Toy building bricks made from recycled ABS material

Abstract

The present invention relates to toy building elements made from recycled acrylonitrile-butadiene-styrene (ABS) material and manufactured by processing a resin including recycled ABS polymer.

Description

Field of the Invention

[0001] The present invention relates to toy building elements made from recovered (recycled) acrylonitrile-butadiene-styrene (ABS) material and manufactured by processing a resin comprising recycled ABS polymer. Background Art

[0002] Toy building elements have been manufactured and sold for many years. Traditionally, such toy building elements have been made from petroleum-based polymers such as ABS.

[0003] ABS is an engineering thermoplastic polymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The proportions may be 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene. ABS consists of an amorphous continuous phase and a rubbery (rubber) dispersed phase. Poly(styrene-co-acrylonitrile) (SAN) copolymer forms the continuous phase, and the second phase consists of dispersed butadiene or butadiene copolymer. The butadiene particles have a layer of SAN grafted onto their surface, which makes the two phases compatible. The properties of ABS derive from the composition, the thermoplastic and rubbery phase properties and the interaction between them. Therefore, the content and molecular weight of SAN control properties such as processability, heat resistance, surface hardness and chemical resistance. The butadiene content contributes mainly to toughness.

[0004] ABS can be produced by emulsion polymerization and bulk polymerization. Depending on whether ABS is produced by emulsion or bulk polymerization, ABS materials with different properties are obtained. For example, when ABS is produced by emulsion polymerization, a high gloss surface of the ABS material can be obtained, while when the ABS material is produced by bulk polymerization, a low surface gloss is generally obtained.

[0005] Growing concerns over dwindling petroleum resources and the effects of global warming have prompted the development of recycled ABS and technologies for producing ABS polymers by using biomass as a renewable resource.

[0006] ABS can be produced by using biomass as a renewable resource. WO 2015 / 034948A1 describes a method for producing bio-based organic chemicals such as bio-acrylic acid, bio-acrylonitrile and bio-1,4-butadiene using a renewable carbon source as a raw material. In the first stage, bio-1,3-propanediol is obtained from a renewable carbon source by microbial fermentation, and in the second stage, bio-1,3-propanediol is converted into bio-acrylic acid or bio-acrylonitrile or bio-1,4-butanediol.

[0007] ABS can also be produced by using materials that have been obtained using carbon capture technology, i.e., the material has been produced using carbon monoxide and / or carbon dioxide that has been captured directly from the air or from gases from industrial processes. Such carbon capture technologies include, for example, absorption, adsorption, chemical cyclization, and membrane separation technologies. The captured carbon oxides can then be converted into hydrocarbons, such as alcohols or ethanol, which can be used as a source for preparing new monomers or polymers.

[0008] ABS can also be obtained through mechanical or chemical recycling of ABS materials.

[0009] Mechanical recycling of ABS involves only mechanical processes such as grinding, washing, separation, drying, regranulation and compounding. In a typical recycling process, waste ABS plastics are collected and washed to remove contaminants. The clean plastic is then ground into flakes that can be compounded and granulated or reprocessed into pellets.

[0010] One problem associated with the use of mechanically recycled ABS materials is that the properties of the recycled ABS materials are generally worse than those of virgin ABS materials. This is due to degradation phenomena that occur during the life of the ABS and during melt reprocessing operations that accelerate degradation. During reprocessing, the ABS material is subjected to high temperatures and shear stresses, which lead to different types of degradation reactions. The degree of degradation depends on the number of cycles and the processing temperature. It is also expected that for post-consumer recycled ABS, exposure to light, elevated temperatures and chemicals during use will cause further degradation. It is believed that ABS degrades due to chain scission and crosslinking, producing oligomeric products that can migrate to the surface and brittle crosslinked polybutadiene particles. Chemical changes have a significant negative impact on, for example, impact strength, and it is necessary to improve the properties of the recycled polymer by adding suitable additives or by blending it with the virgin polymer.

[0011] Another problem associated with the use of mechanically recycled ABS materials is the presence of hazardous and / or unacceptable additives and other unwanted substances in the waste ABS for recycling. ABS waste is usually washed before recycling, but the washing step does not remove all additives and other unwanted substances present in the waste. Some types of additives may be dangerous, so their presence in recycled ABS materials is unacceptable when used to make toys such as toy building elements. In particular, substances classified as 1A, 1B or 2 carcinogenic, mutagenic or reproductive toxic (CMR) according to Regulation (EC) No 1272 / 2008 are unwanted substances in recycled materials. In addition, the presence of toxic metals must be avoided. Flame retardants in waste from WEEE (waste electrical and electronic equipment) are another example of unacceptable types of additives. Other types of additives that may be present in waste ABS include pigments, such as iron oxide, which contribute to the continuous degradation of ABS materials during their life before ABS items are discarded as waste. Other types of additives may be impact modifiers that affect the impact strength of the recycled ABS material, lubricants that may affect material processing and friction properties, and colorants that may affect both the color and mechanical properties of the recycled ABS material. ABS waste may also contain unwanted substances that have been absorbed during the use phase. Such substances may include organic solvents, detergents, and food ingredients. ABS waste may also contain decorations that include other monomers and solvents.

[0012] Another problem associated with using mechanically recycled ABS polymer is that recycled ABS is only commercially available in dark grey and black. Suitable coloring processes must be developed to produce brightly colored toys made from recycled ABS material.

[0013] Chemical recycling of ABS refers to any process by which ABS waste is converted by chemical methods into its virgin monomers and / or oligomers, which can be used to produce new virgin polymers to form ABS articles. Chemical recycling methods of this type include pyrolysis and chemical depolymerization. Chemical recycling also refers to any process in which the ABS waste can be dissolved using a suitable solvent and then the dissolved ABS polymer is recovered, usually by precipitation of the polymer or by evaporation of the solvent. This type of chemical recycling process is often referred to as "solvent dissolution."

[0014] Pyrolysis refers to the decomposition of ABS materials at elevated temperatures in the absence of oxygen. Pyrolysis converts the plastic into pyrolysis oil which can be further refined. New virgin polymers can then be prepared from the resulting oil by known polymerization methods.

[0015] Chemical depolymerization is the process of using chemicals to decompose a polymer into monomers, oligomers, or a mixture of monomers and / or oligomers and / or their intermediates. The process removes additives and colorants from the monomers / intermediates. New virgin polymers can be produced by polymerization of monomers. Currently, there is no commercially available technology suitable for depolymerization of ABS waste. However, new virgin ABS polymers can be made by polymerization of monomers that have been recycled by depolymerization of other types of plastic waste. For example, styrene monomers can be recycled by depolymerization of polystyrene, as described in WO 2016 / 049782.

[0016] Solvent dissolution involves the selective extraction of the polymer using a solvent. Any additives and colorants are removed and the resulting polymer is usually recovered by precipitation of the polymer or by evaporation of the solvent. The polymer chains and structure are not decomposed. Dissolution-based ABS recovery technologies have also been developed, with many solvents proposed for dissolving ABS, such as acetone and tetrahydrofuran (THF).

[0017] One problem associated with using ABS polymer recovered from the solvent dissolution cycle is that the solvent extraction also removes all additives. This means that the recycled ABS material will not have the desired properties, such as viscosity, mold release, friction, fillers and flame retardants, and may require new protective additives, such as heat stabilizers, antioxidants, UV stabilizers, etc.

[0018] Another problem associated with using ABS polymer recovered from a solvent dissolution recovery process is that the solvent extraction will contain a mixture of different SAN chains and butadiene spheres. Compensating for the unforeseen mixture of material components is a challenge. Thus, it may be necessary to add short or long chain SAN to change rheology or stiffness, and butadiene spheres may need to be added to improve impact properties. It may also be necessary to add different types of additives to compensate for additives lost during the solvent dissolution process.

