Toy building blocks made from recycled ABS material

Abstract

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

Description

Technical Field

[0001] The present invention relates to toy assembly elements made of recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing a resin containing recycled ABS polymer.

Background Art

[0002] Toy assembly elements have been manufactured and put on the market for many years.

[0003] Conventionally, such toy assembly elements have been made of petroleum-based polymers, such as ABS.

[0004] ABS is an engineering thermoplastic polymer produced by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The ratio may vary such that acrylonitrile is 15 to 35%, butadiene is 5 to 30%, and styrene is 40 to 60%. ABS consists of an amorphous-continuous phase and a rubbery dispersed phase. The poly(styrene-co-acrylonitrile) (SAN) copolymer forms a continuous phase and a second phase consisting 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 are obtained by the composition, thermoplasticity and characteristics of the rubbery phase, as well as the interaction between them. Thus, the SAN content and molecular weight control properties such as processability, heat resistance, surface hardness and chemical resistance. The butadiene content mainly contributes to toughness.

[0005] ABS can be produced by emulsion polymerization and bulk polymerization. ABS materials with different properties are obtained depending on whether the ABS is produced by emulsion or bulk polymerization. For example, a strong glossy surface of an ABS material can be obtained when the ABS is produced by emulsion polymerization, while a weak surface gloss is usually obtained when the ABS material is produced by bulk polymerization.

[0006] Growing concerns about the depletion of petroleum resources and the impact of global warming are encouraging the development of technologies for recycling ABS and technologies for producing ABS polymers using biomass as a renewable resource.

[0007] ABS can be produced by using biomass as a renewable resource. WO2015 / 034948 A1 describes a method for producing bio-based organic chemicals, such as bioacrylic acid, bioacrylonitrile, and bio-1,4-butadiene, using a renewable carbon source as raw material. In the first step, bio-1,3-propanediol is derived from a renewable carbon source via microbial fermentation, and in the second step, bio-1,3-propanediol is converted to bioacrylic acid, or bioacrylonitrile, or bio-1,4-butadiol.

[0008] ABS can also be produced by using materials obtained using carbon capture techniques, i.e., carbon monoxide and / or carbon dioxide captured directly from air or from gases by industrial processes. Such carbon capture techniques include, for example, absorption, adsorption, chemical looping, and membrane separation techniques. The captured carbon monoxide can then be converted into hydrocarbons, such as methanol or ethanol, which can be used as a source for creating new monomers or polymers.

[0009] ABS can also be obtained through mechanical or chemical recycling of ABS material.

[0010] Mechanical recycling of ABS involves only mechanical processes, such as crushing, washing, separation, drying, regranulation, and compounding. In a typical recycling process, waste ABS plastic is collected and washed to remove impurities. The cleaned plastic is then crushed into flakes, which can be compounded and pelletized, or reprocessed into granules.

[0011] One of the problems associated with the use of mechanically recycled ABS material is that the properties of recycled ABS material are generally inferior to those of virgin ABS material. This is due to the decomposition phenomenon that occurs during the service life of ABS and during melt-reprocessing, which accelerates the decomposition effect. During reprocessing, the ABS material is subjected to high temperatures and shear stress, which trigger different types of decomposition reactions. The degree of decomposition depends on the number of cycles and the processing temperature. In used recycled ABS, further decomposition is also expected due to exposure to light, rising temperatures, and chemicals during use. It is thought that ABS decomposes due to chain breaking and crosslinking, producing oligomeric products that can migrate to the surface, and fragile crosslinked polybutadiene particles. Chemical changes have a significantly adverse effect, for example, on impact strength, and it is necessary to improve the performance of recycled polymers by adding suitable additives or by blending them with virgin polymers.

[0012] Another issue concerning the use of mechanically recycled ABS material is the presence of hazardous and / or unacceptable additives, as well as other undesirable substances, in the waste ABS used for recycling. While ABS waste is typically cleaned before recycling, this cleaning step does not remove all additives and other undesirable substances present in the waste. Some types of additives can be hazardous and are therefore unacceptable in recycled ABS material, especially when used to manufacture toys, e.g., toy assembly components. More specifically, substances classified as carcinogenic, mutagenic, or reproductively toxic (CMR) under Regulation (EC) No 1272 / 2008, in categories 1A, 1B, or 2, are undesirable in recycled materials. The presence of toxic metals must also be avoided. Flame retardants in waste from WEEE (Waste Electrical and Electronic Equipment) are another example of an unacceptable type of additive. Other types of additives that may be present in waste ABS include pigments, e.g., iron oxide, which contribute to the continuous decomposition of the ABS material during the item's service life before the ABS item is disposed of as waste. Other types of additives may include impact modifiers that affect the impact strength of recycled ABS material, lubricants that may affect material processability and friction, and colorants that may affect both the color and mechanical properties of recycled ABS material. ABS waste may also contain undesirable substances absorbed during the use phase. Such substances may include organic solvents, cleaning agents, and food components. ABS waste may also contain decorations that include other monomers and solvents.

