammonium octamolybdate (AOM), diacetylene and leuco dyes, or combinations thereof. 28. The plastic product, method, use, mixture or plastic material according to embodiment 26 or 27, wherein the colour forming compound is selected from calcined kaolin, ammonium octamolybdate (AOM) and diacetylene, or a combination thereof. 29. A plastic product, method, use, mixture, or plastic material according to any of the preceding embodiments, wherein the color-forming compound is sodium molybdate dihydrate, and preferably, the plastic material comprises PET, r-PET and / or PET-G. 30. A plastic product, method, use, mixture, or plastic material according to any one of the preceding embodiments, wherein the color-forming compound is potassium bicarbonate. 31. A plastic product, method, use, mixture or plastic material according to any one of the preceding embodiments, wherein the colour forming compound is ammonium pentaborate tetrahydrate. 32. A plastic product, method, use, mixture or plastic material according to any one of the preceding embodiments, wherein the colour forming compound is ammonium pentaborate octahydrate. 33. The radiation used to form the mark or image is infrared (IR) radiation having a wavelength between 700 nm and 1 mm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 33. The plastic product, method, use, mixture, or plastic material according to any one of embodiments 29 to 32, wherein the plastic product, method, use, mixture, or plastic material is applied using a laser. 34. A plastic product, method, use, mixture, or plastic material according to any of the preceding embodiments, wherein the colour-forming compound is kaolin, e.g. calcined kaolin, and preferably the plastic material comprises PET, r-PET and / or PET-G. 35. The plastic product, method, use, mixture, or plastic material according to embodiment 34, wherein the colour forming compound is calcined kaolin. 36. The plastic product, method, use, mixture or plastic material according to any of the preceding embodiments, wherein the colour forming compound is an oxyanion of a polyvalent metal or oxoacid and / or a hydrate thereof, preferably an ammonium salt of an oxyanion of molybdenum, more preferably ammonium octamolybdate (AOM), and optionally the plastic material has a melting temperature lower than the decomposition temperature of the oxyanion of the polyvalent metal or oxoacid and / or a hydrate thereof, preferably the plastic material comprises LDPE, HDPE and / or PP, most preferably HDPE. 37. The plastic product, method, use, mixture or plastic material according to embodiment 36, wherein the colour-forming compound is an oxyanion of a polyvalent metal or oxoacid and / or a hydrate thereof, preferably an ammonium salt of an oxyanion of molybdenum, more preferably ammonium octamolybdate (AOM), and the plastic material comprises LDPE, HDPE and / or PP, preferably HDPE. 38. A plastic product, method, use, mixture, or plastic material according to embodiment 36 or 37, wherein the colour forming compound is ammonium octamolybdate (AOM) and the plastic material comprises LDPE, HDPE and / or PP, preferably HDPE. 39. The plastic product, method, use, mixture or plastic material according to any of the preceding embodiments, wherein the colour-forming compound is an oxyanion of a polyvalent metal or oxoacid and / or a hydrate thereof, preferably an ammonium salt of an oxyanion of molybdenum, more preferably ammonium octamolybdate (AOM), and optionally the plastic material has a melting temperature higher than the decomposition temperature of the oxyanion of the polyvalent metal or oxoacid and / or a hydrate thereof, preferably the plastic material comprises PET, r-PET and / or PET-G. 40. A plastic product, method, use, mixture, or plastic material according to any one of embodiments 1 to 28, wherein the color-forming compound is a diacetylene. 41. The radiation used to form the mark or image is UV radiation having a wavelength of 10 to 400 nm, e.g., 250 to 370 or 405 nm, optionally followed by near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, e.g., infrared (IR) radiation (CO) having a wavelength of 9300, 9600, 10200 or 10600 nm. 2 41. The plastic product, method, use, mixture or plastic material according to embodiment 40, wherein the radiation is infrared (IR) radiation having a wavelength between 700 nm and 1 mm, including near infrared (NIR) radiation having a wavelength between 700 and 1600 nm, e.g. between 950 and 1100 nm. 42. The plastic product, method, use, mixture, or plastic material according to any one of the preceding embodiments, wherein the color-forming compound is a leuco dye and the plastic material or plastic product further comprises an acid generator. 43. The plastic product, method, use, mixture, or plastic material of embodiment 42, wherein the plastic material has a lower melting temperature than at least one of the leuco dye and the acid generator. 44. Leuco dyes are 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]phthalide, 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(2-methyl-1-octyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one, 3,3'-bis(1-n-octyl-2-methylindol-3-yl)phthalide, N,N-dimethyl-4-[2-[2-(octyloxy)phenyl]-6-phenyl-4-pyridinyl]-benzene amine, 6'-(diethylamino)-2'-[(dimethylphenyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 2'-anilino-6'-[ethyl(p-tolyl)amino]-3'-methylspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one (CAS number 59129-79-2), 4,4'-[(9-butyl-9H-carbazol-3-yl)methylene]bis[N-methyl-N-phenylaniline] phosphorus] (CAS number 67707-04-4), 6'-(diethylamino)-3-oxo-spiro[isobenzofuran-1(3H),9'-(9H)xanthene]-2' carboxylic acid ethyl ester (CAS number 154306-60-2), 2'-anilino-6'-(dibutylamino)-3'-methyl-3H-spiro[2-benzofuran-1,9'-xanthene]-3-one (CAS number 89331-94-2), 6'-(diethylamino)-3'-methyl-2'-(phenylamino)spiro 44. The plastic product, method, use, mixture or plastic material according to embodiment 42 or 43, which is selected from [2-benzofuran-3,9'-xanthene]-1-one (CAS number 29512-49-0) and 2'-(dibenzylamino)-6'-(diethylamino)fluoran (CAS number 34372-72-0), preferably Blue 3-CVL 6-(dimethylamino)-3,3-bis-[4-(dimethylamino)phenyl)phthalide (CAS number 1522-42-7). 45. The plastic product, method, use, mixture, or plastic material according to any one of embodiments 42 to 44, wherein the acid generator is ammonium sulfate. 46. ​​The radiation used to form the image is infrared (IR) radiation having a wavelength of 700 nm to 1 mm, for example infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO 2 46. ​​The plastic product, method, use, mixture, or plastic material according to any one of embodiments 42 to 45, wherein the plastic product, method, use, mixture, or plastic material is applied using a laser. 47. A plastic product, method, use, mixture, or plastic material according to any of the preceding embodiments, wherein the plastic material or plastic product further comprises a NIR absorber, or the NIR absorber is contacted with the plastic material to form a plastic material further comprising a NIR absorber suitable for forming a plastic product further comprising the NIR absorber. 48. A plastic product, method, use, mixture, or plastic material according to embodiment 47, wherein the NIR absorber is present as particles of NIR absorber. 49. A plastic product, method, use, mixture, or plastic material according to embodiment 47, in which the NIR absorber and color-forming compound, and, if present, the acid generator, are present as combined particles. 50. The plastic product, method, use, mixture, or plastic material according to embodiment 49, when dependent on embodiments 42-46, in which the color-forming compound is a leuco dye and a NIR absorber, and the leuco dye and the acid generator are present as combined particles. 51. The plastic product, method, use, mixture, or plastic material according to any of embodiments 47 to 50, wherein near infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example 950 to 1100 nm, is also selected as the radiation used to form the mark or image.