[0019] The main problem associated with the use of recycled ABS, regardless of how it is produced, is the recovery of a polymer composition that is not uniform compared to the virgin polymer composition. The extent of the variation depends mainly on the waste material: the more uniform the waste material, the smaller the degree of variation. It must be expected that recycled ABS has a large variation in the ratio between styrene, butadiene and acrylonitrile, the chain length of the SAN copolymer, the size and size distribution of the butadiene spheres and the degree of SAN grafting on the surface of the butadiene spheres. Therefore, more efforts are needed to produce recycled ABS that is suitable and advantageous for the manufacture of articles such as toy building elements, so as to obtain articles with satisfactory properties, such as satisfactory impact strength, surface friction and color. In particular, if it is intended to manufacture an article with a surface gloss, it is important to know in advance that the ABS waste has been produced by emulsion polymerization and that it also contains butadiene spheres of suitable size, because the size of the butadiene spheres in the ABS material has proven to be important for obtaining a smooth surface of the finished product. Summary of the invention

[0020] The present invention relates to toy building elements made from recycled ABS (Acrylonitrile-Butadiene-Styrene) material and manufactured by processing a resin comprising recycled ABS polymers. The inventors of the present invention surprisingly found that toy building elements can be manufactured by processing a resin comprising recycled ABS polymers.

[0021] In a first aspect, the present invention relates to a toy building element made from recycled ABS material.

[0022] In a second aspect, the present invention relates to a method for manufacturing toy building elements made from recycled ABS material. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 shows the traditional box-shaped 2*4 bricks.

[0024] Figure 2 A method for manufacturing toy building elements by processing a resin comprising mechanically recycled ABS polymer and / or chemically recycled ABS polymer recycled from a dissolution recycling process is shown.

[0025] Figure 3 A method for manufacturing toy building elements by processing a resin comprising mechanically recycled ABS polymer is shown.

[0026] Figure 4 A method for manufacturing toy building elements by processing a resin comprising mechanically recycled ABS polymer is shown, wherein the waste ABS material is waste toy building elements.

[0027] Figure 5A method of manufacturing toy building elements by processing a resin comprising chemically recycled ABS polymer recovered from a dissolution recycling process is shown. In this embodiment, both the SAN phase and the butadiene spheres are recovered.

[0028] Figure 6 A method for manufacturing toy building elements by processing a resin comprising chemically recycled ABS polymers recovered from a dissolution recycling process is shown. In this embodiment, only the SAN phase is recycled and mixed with additives and virgin butadiene and optionally other ABS polymers.

[0029] Figure 7 A method for manufacturing toy building elements by processing a resin comprising chemically recycled ABS polymer recovered from a dissolution recycling process is shown. In this embodiment, only the SAN phase is recycled and mixed with additives and virgin ABS with a high butadiene content. DETAILED DESCRIPTION

[0030] The present invention relates to toy building elements made from recycled ABS material.

[0031] The term "toy building element" as used herein comprises conventional toy building elements in the form of box-shaped building bricks provided with a knob on the upper side and a complementary tube on the lower side. Figure 1 The conventional box-shaped toy building bricks were first disclosed in US 3,005,282 and marketed under the trade name and The term also includes other similar box-shaped building bricks which are produced by companies other than the LEGO Group and therefore sold under trademarks other than the LEGO trademark.

[0032] The term "toy building element" also includes other kinds of toy building elements forming part of a toy building set, which typically comprises a plurality of building elements which are compatible and can therefore be interconnected with one another. Such toy building sets are also sold under the trademark LEGO, e.g. Bricks, Technic and Some of these toy building sets include toy building figures, e.g. Miniature figures (see for example US 05 / 877,800) which have a complementary tube on the underside so that the figure can be connected to other toy building elements in a toy building set. The term "toy building element" also includes such toy building figures. The term also includes similar toy building elements which are produced by other companies than the LEGO Group and are therefore sold under other trademarks than the trademark LEGO.

[0033] Toy building elements can be of various shapes, sizes and colors. Bricks and One difference between bricks is The size of the bricks is Twice the size of the brick in all dimensions. Traditional box shape with 4*2 knobs on the upper side The dimensions of the toy building bricks are about 3.2 cm long, about 1.6 cm wide, and about 0.96 cm high (excluding the knobs), and the diameter of each knob is about 0.48 cm. In contrast, the dimensions of the bricks with 4*2 knobs on the upper side are about 6.4 cm long, about 3.2 cm wide, and about 1.92 cm high (excluding the knobs), and the diameter of each knob is about 0.96 cm.

[0034] The toy building element is manufactured from recycled ABS material and the element is made by processing a resin comprising mechanically recycled ABS polymer and / or chemically recycled ABS polymer recovered from a solvent dissolution recycling process.

[0035] As used herein, the term "recycled ABS material" refers to an ABS material obtained by processing a resin including a recycled ABS polymer. The recycled ABS polymer is obtained from ABS waste. The ABS waste can be a mechanically recycled ABS material or a chemically recycled ABS material. The recycled ABS polymer in the resin is a mechanically recycled ABS polymer and / or a chemically recycled ABS polymer recovered from a solvent dissolution recovery process. In addition, the resin may also include virgin ABS polymer and / or a chemically recycled ABS polymer recovered from a pyrolysis recovery method and / or a recycled ABS polymer recovered from a chemical depolymerization recovery method.

[0036] "Mechanically recycled ABS material" refers to ABS material that has been recycled through mechanical recycling of ABS material. Mechanical recycling involves only mechanical processes such as grinding, washing, separation, drying, regranulation and compounding. In a typical recycling process, ABS waste is collected and washed to remove contaminants. The clean plastic is then ground into flakes, which can be blended and granulated or reprocessed into pellets.

[0037] "Chemically recycled ABS material" includes ABS material made from ABS waste that has been subjected to pyrolysis, chemical depolymerization, solvent dissolution, or any other suitable chemical recycling method.

[0038] "Pyrolysis" refers to the decomposition of ABS materials into pyrolysis oils at elevated temperatures in the absence of oxygen. New virgin polymers can then be prepared from the resulting oils by known polymerization methods.

[0039] "Chemical depolymerization" refers to the process of using chemical reagents to decompose polymers into monomers, monomer mixtures or their intermediates. New native polymers can be produced by polymerization of monomers.

[0040] "Solvent dissolution" refers to the selective extraction of the polymer using a solvent. The extracted polymer is recovered by precipitation of the polymer or by evaporation of the solvent. The polymer chains and structure are not decomposed. Butadiene is present in the ABS as distinct small globules. Solvent dissolution does not change the chemical bonds in the polymer chains, but there is a risk of physical changes in the shape and size of the butadiene globules. Therefore, it may be necessary to discard the butadiene globules during solvent dissolution.

[0041] The term "recycled ABS polymer" refers to ABS polymers included in mechanically recycled ABS waste or polymers chemically recovered from ABS waste in a solvent dissolution process. The term also refers to virgin ABS polymers produced in a pyrolysis recycling process or a chemical depolymerization recycling process. When the term refers to virgin ABS polymers, it also includes polymers in which only one or two monomers have been recovered by pyrolysis or chemical depolymerization. For example, the term includes ABS polymers in which some or all of the styrene monomers have been recovered by chemical depolymerization of polystyrene, while the acrylonitrile and butadiene monomers may be non-recycled monomers produced by conventional manufacturing methods.