[0013] Another problem with the use of mechanically recycled ABS polymer is that recycled ABS is only commercially available in dark gray and black. In order to produce toys made from recycled ABS material that are colored in brighter colors, suitable coloring processes must be developed.

[0014] Chemical recycling of ABS refers to any process in which ABS waste is chemically converted back into its original monomers and / or oligomers, which can then be used to produce new virgin-like polymers to create ABS items. This type of chemical recycling process includes pyrolysis and chemical depolymerization. Chemical recycling also refers to any process in which ABS waste may be dissolved using a suitable solvent, and the dissolved ABS polymer is then recovered, typically by precipitation of the polymer or by evaporation of the solvent. This type of chemical recycling process is typically called "solvent dissolution."

[0015] Pyrolysis refers to the breakdown of ABS material at elevated temperatures without oxygen. Pyrolysis breaks down the plastic into a pyrolysis oil, which can be further refined. Novel virgin-like polymers can then be produced from the resulting oil by known polymerization processes.

[0016] Chemical depolymerization is the process of breaking down a polymer into monomers, oligomers, or mixtures of monomers and / or oligomers, and / or intermediates thereof, using chemicals. The process removes additives and colorants from the monomers / intermediates. New virgin-like polymers can be produced by polymerizing monomers. Currently, there are no commercially available technologies suitable for the depolymerization of ABS waste. However, new virgin ABS polymers can be produced by polymerizing monomers recovered from the depolymerization of other types of plastic waste. For example, as described in WO2016 / 049782, styrene monomers can be recovered by the depolymerization of polystyrene.

[0017] Solvent dissolution involves the selective extraction of polymers using a solvent. Any additives and colorants are removed, and the resulting polymer is recovered, typically by precipitation or evaporation of the solvent. The polymer chains and structure remain intact. Techniques for recycling ABS based on dissolution have also been developed, with several solvents, such as acetone and tetrahydrofuran (THF), suggested for dissolving ABS. [Prior art documents] [Patent Documents]

[0018] [Patent Document 1] WO2015 / 034948 A1 [Patent Document 2] WO2016 / 049782 [Patent Document 3] US3,005,282 [Patent Document 4] US05 / 877,800 [Patent Document 5] WO2014 / 005591 [Patent Document 6] US4,616,064 [Patent Document 7] WO2018 / 089573 Paragraphs

[0043] to

[0072] [Patent Document 8] US5,409,967 [Overview of the Initiative] [Problems that the invention aims to solve]

[0019] One of the problems with using ABS polymers recovered from solvent dissolution recycling processes is that solvent extraction also removes all additives. This means that recycled ABS material may lack the desired properties, such as viscosity, mold release, friction, fillers, and flame retardants, and may require new protective additives, such as heat stabilizers, antioxidants, and UV stabilizers.

[0020] Another problem related to the use of ABS polymers recovered from the solvent dissolution recycling process is that the solvent extraction contains a mixture of different SAN chains and butadiene spheres. Compensating for the unpredictable mixture of material components is a difficult problem. Therefore, it may be necessary to add short-chain or long-chain SAN to modify the rheology or degree of curing, and it may be necessary to add butadiene spheres to improve the impact properties. It may also be necessary to add different types of additives to compensate for the loss of additives during the solvent dissolution process.

[0021] The main problem related to the use of recycled ABS is the recovery of a polymer composition that is not very uniform compared to virgin polymer compositions, regardless of how it is manufactured. The degree of variation is mainly determined by the waste material: the more uniform the waste material, the lower the degree of variation. Recycled ABS is expected to have high variability with respect to the ratio between styrene, butadiene and acrylonitrile, the length of the SAN copolymer chains, the size and size distribution of the butadiene spheres, and the extent of SAN grafting to the surface of the butadiene spheres. Therefore, further significant efforts are required to produce a suitable and useful recycled ABS for manufacturing items, such as toy assembly elements, in order to obtain items with satisfactory properties, such as satisfactory impact strength, surface friction and color. Specifically, when the production of items with a glossy surface is targeted, it is necessary to recognize in advance that the ABS waste material was produced by emulsion polymerization, and since the size of the butadiene spheres in the ABS material is known to be important for obtaining the glossy surface of the finished item, it is important to contain butadiene spheres of a suitable size.