Claims

1. A plastic product formed from a plastic material in which a color-developing compound is incorporated, wherein the plastic product is a plastic premolded article or a plastic package, and the color-developing compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, or a combination thereof.

2. A plastic product formed from a plastic material in which a color-developing compound is incorporated, wherein the plastic product is produced by forming the plastic material in which the color-developing compound is incorporated into a plastic product, the plastic product is a plastic premolded article or a plastic package, and the color-developing compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, or a combination thereof.

3. A method for forming a mark or image on a plastic product, the method comprising the step of exposing the plastic product to radiation to form the mark or image at the location to which the radiation is applied, wherein the plastic product is formed of a plastic material in which a color-developing compound is incorporated, the plastic product is a plastic premolded article or plastic packaging, and the color-developing compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, or a combination thereof.

4. A method for producing a plastic product formed from a plastic material in which a color-developing compound is incorporated, the method comprising the step of forming the plastic material in which particles of the color-developing compound are incorporated into a plastic product, wherein the plastic product is a plastic premolded article or a plastic packaging, and the color-developing compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, or a combination thereof.

5. A method for producing a plastic premolded article and, optionally, a plastic bottle, wherein the plastic premolded article or plastic bottle is formed from a plastic material in which a color-developing compound is incorporated, and the method is A step of forming a plastic premolded article from a plastic material in which the color-developing compound is incorporated, wherein the color-developing compound is selected from inorganic hydrates, potassium bicarbonate, kaolin, or a combination thereof, and The optional step of forming the plastic premolded product into a plastic bottle. Methods that include...

6. The plastic product according to claim 2, wherein the plastic product is exposed to radiation to form a mark or image.

7. The method according to claim 4 or 5, further comprising the step of exposing the plastic product to radiation to form a mark or image.

8. The plastic product according to claim 1 or 2, wherein the plastic product is a plastic premolded article or a plastic container, preferably a plastic container, more preferably a plastic box, a plastic pouch, a plastic bottle, a plastic blister pack, or a plastic clamshell pack, even more preferably a plastic pouch or a plastic bottle, and most preferably a plastic bottle.