[0042] In some embodiments, the recycled ABS material comprises recycled ABS polymer obtained from mechanically recycled ABS waste. In other embodiments, the recycled ABS material comprises recycled ABS polymer obtained from chemically recycled ABS waste, wherein the ABS polymer has been recovered using a solvent dissolution recovery method. In other embodiments, the recycled ABS material comprises a mixture of recycled ABS polymers obtained from mechanically recycled ABS waste and chemically recycled ABS waste, wherein the ABS polymer has been recovered using a solvent dissolution recovery method. In further embodiments, the recycled ABS material may also include virgin ABS polymer and / or virgin ABS polymer, i.e., recycled ABS polymer recovered from a pyrolysis recovery method and / or from a chemical depolymerization recovery method.

[0043] The toy building elements are manufactured by injection molding (injection molding) or by additive manufacturing techniques or by a combination of injection molding and additive manufacturing techniques. Alternatively, the toy building elements are manufactured by extrusion, optionally followed by molding using thermoforming or similar techniques.

[0044] Injection molding of toy building elements is a traditional way of manufacturing toy building bricks. This manufacturing technique has been used for many years and is well known to those skilled in the art. In some embodiments, the toy building elements are manufactured by injection molding a resin comprising recycled ABS polymer. In other embodiments, the toy building elements are manufactured by two-component injection molding, wherein one component is a resin comprising recycled ABS polymer. In other embodiments, the toy building elements are manufactured by multi-component injection molding, wherein at least one component is a resin comprising recycled ABS polymer.

[0045] In recent years, new additive manufacturing techniques have been developed for building objects in, for example, polymer materials. As used herein, the terms "additive manufacturing" or "additively manufactured" refer to building bricks in an additive manner, i.e., by adding new material on top of a substrate or on top of newly added material, by repeatedly solidifying a thin liquid layer or droplets on a substrate or on previously solidified liquid layers or droplets, or by repeatedly printing a thermoplastic polymer material on a substrate or on previously printed plastic material, or by repeatedly welding in an additive manner with plastic materials, for example by using a laser.

[0046] In some embodiments, the toy building elements are manufactured by injection molding. In other embodiments, the toy building elements are manufactured by additive manufacturing. In other embodiments, the toy building elements are manufactured by a combination of injection molding and additive manufacturing. Such a combined manufacturing technique is described, for example, in WO 2014 / 005591, where toy building elements with a high degree of design individuality are manufactured by adding material in a layer-by-layer manner on the surface of conventional injection-molded box-shaped building bricks.

[0047] In other embodiments, the toy building element is manufactured by extrusion. Optionally, the extrusion process is followed by molding using thermoforming or similar techniques.

[0048] It is known that the size of the butadiene spheres in the ABS material affects the glossiness of the surface of the object made from the ABS material. In the toy industry, the glossy surface is most often targeted. Therefore, in a preferred embodiment, the size of the butadiene spheres in the recycled ABS material is less than or equal to 0.5 microns.

[0049] One of the main problems with using recycled ABS material to make new toy building elements is the loss of mechanical properties, in particular impact strength. Sometimes, this problem can be at least partially solved by adding virgin ABS polymer to the resin before processing the resin into toy building elements. Alternatively, the problem can be solved by adding virgin ABS polymer or a mixture of virgin ABS polymer and virgin ABS polymer.

[0050] In one embodiment, the resin further comprises virgin ABS polymer. In some embodiments, the amount of virgin ABS polymer is at least 5% by weight of the total amount of polymer in the resin, such as at least 10% by weight, at least 30% by weight, at least 50% by weight, at least 70% by weight, or at least 90% by weight. In other embodiments, the amount of virgin ABS polymer is 5-95% by weight of the total amount of polymer in the resin, such as 10-95% by weight, 30-95% by weight, 50-95% by weight, 70-95% by weight, or 80-95% by weight. In other embodiments, the amount of virgin ABS polymer is 5-50% by weight of the total amount of polymer in the resin, such as 5-30% by weight, 5-20% by weight, or 5-10% by weight.

[0051] In other embodiments, resin includes virgin ABS polymer.Term " virgin ABS polymer " used herein refers to the ABS polymer of chemical recovery collected from pyrolysis recovery method and / or chemical depolymerization recovery method.In some embodiments, the amount of virgin ABS polymer is at least 5 weight % of the total amount of polymer in resin, such as at least 10 weight %, at least 30 weight %, at least 50 weight %, at least 70 weight % or at least 90 weight %.In other embodiments, the amount of virgin ABS polymer is 5-95 weight % of the total amount of polymer in resin, such as 10-95 weight %, 30-95 weight %, 50-95 weight %, 70-95 weight % or 80-95 weight %.In other embodiments, the amount of virgin ABS polymer is 5-50 weight % of the total amount of polymer in resin, such as 5-30 weight %, 5-20 weight % or 5-10 weight %.

[0052] In other embodiments, the resin includes a mixture of virgin ABS polymer and virgin ABS polymer. In some embodiments, the total amount of virgin ABS polymer and virgin ABS polymer is at least 5% by weight of the total amount of polymer in the resin, such as at least 10% by weight, at least 30% by weight, at least 50% by weight, at least 70% by weight, or at least 90% by weight. In other embodiments, the total amount of virgin ABS polymer and virgin ABS polymer is 5-95% by weight of the total amount of polymer in the resin, such as 10-95% by weight, 30-95% by weight, 50-95% by weight, 70-95% by weight, or 80-95% by weight. In other embodiments, the total amount of virgin ABS polymer and virgin ABS polymer is 5-50% by weight of the total amount of polymer in the resin, such as 5-30% by weight, 5-20% by weight, or 5-10% by weight.

[0053] In a preferred embodiment, the recycled ABS waste is discarded toy building elements, whereby the recycled material is very similar to the virgin material, except that the recycled material has been processed into toy building elements which have then been ground into pellets or flakes. In such cases, it has surprisingly been found that toy building elements made entirely of mechanically recycled toy building elements having satisfactory mechanical properties, i.e. impact strength, can be manufactured even without introducing new additives for improving the mechanical properties, such as impact modifiers.

[0054] In some embodiments, the resin does not contain any virgin ABS polymer. In other embodiments, the amount of virgin ABS polymer is 0-95% by weight of the total amount of polymer in the resin, such as 0-50% by weight, 0-25% by weight, 0-10% by weight, or 0-5% by weight.

[0055] The weight ratio between the mechanically recycled ABS polymer and the virgin ABS polymer may be in the range of 100:0 to 1:99, such as 100:0 to 10:90, 90:10 to 50:50, or 50:50 to 90:10.

[0056] In certain embodiments, the recycled ABS waste is subjected to a solvent dissolution recovery process. In this process, the ABS polymer from the waste is dissolved in a solvent and then the dissolved ABS polymer is recovered, typically by precipitation of the polymer or by evaporation of the solvent. In the dissolved state, the polymer can separate into two phases; one phase contains poly(styrene-co-acrylonitrile) chains, also known as a SAN phase, and the other phase contains a butadiene copolymer, also known as butadiene spheres.

[0057] In some embodiments, it may be appropriate to recycle both the SAN phase and the butadiene spheres, while in other embodiments, it may be appropriate to recycle only the SAN phase. In some cases where only the SAN phase is appropriately recycled, the recycled SAN copolymer may be mixed with butadiene, which may be virgin butadiene or recycled butadiene or a mixture thereof. In other cases where only the SAN phase is appropriately recycled, the recycled SAN copolymer may be mixed with ABS having a high butadiene content. The ABS having a high butadiene content may be virgin ABS or recycled ABS or a mixture thereof.

[0058] As used herein, the term "ABS having a high butadiene content" refers to ABS having at least 20 wt% butadiene.