Means for Solving the Problems

[0022] The present invention relates to a toy assembly element made of recycled ABS (acrylonitrile-butadiene-styrene) material and manufactured by processing a resin containing a recycled ABS polymer. The inventors have surprisingly found that a toy assembly element can be manufactured by processing a resin containing a recycled ABS polymer.

[0023] In a first aspect, the present invention relates to a toy assembly element made from recycled ABS material.

[0024] In a second aspect, the present invention relates to a method for manufacturing toy assembly elements made from recycled ABS material. [Brief explanation of the drawing]

[0025] [Figure 1] This diagram shows the traditional box-shaped LEGO® bricks, specifically the 2x4 block type. [Figure 2] This figure shows a method for manufacturing toy assembly elements by processing resins containing mechanically recycled ABS polymer and / or chemically recycled ABS polymer recovered from a melting and recycling process. [Figure 3] This figure shows a method for manufacturing toy assembly elements by processing resin containing mechanically recycled ABS polymer. [Figure 4] This figure shows a method for manufacturing toy assembly elements by processing resin containing mechanically recycled ABS polymer, which is a toy assembly element made from discarded ABS material. [Figure 5] This figure shows a method for manufacturing toy assembly elements by processing a resin containing chemically recycled ABS polymer recovered from a melting and recycling process. In this embodiment, both the SAN phase and the butadiene spheres are recycled. [Figure 6] This figure shows a method for manufacturing toy assembly elements by processing a resin containing chemically recycled ABS polymer recovered from a melting and recycling process. In this embodiment, only the SAN phase is recycled and mixed with additives and virgin butadiene, and optionally with further ABS polymer. [Figure 7]This figure shows a method for manufacturing toy assembly elements by processing a resin containing chemically recycled ABS polymer recovered from a melting and recycling process. In this embodiment, only the SAN phase is recycled and mixed with virgin ABS with a high content of additives and butadiene. [Modes for carrying out the invention]

[0026] This invention relates to toy assembly elements made from recycled ABS material.

[0027] As used herein, the term “toy building element” includes traditional toy building elements in the form of box-shaped building blocks having projections on the top surface and complementary tubular parts on the bottom surface. Traditional box-shaped toy building blocks are shown in Figure 1. Traditional box-shaped toy building blocks were first disclosed in US 3,005,282 and are widely sold under the trade names LEGO® and LEGO® DUPLO®. The term also includes other similar box-shaped building blocks produced by companies other than the LEGO Group and therefore sold under other trademarks other than LEGO.

[0028] The term “toy building element” also includes other types of toy building elements that form parts of a toy building set, typically consisting of multiple building elements that fit together and can therefore be connected to one another. Such toy building sets are also sold under the trademark LEGO, e.g., LEGO® bricks, LEGO® Technic, and LEGO® DUPLO®. Some of these toy building sets include toy building figures, e.g., LEGO® Minifigures (see, e.g., US05 / 877,800), which have a complementary tubular section on their underside, so that the figure can be connected to other toy building elements in the toy building set. Such toy building figures are also encompassed by the term “toy building element.” This term also includes similar toy building elements produced by companies other than the LEGO Group and therefore sold under other trademarks that are not LEGO.

[0029] Toy building elements are available in a wide variety of shapes, sizes, and colors. One difference between LEGO® bricks and LEGO® DUPLO® bricks is size; LEGO® DUPLO® bricks are twice the size of LEGO® bricks in all dimensions. A traditional box-shaped LEGO® toy building block with 4x2 protrusions on top measures approximately 3.2 cm long, 1.6 cm wide, and 0.96 cm high (excluding protrusions), with each protrusion having a diameter of approximately 0.48 cm. In contrast, a LEGO® DUPLO® brick with 4x2 protrusions on top measures approximately 6.4 cm long, 3.2 cm wide, and 1.92 cm high (excluding protrusions), with each protrusion having a diameter of approximately 0.96 cm.

[0030] The toy assembly elements are made from recycled ABS material, which is manufactured by processing resins containing mechanically recycled ABS polymer and / or chemically recycled ABS polymer recovered from a solvent dissolution recycling process.

[0031] As used herein, the term “recycled ABS material” refers to ABS material obtained by processing a resin containing recycled ABS polymer. The recycled ABS polymer is obtained from ABS waste. The ABS waste may be mechanically recycled ABS material or chemically recycled ABS material. The recycled ABS polymer in the resin is mechanically recycled ABS polymer and / or chemically recycled ABS polymer recovered from a solvent dissolution recycling process. Furthermore, the resin may further contain virgin ABS polymer and / or chemically recycled ABS polymer recovered from a pyrolysis recycling process and / or recycled ABS polymer recovered from a chemical depolymerization recycling process.