9. The method according to claim 3 or 4, wherein the plastic product is a plastic premolded article or a plastic container, preferably a plastic container, more preferably a plastic box, a plastic pouch, a plastic bottle, a plastic blister pack, or a plastic clamshell pack, even more preferably a plastic pouch or a plastic bottle, and most preferably a plastic bottle.

10. The color-developing compound is present in the plastic product in an amount of less than 15% by weight, or The plastic material used to form the plastic product contains less than 15% by weight of the color-developing compound. The plastic product according to claim 1 or 2.

11. The color-developing compound is present in the plastic product in an amount of less than 15% by weight, or The plastic material used to form the plastic product contains less than 15% by weight of the color-developing compound. The method according to claim 3, 4, or 5.

12. The aforementioned plastic material is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene (PCTFE), cyclic olefin copolymer (COC), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), polycarbonate (PC), poly(lactic acid) (PLA), polyethylene terephthalate (PET), polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), low-density polyethylene (LDPE), or polystyrene (PS), or a combination thereof, preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), recycled polyethylene terephthalate A phthalate (r-PET), low-density polyethylene (LDPE), polyethylene terephthalate glycol (PET-G), or polystyrene (PS), or a combination thereof, more preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low-density polyethylene (HDPE), high-density polyethylene (HDPE), and polypropylene (PP), or a combination thereof, more preferably polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low-density polypropylene (LDPE), high-density propylene (HDPE), and polypropylene (PP), or a combination thereof, more preferably polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET), or polyethylene terephthalate glycol (PET-G),The plastic product according to claim 1 or 2, more preferably comprising polyethylene terephthalate (PET) as the plastic material.

13. The aforementioned plastic material is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene (PCTFE), cyclic olefin copolymer (COC), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), polycarbonate (PC), poly(lactic acid) (PLA), polyethylene terephthalate (PET), polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), low-density polyethylene (LDPE), or polystyrene (PS), or a combination thereof, preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), recycled polyethylene terephthalate A phthalate (r-PET), low-density polyethylene (LDPE), polyethylene terephthalate glycol (PET-G), or polystyrene (PS), or a combination thereof, more preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low-density polyethylene (HDPE), high-density polyethylene (HDPE), and polypropylene (PP), or a combination thereof, more preferably polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET), polyethylene terephthalate glycol (PET-G), low-density polypropylene (LDPE), high-density propylene (HDPE), and polypropylene (PP), or a combination thereof, more preferably polyethylene terephthalate (PET), recycled polyethylene terephthalate (r-PET), or polyethylene terephthalate glycol (PET-G),The method according to claim 3, 4, or 5, more preferably comprising polyethylene terephthalate (PET) as the plastic material.

14. The method according to claim 3 or the plastic product according to claim 6, wherein the radiation is applied from a laser source(s), a lamp or an LED, preferably from a laser source(s).

15. The radiation is selected from ultraviolet (UV) radiation having a wavelength of 10 to 400 nm, visible light having a wavelength of 400 to 700 nm, and near-infrared (NIR) radiation having a wavelength of 700 to 1600 nm, and infrared (IR) radiation having a wavelength of 700 nm to 1 mm, preferably the radiation is selected from UV radiation having a wavelength of 10 to 400 nm, and near-infrared (NIR) radiation having a wavelength of 700 to 1600 nm, and infrared (IR) radiation having a wavelength of 700 nm to 1 mm, more preferably the radiation is UV radiation having a wavelength of 250 to 370 or 405 nm, and infrared (IR) radiation having a wavelength of 9300, 9600, 10200 or 10600 nm (CO2). ２ The radiation is selected from infrared radiation having wavelengths of 700 nm to 1 mm and near-infrared (NIR) radiation having wavelengths of 700 to 1600 nm (applied using a laser), and more preferably the radiation is infrared (IR) radiation (CO) having wavelengths of 9300, 9600, 10200 or 10600 nm. ２ The radiation is selected from infrared radiation having wavelengths of 700 nm to 1 mm (applied using a laser) and near-infrared (NIR) radiation having wavelengths of 700 to 1600 nm, for example, 950 to 1100 nm, and more preferably the radiation is infrared (IR) radiation (CO) having a wavelength of 10600 nm. ２ The method according to claim 3 or the plastic product according to claim 6, wherein the application is by using a laser and near-infrared (NIR) radiation having a wavelength of 700 to 1600 nm, for example, 950 to 1100 nm.

16. The plastic product according to claim 1 or 2, wherein the color-developing compound is selected from sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, ammonium pentaborate octahydrate, potassium bicarbonate, kaolin, for example, calcined kaolin, or a combination thereof.

17. The method according to claim 3, 4, or 5, wherein the color-developing compound is selected from sodium molybdate dihydrate, ammonium pentaborate tetrahydrate, ammonium pentaborate octahydrate, potassium bicarbonate, kaolin, for example, calcined kaolin, or a combination thereof.