[0059] In other embodiments, the resin includes mechanically recycled ABS polymer and chemically recycled ABS polymer recovered from a solvent dissolution recovery process. In some embodiments, the resin additionally includes virgin ABS polymer.

[0060] Alternatively, the resin comprises mechanically recycled ABS polymer, recycled SAN copolymer and additional ABS with high butadiene content. The ABS with high butadiene content may be virgin ABS or recycled ABS or a mixture thereof.

[0061] In other embodiments, the resin comprises mechanically recycled ABS polymer and a SAN phase recovered from ABS waste that has been subjected to a solvent dissolution recovery process. In this embodiment, it may be suitable to further add butadiene or ABS with a high butadiene content or a mixture thereof. Butadiene and ABS with a high butadiene content may be of virgin or recycled origin or a mixture thereof.

[0062] In a practical injection molding system, the amount of ABS recycled is determined by the volume ratio of the mold and the mold runner system. When a new production starts, the mold is fed with virgin material in the first run. The material that remains in the runner system and therefore does not form part of the final injection molded component is ground back into the form of pellets or flakes or the like and used as recycled material, which is mixed with virgin material and fed into the mold again. Such recycling continues until a steady state is reached, in which the amount of recycled material will represent a certain constant percentage of the input material, and in which the rest of the material will be virgin material. This constant percentage of recycled material will be referred to as "% recycled material after steady state".

[0063] The inventors of the present invention have surprisingly found that a significant increase in Charpy V-notch is observed for molded components produced in molds run with low % recycled material after steady state. A specific example is described in Example 2, where a mold run with 42% recycled material after steady state (Mold 1) produced a molded bar with a relative Charpy V-notch value of 108%. Another mold run with 90% recycled material after steady state (Mold 2) showed no decrease in the relative Charpy V-notch value. These findings are very unexpected because a decrease in the relative Charpy V-notch value would be expected when ABS material is recycled.

[0064] Therefore, in a particularly preferred embodiment of the invention, the toy building element is produced by injection moulding using a mould operating with 20-95 wt. %, for example 30-90 wt. %, of the recycled material after steady state.

[0065] The resin processed into the toy building elements may include bio-based ABS polymers and / or hybrid bio-based ABS polymers.

[0066] As used herein, the term "bio-based ABS polymer" refers to an ABS polymer produced by chemical or biochemical polymerization of monomers derived from biomass. In some embodiments, the bio-based polymer is produced by chemical polymerization of monomers, all of which are derived from biomass. In other embodiments, the bio-based polymer is produced by biochemical polymerization of monomers, all of which are derived from biomass.

[0067] As used herein, the term "hybrid bio-based ABS polymer" refers to an ABS polymer produced by polymerization wherein at least one ABS monomer is derived from biomass and at least one ABS monomer is derived from petroleum, a petroleum byproduct, or a petroleum-derived feedstock. The ABS monomers may be virgin monomers, chemically recycled monomers, or a mixture of virgin monomers and recycled monomers. The polymerization process is typically a chemical polymerization process.

[0068] In some embodiments, at least a portion of the recycled ABS polymer is a bio-based ABS polymer and / or a hybrid bio-based ABS polymer. In other embodiments, at least a portion of the virgin ABS polymer is a bio-based ABS polymer and / or a hybrid bio-based ABS polymer. In other embodiments, at least a portion of the recycled ABS polymer and at least a portion of the virgin ABS polymer is a bio-based ABS polymer and / or a hybrid bio-based ABS polymer.

[0069] In other embodiments, the toy building elements may include ABS polymers produced using carbon capture technology. As used herein, the term "ABS polymers produced using carbon capture technology" refers to polymers that contain carbon atoms from carbon monoxide and / or carbon dioxide that are captured directly from the air or from gases from industrial processes.

[0070] In one embodiment, the total amount of ABS polymer in the resin is at least 50 wt % relative to the total weight of the resin. In other embodiments, the total amount of ABS polymer is at least 60 wt % or at least 70 wt % or at least 80 wt % relative to the total weight of the resin. In other embodiments, the total amount of ABS polymer is at least 85 wt %, such as at least 90 wt %, relative to the total weight of the resin.

[0071] In another embodiment, the total amount of ABS polymer in the resin is 50-99 wt % relative to the total weight of the resin. In other embodiments, the total amount of ABS polymer is 60-95 wt % or 70-90 wt % or 80-85 wt % relative to the total weight of the resin. In other embodiments, the total amount of ABS polymer is 85-97 wt % or 90-97 wt % or 90-95 wt % or 90-92 wt % relative to the total weight of the resin.

[0072] As used herein, the term "total amount of ABS polymer in the resin" refers to the total amount of ABS polymer in the resin, regardless of whether the ABS polymer is recycled ABS polymer, virgin ABS polymer, bio-based ABS polymer, hybrid bio-based ABS polymer and / or ABS polymer produced using carbon capture technology.

[0073] It may be beneficial to add additives to the resin comprising recycled ABS polymer to improve the properties of toy building elements manufactured by processing the resin. In some embodiments, the resin comprising recycled ABS polymer includes one or more additives, such as impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers, and plasticizers.

[0074] The impact modifier may be a reactive impact modifier or it may be a non-reactive impact modifier. In some embodiments, the resin of the recycled ABS polymer may include reactive and non-reactive impact modifiers. In a preferred embodiment, the resin includes a reactive impact modifier.

[0075] As used herein, the term "impact modifier" refers to an agent that increases the impact strength of an injection molded ABS component when added to the resin.

[0076] The reactive impact modifier has functionalized end groups. Functionalization has two purposes: 1) to bind the impact modifier to the polymer matrix, and 2) to modify the interfacial energy between the polymer matrix and the impact modifier to enhance dispersion. Preferred examples of such functionalized end groups include glycidyl methacrylate, maleic anhydride, and carboxylic acids.

[0077] In the present invention, reactive impact modifiers are preferred. In a preferred embodiment, the impact modifier is a copolymer of formula X / Y / Z, wherein X is an aliphatic or aromatic hydrocarbon polymer having 2-8 carbon atoms, Y is a moiety comprising an acrylate or methacrylate having 3-6 and 4-8 carbon atoms, respectively, and Z is a moiety comprising methacrylic acid, glycidyl methacrylate, maleic anhydride or carboxylic acid.

[0078] In a preferred embodiment, the impact modifier can be described by the following formula:

[0079]

[0080] in

[0081] n is an integer from 1 to 4,

[0082] m is an integer from 0 to 5,

[0083] k is an integer from 0 to 5, and

[0084] R is an alkyl group of 1 to 5 carbon atoms or 1 hydrogen atom.

[0085] X accounts for 40-90% (wt / wt) of the impact modifier, and Y accounts for 0-50% (wt / wt) of the impact modifier, such as 10-40% (wt / wt), preferably 15-35% (wt / wt), most preferably 20-35% (wt / wt), and Z accounts for 0.5-20% (wt / wt), preferably 2-10% (wt / wt), most preferably 3-8% (wt / wt) of the impact modifier.

[0086] In other embodiments, X comprises 70-99.5% (wt / wt), preferably 80-95% (wt / wt), most preferably 92-97% (wt / wt) of the impact modifier, and Y comprises 0% (wt / wt) of the impact modifier, and Z comprises 0.5-30% (wt / wt), preferably 5-20% (wt / wt), most preferably 3-8% (wt / wt) of the impact modifier.