[0032] "Mechanically recycled ABS material" refers to ABS material recovered through mechanical recycling. Mechanical recycling involves only mechanical processes, such as crushing, washing, separation, drying, regranulation, and compounding. In a typical recycling process, ABS waste is collected and washed to remove impurities. The cleaned plastic is then crushed into flakes, which can be compounded and pelletized, or reprocessed into granules.

[0033] "Chemically recycled ABS material" includes ABS material made from ABS waste material that has undergone thermal decomposition, chemical depolymerization, solvent dissolution, or any other suitable chemical recycling process.

[0034] "Pyrolysis" refers to the breakdown of ABS material into a pyrolysis oil at elevated temperatures without oxygen. Novel virgin-like polymers can then be produced from oils generated by known polymerization processes.

[0035] "Chemical depolymerization" refers to the process by which a polymer is broken down into monomers, mixtures of monomers, or intermediates using chemical agents. New virgin-like polymers can be produced by monomer polymerization.

[0036] "Solvent dissolution" refers to the selective extraction of polymers using a solvent. The extracted polymer is recovered by precipitation or by evaporation of the solvent. The polymer chains and structure remain intact. Butadiene is present in ABS as individual spheres. Solvent dissolution does not alter the chemical bonds in the polymer chains, but there is a risk regarding physical changes in the shape and size of the butadiene spheres. Therefore, it may be necessary to dispose of the butadiene spheres during the solvent dissolution process.

[0037] The term "recycled ABS polymer" refers to ABS polymers contained in mechanically recycled ABS waste or polymers chemically recovered from ABS waste in solvent dissolution processes. This term also refers to virgin-like ABS polymers produced in pyrolysis recycling processes or chemical depolymerization recycling processes. When this term refers to virgin-like ABS polymers, it also includes polymers in which only one or two monomers are recycled by pyrolysis or chemical depolymerization. For example, this term may include ABS polymers in which some or all of the styrene monomer is recycled by the chemical depolymerization of polystyrene, while the acrylonitrile and butadiene monomers may be non-recycled monomers produced by conventional manufacturing methods.

[0038] In some embodiments, the recycled ABS material comprises recycled ABS polymers obtained from mechanically recycled ABS waste. In other embodiments, the recycled ABS material comprises recycled ABS polymers obtained from chemically recycled ABS waste, the ABS polymers being recovered using a solvent dissolution recycling process. In yet another embodiment, the recycled ABS material comprises a mixture of recycled ABS polymers obtained from mechanically recycled ABS waste and chemically recycled ABS waste, the ABS polymers being recovered using a solvent dissolution recycling process. In further embodiments, the recycled ABS material may further comprise virgin ABS polymers and / or virgin-like ABS polymers, i.e., recycled ABS polymers recovered from a pyrolysis recycling process and / or a chemical depolymerization recycling process.

[0039] Toy assembly elements are manufactured by injection molding, additive manufacturing techniques, or a combination of injection molding and additive manufacturing techniques. Alternatively, toy assembly elements are manufactured by extrusion, optionally followed by thermoforming or similar molding techniques.

[0040] Injection molding of toy assembly elements is a traditional method of manufacturing toy assembly blocks. This manufacturing technique has been in use for many years and is well known to those skilled in the art. In some embodiments, toy assembly elements are manufactured by injection molding of a resin containing recycled ABS polymer. In other embodiments, toy assembly elements are manufactured by two-component injection molding, one of which is a resin containing recycled ABS polymer. In yet another embodiment, toy assembly elements are products of multi-component injection molding, at least one of which is a resin containing recycled ABS polymer.

[0041] In recent years, new additive manufacturing techniques have been developed for assembling objects, for example, from polymer materials. As used herein, the terms “additive manufacturing” or “manufactured additively” mean that a block is assembled in an additive manner, that is, by adding new material to a substrate or a newly added material, by repeatedly solidifying thin liquid layers or droplets on a substrate or a previously solidified liquid layer or droplet, by repeatedly printing with a thermoplastic polymer material on a substrate or a previously printed plastic material, or by repeatedly brazing plastic materials in an additive manner, for example, using a laser.

[0042] In some embodiments, toy assembly elements are manufactured by injection molding. In other embodiments, toy assembly elements are manufactured by additive manufacturing. In yet another embodiment, toy assembly elements are manufactured by a combination of injection molding and additive manufacturing. Such combined manufacturing techniques are described, for example, in WO2014 / 005591, in which toy assembly elements with advanced design individuality are manufactured by adding material layer by layer to the surface of conventional injection-molded box-shaped assembly blocks.