[0087] Suitable examples of specific impact modifiers that can be used in the resins of the present invention include ethylene-ethylene acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate. Commercially available impact modifiers include Paralid TM EXM-2314 (acrylic acid copolymer from Dow Chemical Company), AX8700, AX8900、Lotader AX8950 and AX8840 (manufactured by Arkema) and PTW (manufactured by DuPont).

[0088] Other suitable examples of specific impact modifiers that can be used in the resins of the present invention include anhydride-modified ethylene acrylates. Commercially available impact modifiers include 3210, 3410, 4210, 3430, 4402, 4503, 4613, 4700, 5500, 6200, 8200, HX8210, HX8290, LX4110, TX8030 (manufactured by Arkema), 21E533, 21E781, 21E810 and 21E830 (manufactured by DuPont).

[0089] In other embodiments, the impact modifier is a modified ethylene vinyl acetate, such as 1123 or 1124 (manufactured by DuPont); acid-modified ethylene acrylates, such as 2002 or 2022 (manufactured by DuPont); modified ethylene acrylates, such as 22e757, 22E780 or 22E804 (manufactured by DuPont), anhydride-modified ethylene vinyl acetate, such as 30E670, 30e671, 30E753 or 30E783 (manufactured by DuPont); and acid / acrylate-modified ethylene vinyl acetate, such as 3101 or 3126 (manufactured by DuPont), anhydride-modified ethylene vinyl acetate, such as E418, 3810, 3859, 3860 or 3861 (manufactured by DuPont), anhydride-modified ethylene-vinyl acetate, such as 3930 or 39E660 (manufactured by DuPont); and anhydride-modified high-density polyethylene, such as 4033 or 40E529 (manufactured by DuPont); anhydride-modified linear low-density polyethylene, such as 4104, 4105, 4109, 4125, 4140, 4157, 4164, 41e556, 41e687, 41e710, 41e754, 41e755, 41e762, 41e766, 41e850, 41E865 or 41E871 (manufactured by DuPont); anhydride-modified low-density polyethylene, such as 4206, 4208, 4288 or 42E703 (manufactured by DuPont); or anhydride-modified polypropylene, such as 50e571, 50e662, 50e725, 50e739, 50E803 or 50E806 (manufactured by DuPont).

[0090] Other suitable impact modifiers include maleic anhydride grafted impact modifiers. Specific implementations of such impact modifiers include chemically modified ethylene acrylate copolymers, such as A560 (manufactured by DuPont), anhydride-modified polyethylene, e.g. E158 (manufactured by DuPont), an anhydride-modified polyethylene resin, such as E564 or E589 or E226 or E528 (manufactured by DuPont), anhydride-modified high-density polyethylene, such as E100 or E265 (manufactured by DuPont), anhydride-modified ethylene copolymers such as N525 (manufactured by DuPont), or chemically modified propylene copolymers such as E353 (manufactured by DuPont).

[0091] Other suitable impact modifiers include ethylene-acid copolymer resins, such as copolymers based on ethylene-methacrylic acid (EMAA) and copolymers based on ethylene-acrylic acid (EAA). Specific examples of ethylene-methacrylic acid based copolymer impact modifiers include 403, 407HS, 411HS, 0609HSA, 0903, 0903HC, 908HS, 910, 910HS, 1202HC, 599, 699, 925 and 960 (manufactured by DuPont). Specific examples of ethylene-acrylic acid based copolymers are 30707, 30907, 31001, 3990 and AE (manufactured by DuPont). Other specific examples of ethylene copolymers based on ethylene-acrylic acid (EAA) include Escor™ 5000, Escor™ 5020, Escor™ 5050, Escor™ 5080, Escor™ 5100, Escor™ 5200 and Escor™ 6000 (manufactured by Exon Mobile Chemical).

[0092] Other suitable impact modifiers include ionomers of ethylene acid copolymers. Specific examples of such impact modifiers include 1601, 1601-2, 1601-2LM, 1605, 8150, 8320, 8528 8660 (manufactured by DuPont).

[0093] In other embodiments, the impact modifier is an alkyl methacrylate-organic silicone / alkyl acrylate graft copolymer. The "alkyl methacrylate" of the graft copolymer can be selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate. The "silicone / alkyl acrylate" in the graft copolymer refers to a polymer obtained by polymerizing a mixture of an organic silicone monomer and an alkyl acrylate monomer. The organic silicone monomer can be selected from dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. The alkyl monomer can be selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and butyl methacrylate. The graft copolymer is in the form of a core-shell rubber and has a grafting rate of 5 to 90% (wt / wt), a core glass transition temperature of -150 to -20 degrees Celsius, and a shell glass transition temperature of 20 to 200 degrees Celsius. In one embodiment of the present invention, the graft copolymer is a methyl methacrylate-organic silicon / butyl acrylate graft copolymer. Specific examples include S-2001, S-2100, S-2200 and S-2501 manufactured by Mitsubishi Rayon Co., Ltd. of Japan.

[0094] Other suitable impact modifiers include the siloxane polymers mentioned in US 4,616,064, which comprise siloxane units, and at least one of carbonate, urethane or amide units.

[0095] Suitable impact modifiers also include those mentioned in paragraphs

[0043] to

[0072] of WO 2018 / 089573.

[0096] Other suitable impact modifiers include core-shell impact modifiers such as those mentioned in US 5,409,967.

[0097] The resin comprising recycled ABS polymer may also include a filler. Suitable examples of fillers include inorganic particulate materials, nanocomposites or mixtures thereof.

[0098] Suitable examples of inorganic particulate materials include inorganic oxides such as glass, MgO, SiO2, TiO2 and Sb2O3; hydroxides such as Al(OH)3 and Mg(OH)2; salts such as CaCO3, BaSO4, CaSO4 and phosphates; silicates such as talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feldspar and asbestos; metals such as boron and steel; carbon-graphite such as carbon fibers, graphite fibers and flakes, carbon nanotubes and carbon black. Suitable examples of inorganic particulate materials also include surface treated and / or surface modified SiO2 and TiO2, such as TiO2 surface modified with alumina.

[0099] Suitable examples of nanocomposites include clay-filled polymers such as clay / low density polyethylene (LDPE) nanocomposites, clay / high density polyethylene (HDPE) nanocomposites, acrylonitrile-butadiene-styrene (ABS) / clay nanocomposites, polyimide (PI) / clay nanocomposites, epoxide / clay nanocomposites, polypropylene (PP) / clay nanocomposites, poly(methyl methacrylate) (PMMA) / clay nanocomposites, and polyvinyl chloride (PVC) / clay nanocomposites; alumina-filled polymers such as epoxide / alumina nanocomposites, PI / clay nanocomposites, epoxide / clay nanocomposites, polypropylene (PP) / clay nanocomposites, poly(methyl methacrylate) (PMMA) / clay nanocomposites, and polyvinyl chloride (PVC) / clay nanocomposites; MMA / alumina nanocomposites, PI / alumina nanocomposites, PP / alumina nanocomposites, LDPE / alumina nanocomposites and cross-linked polyethylene (XLPE) / alumina nanocomposites; barium titanate-filled polymers, such as HDPE / barium titanate nanocomposites and polyetherimide (PEI) / barium titanate nanocomposites; silica-filled polymers, such as PP / silica nanocomposites, epoxide / silica nanocomposites, PVC / silica nanocomposites, PEI / silica nanocomposites, PI / silica nanocomposites, ABS / silica nanocomposites and PMMA / silica nanocomposites; and zinc oxide-filled polymers, such as LDPE / zinc oxide nanocomposites, PP / zinc oxide nanocomposites, epoxide / zinc oxide nanocomposites and PMMA / zinc oxide nanocomposites.

[0100] The resin comprising recycled ABS polymer may also include an antioxidant. Suitable examples of antioxidants include phosphites, phenols, amines, and any mixtures thereof.

[0101] The resin comprising recycled ABS polymer may also comprise a lubricant. In order to obtain toy building elements with satisfactory surface properties (such as satisfactory surface friction), the addition of a lubricant may be very important. Suitable examples of lubricants include fatty acids, fatty acid amides and bisamides, fatty acid esters, stearic acid, metal stearates, inorganic stearates, montan wax, paraffin wax, polyethylene wax, polypropylene wax, silicone-based lubricants and any mixtures thereof.

[0102] The resin comprising recycled ABS polymer may also include a flame retardant. Suitable examples of flame retardants include mineral flame retardants, such as magnesium hydroxide or aluminum hydroxide; organic flame retardants, such as carboxylic acid and organophosphorus flame retardants.

[0103] The resin comprising recycled ABS polymer may also include a colorant. Suitable examples of colorants include organic pigments, inorganic pigments, solvent dyes, zinc ferrite, carbon black, titanium dioxide, and aluminum oxide.

[0104] The resin comprising recycled ABS polymer may also include a light stabilizer and / or a UV absorber. Suitable examples of light stabilizers / UV absorbers include benzoates, benzophenones, benzotriazoles, hindered amines and triazines.

[0105] The resin comprising recycled ABS polymer may also include a plasticizer. Suitable examples of plasticizers include hydrocarbon process oils, phosphate esters such as or for example triphenyl phosphate and resorcinol bis(diphenyl phosphate), or oligomeric phosphate esters, long chain fatty acids and aromatic sulfonamides.

[0106] The type and kind of ABS waste is important for the uniformity of the ABS polymer in the resin. The more uniform the waste, the more uniform the resin. Advantageously, a resin with recycled ABS polymer of uniform length and crosslinking and butadiene sphere size is used. In one embodiment, the recycled ABS polymer is produced from ABS waste from the toy industry.

[0107] In a preferred embodiment, ABS waste is discarded toy building elements. The main advantage of using discarded toy building elements from the manufacturer's own production plant is that its chemical composition is known and it is also known how to treat the material. If the waste is color sorted before recycling, it is easier to produce recycled toy building elements with uniform color. If the waste is not color sorted before recycling, it may be necessary to first remove the colorant and then add new colorant in order to obtain a final toy building element with a satisfactory color.

[0108] Some ABS waste contains harmful additives, so their presence in recycled ABS materials is unacceptable when used to make toys such as toy building elements. Examples of such harmful additives include harmful flame retardants, such as halogenated flame retardants; plasticizers, such as phthalates and bisphenol A; harmful lubricants, such as fluoropolymers; and inorganic materials, such as cadmium and manganese. Other types of additives that may be present in waste ABS include pigments, such as iron oxide, which contribute to the continued degradation of the ABS material during the life of the item before it is disposed of as waste.

[0109] Typically, recycled ABS material must meet the requirements set out in, for example, Regulation (EC) No 1907 / 2006 and the Toy Safety Directive (2009 / 48 / EC), otherwise the ABS waste is not suitable for use in the manufacture of toy building elements.

[0110] In particular, the amount of substances classified as carcinogenic, mutagenic or reprotoxic (CMR) category 1A, 1B or 2 under Regulation (EC) No 1272 / 2008 must be below certain limits. Thus, the total content of carcinogenic substances for categories 1A and 1B must be 1000 ppm or less, while the total content of carcinogenic substances for category 2 must be 10,000 ppm or less. The total content of mutagenic substances for categories 1A and 1B must be 1000 ppm or less, while the total content of mutagenic substances for category 2 must be 10,000 ppm or less. The total content of reproductive toxic substances for categories 1A and 1B must be 3000 ppm or less, while the total content of reproductive toxic substances for category 2 must be 30,000 ppm or less.

[0111] It is also important that the metal content in ABS scrap is below the migration limits set, for example, in the Toy Safety Directive (2009 / 48 / EC), otherwise the scrap is unsuitable for use in the manufacture of toy building elements. In particular, the following migration limits must not be exceeded: Aluminium: 70,000 mg / kg; Antimony: 560 mg / kg; Arsenic: 47 mg / kg; Barium: 18,750 mg / kg; Boron: 15,000 mg / kg; Cadmium: 17 mg / kg; Chromium (III): 460 mg / kg; Chromium (IV): 0.053 mg / kg; Cobalt: 130 mg / kg; Copper: 7,700 mg / kg; Lead: 160 mg / kg; Manganese: 15,000 mg / kg; Mercury: 94 mg / kg; Nickel: 930 mg / kg; Selenium: 460 mg / kg; Strontium: 56,000 mg / kg; Tin: 180,000 mg / kg; Organic tin: 12 mg / kg; and Zinc: 46,000 mg / kg.

[0112] In order to obtain harmless ABS waste with uniform physical and chemical properties, it may be beneficial or even necessary to screen the waste before recycling. Such screening may include analytical methods for quantifying the ratio of butadiene copolymer to SAN, detecting and / or quantifying carcinogens, mutagens, substances toxic to reproduction, antioxidants, heavy metals, halogenated substances, lubricants, flame retardants, colorants, etc. Suitable analytical methods may include attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) to determine the ratio of butadiene copolymer to SAN. Thermogravimetric analysis (TGA) and / or differential scanning calorimetry-oxidation induction time (DSC-OIT) for determining the thermal oxidative stability of the waste material. X-ray fluorescence spectroscopy (XRF) for determining the amount of heavy metals and / or halogenated substances, etc. It may also be necessary to screen ABS waste for the size of butadiene spheres and study how the spheres are distributed in the SAN phase. Direct methods for determining the distribution of butadiene spheres in the SAN phase include scanning electron microscopy (SEM) and transmission electron microscopy (TEM), while indirect methods include measuring the gloss of re-injection molded components.

[0113] The invention also relates to a method for producing a toy building element. Figure 2 shown.

[0114] a) Provide and screen ABS waste,

[0115] b) recovering recycled ABS polymer from the screened ABS waste by subjecting the ABS waste of step a to a grinding and / or solvent dissolution recovery process,

[0116] c) obtaining a resin by mixing the recovered ABS polymer of step b with one or more additives and optionally one or more ABS polymers selected from the group consisting of virgin ABS polymer, chemically recycled ABS polymer recovered from pyrolysis and chemically recycled ABS polymer recovered from chemical depolymerization, and

[0117] d) manufacturing toy building elements by processing the resin of step c

[0118] Suitable resins obtained in step c and processed in step d include those mentioned above.

[0119] The recycled ABS polymer in the resin is derived from ABS scrap that has been subjected to one or more screening processes prior to introduction into the resin so that only material including non-hazardous and / or acceptable additives is introduced into the resin.

[0120] In step a, the ABS waste is screened to obtain at least one property selected from the following:

[0121] The amount of a substance classified as carcinogenic, mutagenic or toxic for reproduction (CMR) category 1A, 1B or 2 according to Regulation (EC) No 1272 / 2008,

[0122] migration limits of one or more metals selected from the group consisting of aluminum, antimony, arsenic, barium, boron, cadmium, chromium III, chromium IV, cobalt, copper, lead, manganese, mercury, selenium, strontium, tin, organotin and zinc,

[0123] The amount of oxide,

[0124] The amount of phthalates,

[0125] The amount of flame retardant,

[0126] Ratio of butadiene copolymer to SAN,

[0127] the size and size distribution of the butadiene spheres, and

[0128] Crosslinking level of butadiene spheres.