[0043] In yet another embodiment, the toy assembly elements are manufactured by extrusion. Optionally, the extrusion process is followed by molding using thermoforming or a similar technique.

[0044] It is well known that the size of butadiene spheres in ABS material affects the glossiness of the surface of items manufactured from ABS material. In the toy industry, a glossy surface is very often a target. Therefore, in a preferred embodiment, the size of butadiene spheres in recycled ABS material is 0.5 micrometers or less.

[0045] One of the main problems in manufacturing new toy assembly elements using recycled ABS material is the loss of mechanical properties, specifically impact strength. This problem can sometimes be solved, at least partially, by adding virgin ABS polymer to the resin before processing it into toy assembly elements. Alternatively, this problem can be solved by adding virgin-like ABS polymer, or a mixture of virgin and virgin-like ABS polymers.

[0046] In one embodiment, the resin further comprises a virgin ABS polymer. In some embodiments, the amount of virgin ABS polymer is at least 5 wt% of the total amount of polymers in the resin, for example, at least 10 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt%, or at least 90 wt%. In other embodiments, the amount of virgin ABS polymer is in the range of 5 to 95 wt% of the total amount of polymers in the resin, for example, 10 to 95 wt%, 30 to 95 wt%, 50 to 95 wt%, 70 to 95 wt%, or 80 to 95 wt%. In yet another embodiment, the amount of virgin ABS polymer is in the range of 5 to 50 wt% of the total amount of polymers in the resin, for example, 5 to 30 wt%, 5 to 20 wt%, or 5 to 10 wt%.

[0047] In other embodiments, the resin comprises a virgin-like ABS polymer. As used herein, the term “virgin-like ABS polymer” means a chemically recycled ABS polymer recovered from a pyrolysis recycling process and / or a chemical depolymerization recycling process. In some embodiments, the amount of virgin-like ABS polymer is at least 5 wt% of the total amount of polymers in the resin, e.g., at least 10 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt%, or at least 90 wt%. In other embodiments, the amount of virgin-like ABS polymer is in the range of 5 to 95 wt% of the total amount of polymers in the resin, e.g., 10-95 wt%, 30-95 wt%, 50-95 wt%, 70-95 wt%, or 80-95 wt%. In yet another embodiment, the amount of virgin-like ABS polymer is in the range of 5-50 wt% of the total amount of polymers in the resin, e.g., 5-30 wt%, 5-20 wt%, or 5-10 wt%.

[0048] In yet another embodiment, the resin comprises a mixture of virgin and virgin-like ABS polymers. In some embodiments, the combined amount of virgin and virgin-like ABS polymers is at least 5 wt% of the total amount of polymers in the resin, for example, at least 10 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt%, or at least 90 wt%. In other embodiments, the combined amount of virgin and virgin-like ABS polymers is in the range of 5 to 95 wt% of the total amount of polymers in the resin, for example, 10 to 95 wt%, 30 to 95 wt%, 50 to 95 wt%, 70 to 95 wt%, or 80 to 95 wt%. In yet another embodiment, the combined amount of virgin and virgin-like ABS polymers is in the range of 5 to 50 wt% of the total amount of polymers in the resin, for example, 5 to 30 wt%, 5 to 20 wt%, or 5 to 10 wt%.

[0049] In a preferred embodiment, the recycled ABS waste is discarded toy assembly elements, and therefore the recycled material is identical to the virgin material, except that the recycled material is processed into toy assembly elements and then crushed into pellets or flakes. In such cases, it has been surprisingly found that toy assembly elements made solely from mechanically recycled toy assembly elements possess satisfactory mechanical properties, namely impact strength, and can be manufactured without even incorporating new additives to improve the mechanical properties, such as impact resistance modifiers.

[0050] In some embodiments, the resin does not contain any virgin ABS polymer. In other embodiments, the amount of virgin ABS polymer is in the range of 0 to 95 wt% of the total amount of polymer in the resin, for example, 0 to 50 wt%, 0 to 25 wt%, 0 to 10 wt%, or 0 to 5 wt%.

[0051] The weight ratio between mechanically recycled ABS polymer and virgin ABS polymer can range from 100:0 to 1:99, for example, 100:0 to 10:90, 90:10 to 50:50, or 50:50 to 90:10.

[0052] In one embodiment, recycled ABS waste is subjected to a solvent dissolution recycling process. In this process, the ABS polymer from the waste is dissolved in a solvent, and the dissolved ABS polymer is then recovered, typically by precipitation of the polymer or by evaporation of the solvent. In the dissolved state, the polymer may separate into two phases; one phase contains poly(styrene-co-acrylonitrile) chains and is also called the SAN phase, and the other phase contains butadiene copolymer and is also called butadiene spheres.

[0053] In some embodiments, it may be preferable to recycle both the SAN phase and the butadiene spheres, while in other embodiments, it may be preferable to recycle only the SAN phase. In some cases where only the SAN phase is preferably recycled, the recycled SAN copolymer may be mixed with butadiene, which may be virgin butadiene, recycled butadiene, or a mixture thereof. In other cases where only the SAN phase is preferably 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, recycled ABS, or a mixture thereof.

[0054] As used herein, the term “ABS with a high butadiene content” means ABS having at least 20 wt% butadiene.

[0055] In yet another embodiment, the resin comprises mechanically recycled ABS polymer and chemically recycled ABS polymer recovered from a solvent dissolution recycling process. In some embodiments, the resin further comprises virgin ABS polymer.

[0056] Alternatively, the resin may include mechanically recycled ABS polymer, recycled SAN copolymer, and further, ABS having a high butadiene content. The ABS having a high butadiene content may be virgin ABS, recycled ABS, or a mixture thereof.

[0057] In other embodiments, the resin comprises a mechanically recycled ABS polymer and a SAN phase recovered from ABS waste subjected to a solvent dissolution recycling process. In this embodiment, it may be preferable to further add butadiene or ABS having a high content of butadiene, or a mixture thereof. The butadiene and ABS having a high content of butadiene may be of virgin or recycled origin, or a mixture thereof.

[0058] In actual injection molding systems, the amount of recycled ABS is determined by the volume ratio of the mold and the mold runner system. When starting a new production run, the mold is supplied with virgin material from the first run. Material that remains in the runner system and therefore does not form part of the element that will ultimately be injection molded is crushed again into pellets or flakes, mixed with the virgin material, and used as recycled material, which is then supplied back to the mold. This recirculation continues until a steady state is achieved, and the amount of recycled material represents a certain percentage of the input material, with the remainder being virgin material. This certain percentage of recycled material is called "% of recycled material after steady state."

[0059] The inventors unexpectedly found that flowing a low percentage of recycled material after steady state resulted in a significant improvement in the Charpy v-notch of the molded element produced in the mold. A detailed example described in Example 2 is a mold (Mold 1) through which 42% of the recycled material after steady state flowed, producing a molded test piece with a relative Charpy v-notch value of 108%. Another mold (Mold 2) through which 90% of the recycled material after steady state flowed did not show a decrease in the relative Charpy v-notch value. These findings were highly unexpected, as a decrease in the relative Charpy v-notch value was expected when ABS material was recycled.

[0060] Therefore, in a detailed preferred embodiment of the present invention, the toy assembly elements are produced by injection molding using a mold through which 20-95 wt%, for example 30-90 wt%, of the recycled material after steady state flows.

[0061] The resins used in toy assembly elements may include bio-based ABS polymers and / or hybrid bio-based ABS polymers.

[0062] As used herein, the term “bio-based ABS polymer” means an ABS polymer produced by the chemical or biochemical polymerization of monomers derived from biomass. In some embodiments, the bio-based polymer is produced by the chemical polymerization of monomers derived entirely from biomass. In other embodiments, the bio-based polymer is produced by the biochemical polymerization of monomers derived entirely from biomass.

[0063] As used herein, the term “hybrid bio-based ABS polymer” means an ABS polymer produced by polymerization in which at least one ABS monomer is derived from biomass and at least one ABS monomer is derived from petroleum, petroleum by-products, or petroleum-derived raw materials. The ABS monomer may be a virgin monomer, a chemically recycled monomer, or a mixture of virgin and recycled monomers. The polymerization process is typically a chemical polymerization process.

[0064] 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 yet another embodiment, at least a portion of the recycled ABS polymer and at least a portion of the virgin ABS polymer are bio-based ABS polymers and / or hybrid bio-based ABS polymers.

[0065] In yet another embodiment, the toy assembly element may include an ABS polymer produced using carbon capture technology. As used herein, the term “ABS polymer produced using carbon capture technology” means a polymer containing carbon atoms from carbon monoxide and / or carbon dioxide captured directly from air or from gases by industrial processes.