[0129] It is very important that the amount of substances classified as carcinogenic, mutagenic or reprotoxic (CMR) in accordance with Regulation (EC) No 1272 / 2008 as category 1A, 1B or 2 is below the prescribed limits, otherwise the waste is not suitable for the manufacture of toys. Therefore, the total content of carcinogenic substances in categories 1A and 1B must be 1000 ppm or less, while the total content of carcinogenic substances in category 2 must be 10000 ppm or less. The total content of mutagenic substances in categories 1A and 1B must be 1000 ppm or less, while the total content of mutagenic substances in category 2 must be 10000 ppm or less. The total content of reproductive toxic substances in categories 1A and 1B must be 3000 ppm or less, while the total content of reproductive toxic substances in category 2 must be 30000 ppm or less.

[0130] It is also important that the metal content in ABS scrap is below the migration limits set, for example, in the Toy Safety Directive (2009 / 48 / EC), otherwise the scrap is unsuitable for use in the manufacture of toy building elements. In particular, the following migration limits must not be exceeded: Aluminium: 70,000 mg / kg; Antimony: 560 mg / kg; Arsenic: 47 mg / kg; Barium: 18,750 mg / kg; Boron: 15,000 mg / kg; Cadmium: 17 mg / kg; Chromium (III): 460 mg / kg; Chromium (IV): 0.053 mg / kg; Cobalt: 130 mg / kg; Copper: 7,700 mg / kg; Lead: 160 mg / kg; Manganese: 15,000 mg / kg; Mercury: 94 mg / kg; Nickel: 930 mg / kg; Selenium: 460 mg / kg; Strontium: 56,000 mg / kg; Tin: 180,000 mg / kg; Organic tin: 12 mg / kg; and Zinc: 46,000 mg / kg.

[0131] The amount of iron oxide must also be kept at a very low level in order to avoid chemical degradation of the ABS polymer over time, in particular to avoid the formation of ABS monomers, which leads to poor mechanical properties of the manufactured toy building elements and is therefore a product safety issue. Furthermore, if the ABS waste is intended for use in the manufacture of toys, the amount of toxic compounds such as phthalates and flame retardants must be avoided.

[0132] It is also important to screen the ratio of butadiene copolymer to SAN and the size of butadiene spheres of the waste ABS material. The butadiene content in the ABS material is preferably 15-22 wt % based on the total ABS polymer. The size of the butadiene spheres is preferably less than or equal to 0.5 microns to obtain a glossy surface of the manufactured toy building elements.

[0133] In some cases, the waste ABS material may be very heterogeneous, and in such cases, it may be necessary to sort the waste ABS material prior to screening for the above-mentioned properties.

[0134] In step b, the screened ABS waste is subjected to a grinding and / or solvent dissolution recovery process to recover the recovered ABS polymer.

[0135] Figure 3 and Figure 4 A method for manufacturing toy building elements by processing a resin comprising mechanically recycled ABS polymers is shown in . In the method, screened ABS waste is ground. In the grinding step, the recycled material is crushed / cut into small pieces of material. This step is important in order to obtain a homogeneous material mixture that is easy to mix with additives and optionally other ABS polymers and is also easy to melt during the production of toy building elements, i.e. in injection molding, extrusion or additive manufacturing.

[0136] Figure 5 , 6 7 and 8 show a method for manufacturing toy building elements by processing a resin comprising chemically recycled ABS polymer. In this method, screened ABS waste is subjected to a solvent dissolution recovery process. Typically, the waste ABS material is ground prior to dissolution to facilitate dissolution of the waste material, but the grinding step is not mandatory. During the dissolution step, the ABS waste is dissolved and the ABS polymer can be separated into two phases: one phase comprising poly(styrene-co-acrylonitrile) chains, also known as a SAN phase, and the other phase comprising a butadiene copolymer, also known as butadiene spheres. In some embodiments, both the SAN phase and the butadiene spheres are recycled ( Figure 5 ), while in other embodiments, only the SAN phase is recovered ( Figure 6 and 7 ).

[0137] In step c, the ABS polymer of recovery is mixed with other compounds and forms a resin. Preferably, the mixing step is a compounding step. During mixing, one or more additives are mixed with the ABS polymer of recovery, and optionally, virgin and / or virgin ABS polymer can also be mixed into the resin. Suitable additives include impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers and / or plasticizers. Virgin and / or virgin ABS polymer can be a bio-based ABS polymer and / or a mixed bio-based polymer. In addition, the virgin ABS polymer can be an ABS polymer collected from a chemical pyrolysis recovery process or a chemical depolymerization recovery process.

[0138] In a specific preferred embodiment, Figure 4 As shown in , the waste ABS material is discarded toy building elements. In these embodiments, the addition of additives may not be necessary, because the discarded toy building elements may already have the mechanical properties required to manufacture toy building elements with the desired properties.

[0139] In step d, building brick elements are manufactured by processing the resin obtained in step c. In some embodiments, the toy building elements are manufactured by injection molding. In such embodiments, the mixing of the recycled ABS polymer with additives and / or colorants and optionally other virgin or original ecological ABS polymers can be carried out before the resin is fed to the injection molding machine. In some embodiments, the mixing can be carried out as a dry blending step or a compounding step. In other embodiments, the mixing can be carried out by using a compounding step in an extruder before the injection molding step. In other embodiments, the additives can be mixed into a masterbatch, which is then mixed with the remaining ABS resin during the injection molding machine feed. Alternatively, the mixing can be carried out during the feeding of the resin to the injection molding machine.

[0140] In other embodiments, toy building elements are manufactured by extrusion, optionally followed by molding using thermoforming or similar techniques.

[0141] In some embodiments, the toy building element is manufactured by additive manufacturing. Suitable examples of additive manufacturing techniques are those in which the toy building element is built by photopolymerization additive manufacturing or thermoplastic additive manufacturing, such as liquid-based additive manufacturing, toner-based additive manufacturing, powder-based additive manufacturing or particle-based additive manufacturing.

[0142] Preferably, the method further comprises a step wherein, before the resin obtained in step c is made into a toy building element in step d, the resin is subjected to a quality control, mainly to ensure that important mechanical properties are necessary in order to obtain a final toy building element with the desired properties. Examples of mechanical properties that are typically measured include one or more of impact strength, surface friction, surface gloss and color.

[0143] Example

[0144] In the following examples, it is described how to recycle ABS by regrinding molded components and runners and then using the regrinded material to produce new components by injection molding. In Example 1, all ABS material was recycled, and in Example 2, recycled ABS was mixed with virgin ABS and then injection molded into new components. The impact strength of the injection molded components was tested by the "Charpy V-notch test".

[0145] Charpy V-notch test

[0146] According to ISO 179-1 / 1eA, the cutting size was 6.0 × 4.0 × 50.0 mm using a notch cutter (ZNO, Zwick, Germany) with a notch tip diameter of 0.5 mm. 3 , B×W×H and molded plastic bars in the relevant materials to be tested. The notched specimens were placed under a V-notch reverse pendulum and tested in a pendulum impact tester (HOT, Zwick, Germany) according to the principle described in ISO 179-1:2010.

[0147] Example 1 Properties of ABS from Mechanical Recycling - Complete Recycling of ABS

[0148] The original ABS GP35 (supplied by INEOS Styrolution) was dried at 80°C for 4 hours. ABS was processed into plunger bars and flow channels via injection molding (Arburg, Allrounder 470E 1000-400, 30 mm screw, Germany). 10 plunger bars were tested in the Charpy V-notch test and the results are recorded in the table below as regrinding cycle 0.