[0066] In one embodiment, the total amount of ABS polymer in the resin is at least 50 wt% of the total weight of the resin. In another embodiment, the total amount of ABS polymer is at least 60 wt%, or at least 70 wt%, or at least 80 wt%, of the total weight of the resin. In yet another embodiment, the total amount of ABS polymer is at least 85 wt%, for example, at least 90 wt%, of the total weight of the resin.

[0067] In another embodiment, the total amount of ABS polymer in the resin is 50-99 wt% of the total weight of the resin. In yet another embodiment, the total amount of ABS polymer is 60-95 wt%, or 70-90 wt%, or 80-85 wt%, of the total weight of the resin. In yet another embodiment, the total amount of ABS polymer is 85-97 wt%, or 90-97 wt%, or 90-95 wt%, or 90-92 wt%, of the total weight of the resin.

[0068] As used herein, the term “total amount of ABS polymer in resin” means the total amount of ABS polymer in 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.

[0069] To improve the properties of toy assembly elements manufactured by processing resin, it may be beneficial to add additives to resins containing recycled ABS polymer. In some embodiments, the resin containing recycled ABS polymer includes one or more additives, such as impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers, and plasticizers.

[0070] The impact modifier may be a reactive impact modifier or a non-reactive impact modifier. In some embodiments, the resin of the recycled ABS polymer may contain both reactive and non-reactive impact modifiers. In preferred embodiments, the resin contains a reactive impact modifier.

[0071] As used herein, the term “impact modifier” means an agent that, when added to a resin, enhances the impact strength of injection-molded ABS elements.

[0072] Reactive impact modifiers have functionalized end groups. Functionalization serves two purposes: 1) to bond the impact modifier to the polymer matrix, and 2) to modify the interfacial energy between the polymer matrix and the impact modifier in order to improve dispersion. Preferred examples of such functionalized end groups include glycidyl methacrylate, maleic anhydride, and carboxylic acids.

[0073] In the present invention, reactive impact modifiers are preferred. In preferred embodiments, the impact modifier is a copolymer of formula X / Y / Z, where X is an aliphatic or aromatic hydrocarbon polymer having 2 to 8 carbon atoms, Y is a moiety containing an acrylate or methacrylate having 3 to 6 and 4 to 8 carbon atoms, respectively, and Z is a moiety containing methacrylic acid, glycidyl methacrylate, maleic anhydride, or a carboxylic acid.

[0074] In one preferred embodiment, the impact-resistant modifier is of the formula: [C1] (In the formula, n is an integer from 1 to 4. m is an integer from 0 to 5. k is an integer from 0 to 5. R can be described as an alkyl group consisting of 1 to 5 carbon atoms or 1 hydrogen atom.

[0075] X constitutes 40-90% (wt / wt) of the impact resistance modifier, Y constitutes 0-50% (wt / wt), for example 10-40% (wt / wt), preferably 15-35% (wt / wt), most preferably 20-35% (wt / wt), and Z constitutes 0.5-20% (wt / wt), preferably 2-10% (wt / wt), most preferably 3-8% (wt / wt).

[0076] In other embodiments, X constitutes 70-99.5% (wt / wt), preferably 80-95% (wt / wt), most preferably 92-97% (wt / wt) of the impact resistance modifier, Y constitutes 0% (wt / wt) of the impact resistance modifier, and Z constitutes 0.5-30% (wt / wt), preferably 5-20% (wt / wt), most preferably 3-8% (wt / wt) of the impact resistance modifier.

[0077] Preferred examples of specific impact modifiers that can be used in the resins of the present invention include ethylene-ethylene methacrylate glycidyl and ethylene-butyl methacrylate glycidyl. Commercially available impact modifiers include Paraloid® EXM-2314 (an acrylic copolymer from Dow Chemical Company), Lotader® AX8700, Lotader® AX8900, Lotader AX8750®, Lotader® AX8950 and Lotader® AX8840 (manufactured by Arkema), and Elvaloy® PTW (manufactured by DuPont).

[0078] Other suitable examples of specific impact modifiers that can be used in the resin of the present invention include anhydrous modified ethylene acrylate. Commercially available impact modifiers include Lotader® 3210, Lotader® 3410, Lotader® 4210, Lotader® 3430, Lotader® 4402, Lotader® 4503, Lotader® 4613, Lotader® 4700, Lotader® 5500, Lotader® 6200, Lotad Includes er(registered trademark)8200, Lotader(registered trademark)HX8210, Lotader(registered trademark)HX8290, Lotader(registered trademark)LX4110, Lotader(registered trademark)TX8030 (manufactured by Arkema), Bynel(registered trademark)21E533, Bynel(registered trademark)21E781, Bynel(registered trademark)21E810, and Bynel(registered trademark)21E830 (manufactured by DuPont).