[0149] The remaining flow channel and impact rod were ground into pellets in a plastic grinder. The ground ABS pellets were processed again into impact rods and flow channels, 10 impact rods were used in the Charpy V-notch test, and the results were recorded as Regrinding Cycle 1. In a similar manner, the remaining impact rods and flow channels were ground and reprocessed in up to 10 regrinding cycles.

[0150] Injection molding parameters are as follows:

[0151] Melting temperature: 240℃

[0152] Mold temperature: 30℃

[0153] The results are shown in the following table.

[0154] Regrinding cycles Relative Charpy V-notch value 0 100 1 100 5 95 10 88

[0155] The results show that one regrind cycle does not seem to affect the Charpy V-notch at all, while 5 regrind cycles result in a reduction in the relative Charpy V-notch value from 100 to 95. In the context of producing toy building elements, such a reduction may still be acceptable. A further reduction in the relative Charpy V-notch to 88 was observed after 10 regrind cycles. This indicates that toy building elements made from ABS that has been cycled 10 times will most likely have unacceptable mechanical properties due to insufficient impact strength. Therefore, in order to increase the impact strength to an acceptable level, new or additional impact modifiers need to be mixed into the recycled material.

[0156] Example 2 Properties of ABS from Mechanical Recycling - Partial Recycling of ABS

[0157] Two molds producing components of different sizes were used to test the effect of applying different amounts of mechanically recycled ABS during the injection molding process. In this study, the amount of mechanically recycled ABS was represented by the percentage of the mechanically regrinded runner system that was introduced back into the molding process of the ABS. The two molds applied in this test were configured to run with 42% and 90% regrind in the runners during the molding process. These two molds were used to investigate whether supplementing the regrind ABS with different levels of virgin ABS could help maintain good overall impact properties of the molded components. The above two molds were used to produce input material for 3 additional molds that ran with 37%, 51% and 85% regrind, respectively.

[0158] The original ABS GP35 (supplied by INEOS Styrolution) was dried at 80°C for 4 hours. ABS was processed into LEGO elements via injection molding (Arburg, Allrounder 470E 1000-400, 30 mm screw, Germany) using molds 1 and 2. The molds were fed with regrind and virgin ABS according to the table below. Due to the level of regrind introduced in the process, the molds needed to produce many shots before the entire process stabilized, i.e. before a steady-state situation was reached. The number of shots to ensure a stable process is shown in the table below.

[0159]

[0160] Once a stable process was achieved, samples of the blended material ready for molding were collected and processed into impact bars via injection molding. The molded impact bars were used for Charpy V-notch analysis and the results are shown in the table below.

[0161] Additionally, stable processed material produced by Dies 1 and 2 was used as input material for processing in Dies 3, 4, and 5. Once a stable process was achieved, material samples were collected and used to produce impact bars tested in the Charpy V-notch analysis. The results are shown in the table below.

[0162] Materials used to produce impact rods Relative Charpy V-notch value Native GP-35 100 Mold 1 (after stabilization treatment) 108 Mold 2 (after stabilization) 100 Mold 1 + Mold 3 (after stabilization treatment) 112 Mold 1 + Mold 4 (after stabilization treatment) 109 Mold 1 + Mold 5 (after stabilization treatment) 85 Mold 2 + Mold 3 (after stabilization treatment) 94 Mold 2 + Mold 4 (after stabilization treatment) 86 Mold 2 + Mold 5 (after stabilization treatment) 69

[0163] The results show that adding a certain amount of mechanically recycled ABS to virgin ABS during the injection molding process surprisingly provides an increase in the relative Charpy V-notch value. In particular, Mold 1 run with 42% regrind showed an increase in the relative Charpy V-notch value to 108%. Moreover, when the steady state material from Mold 1 was used as the input material for Mold 3, the relative Charpy V-notch value was further increased to 112% compared to using virgin material. The inventors of the present invention have observed such an increase in the relative Charpy V-notch value by several times, and it can be shown that an improved dispersion of polybutadiene spheres is obtained when recycled ABS material is mixed with virgin ABS.

[0164] The results also show that as the number of recycling cycles of ABS increases, the relative Charpy V-notch value decreases, resulting in a decrease in the impact strength of the injection molded components. The exact Charpy V-notch value that is acceptable when using recycled ABS to produce toy building elements will depend on the type of element being produced; for example, conventional Brick requirement ratio Eventually, however, regardless of the type of element, recycled ABS material is no longer able to produce toy building bricks with satisfactory mechanical properties, and new or additional impact modifiers or virgin ABS need to be mixed with recycled ABS to produce toy building elements with acceptable impact strength.

[0165] The above experimental results show that ABS can be mechanically recycled to some extent, but ultimately the mechanical properties need to be improved in order to produce toy building elements with acceptable mechanical properties, such as acceptable impact strength.

Claims

1. Toy building elements made of ABS (Acrylonitrile Butadiene Styrene) material and manufactured by processing resins comprising mechanically recycled ABS polymers and virgin ABS polymers, The mechanically recycled ABS polymer is regrinded discarded toy building elements and / or mechanically recycled ABS material from mechanically regrinded mold runner systems, and the amount of the mechanically recycled ABS polymer is 20-90 wt % based on the total amount of ABS polymer. 2 . The toy building element according to claim 1 , wherein the toy building element is manufactured by injection molding, extrusion or additive manufacturing technology or by a combination of injection molding and additive manufacturing technology.

3. A toy building element according to any one of claims 1 or 2, wherein the size of the butadiene spheres in the recycled ABS polymer is less than or equal to 0.5 micrometers.

4. The toy building element according to any one of claims 1 or 2, wherein at least a portion of the ABS polymer is a bio-based ABS polymer and / or a hybrid bio-based ABS polymer and / or an ABS polymer produced using carbon capture technology.

5. A toy building element according to any one of claims 1 or 2, wherein the total amount of ABS polymers in the resin is at least 50% by weight relative to the total weight of the resin.

6. A toy building element according to any one of claims 1 or 2, wherein the resin further comprises one or more additives selected from impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers and plasticizers.

7. A toy building element according to any one of claims 1 or 2, wherein the element is produced by injection moulding after steady state using a mould running with 20-90 wt% recycled material; and The ABS material that remains in the mold runner system and does not form the final injection molded component is ground back into pellet or flake form to be used as recycled ABS material.

8. A method for manufacturing a toy building element, comprising the steps of: a) Supply and screen ABS waste from the toy industry, b) recovering recovered ABS polymer from the screened ABS waste by subjecting the ABS waste of step a to grinding, c) obtaining a resin by mixing the recovered ABS polymer of step b with one or more additives and one or more virgin ABS polymers, and d) Manufacturing toy building elements by processing the resin of step c.

9. The method of claim 8, wherein the ABS scrap is screened for at least one property selected from the group consisting of: - ratio of butadiene copolymer to SAN, - the size and size distribution of the butadiene spheres, and - Crosslinking level of butadiene spheres.

10. The method according to any one of claims 8 or 9, wherein the recovered ABS polymer is compounded with one or more additives selected from impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers and plasticizers.

11. Method according to any one of claims 8 or 9, wherein the toy building element is manufactured by injection molding, extrusion or additive manufacturing of the resin obtained in step c or by a combination of injection molding of the resin obtained in step c and additive manufacturing.

12. The method according to any one of claims 8 or 9, wherein the resin obtained in step c is subjected to a quality control before said resin is made into a toy building element in step d.

13. The method of claim 12, wherein the quality control comprises measuring one or more mechanical properties of the resin, wherein the mechanical properties are selected from - impact strength, - surface friction, - surface gloss, and -color.

14. The method according to any one of claims 8 or 9, wherein the ABS waste is discarded toy building elements, and wherein mixing the recovered ABS polymer with one or more additives in step c is optional.

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