[0079] In other embodiments, the impact resistance modifier may be modified ethylene vinyl acetate, e.g., Bynel® 1123 or Bynel® 1124 (manufactured by DuPont), acid-modified ethylene acrylate, e.g., Bynel® 2002 or Bynel® 2022 (manufactured by DuPont), modified ethylene acrylate, e.g., Bynel® 22E757, Bynel® 22E780 or Bynel® 22E804 (manufactured by DuPont), or Water-modified ethylene vinyl acetate, e.g., Bynel® 30E670, Bynel® 30E671, Bynel® 30E753 or Bynel® 30E783 (manufactured by DuPont) and acid / acrylate-modified ethylene vinyl acetate, e.g., Bynel® 3101 or Bynel® 3126 (manufactured by DuPont), anhydride-modified ethylene vinyl acetate, e.g., Bynel® E418, Bynel® 3810, Bynel® Bynel® 3859, Bynel® 3860 or Bynel® 3861 (manufactured by DuPont), anhydrous modified ethylene vinyl acetate, e.g., Bynel® 3930 or Bynel® 39E660 (manufactured by DuPont), and anhydrous modified high-density polyethylene, e.g., Bynel® 4033 or Bynel® 40E529 (manufactured by DuPont), and anhydrous modified linear low-density polyethylene, e.g., Bynel® 4104 Bynel(registered trademark) 4105, Bynel(registered trademark) 4109, Bynel(registered trademark) 4125, Bynel(registered trademark) 4140, Bynel(registered trademark) 4157, Bynel(registered trademark) 4164, Bynel(registered trademark) 41E556, Bynel(registered trademark) 41E687, Bynel(registered trademark) 41E710, Bynel(registered trademark) 41E754, Bynel(registered trademark) 41E755, Bynel(registered trademark) 41E762, Bynel(registered trademark) 41E766, Bynel(registered trademark) 41E850,Bynel® 41E865 or Bynel® 41E871 (manufactured by DuPont), anhydrous modified low-density polyethylene, such as Bynel® 4206, Bynel® 4208, Bynel® 4288, or Bynel® 42E703 (manufactured by DuPont), or anhydrous modified polypropylene, such as Bynel® 50E571, Bynel® 50E662, Bynel® 50E725, Bynel® 50E739, Bynel® 50E803, or Bynel® 50E806 (manufactured by DuPont).

[0080] Other suitable impact modifiers include maleic anhydride graft impact modifiers. Specific examples of such impact modifiers include chemically modified ethylene acrylate copolymers, e.g., Fusabond® A560 (manufactured by DuPont); anhydride-modified polyethylene, e.g., Fusabond® E158 (manufactured by DuPont); anhydride-modified polyethylene resins, e.g., Fusabond® E564 or Fusabond® E589 or Fusabond® E226 or Fusabond® E528 (manufactured by DuPont); anhydride-modified high-density polyethylene, e.g., Fusabond® E100 or Fusabond® E265 (manufactured by DuPont); anhydride-modified ethylene copolymer, e.g., Fusabond® N525 (manufactured by DuPont); or chemically modified propylene copolymer, e.g., Fusabond® E353 (manufactured by DuPont).

[0081] Further suitable impact modifiers include ethylene-acid copolymer resins, such as ethylene-methacrylic acid (EMAA)-based copolymers and ethylene-acrylic acid (EAA)-based copolymers. Specific examples of ethylene-methacrylic acid-based copolymer impact modifiers include Nucrel® 403, Nucrel® 407HS, Nucrel® 411HS, Nucrel® 0609HSA, Nucrel® 0903, Nucrel® 0903HC, Nucrel® 908HS, Nucrel® 910, Nucrel® 910HS, Nucrel® 1202HC, Nucrel® 599, Nucrel® 699, Nucrel® 925, and Nucrel® 960 (manufactured by DuPont). Specific examples of ethylene-acrylic acid (EAA)-based copolymers include Nucrel® 30707, Nucrel® 30907, Nucrel® 31001, Nucrel® 3990, and Nucrel® AE (manufactured by DuPont). Other specific examples of ethylene in ethylene-acrylic acid (EAA)-based copolymers include Escor® 5000, Escor® 5020, Escor® 5050, Escor® 5080, Escor® 5100, Escor® 5200, and Escor® 6000 (manufactured by ExonMobile Chemical).

[0082] Other more suitable impact modifiers include ionomers of ethylene acid copolymers. Specific examples of such impact modifiers include Surlyn® 1601, Surlyn® 1601-2, Surlyn® 1601-2LM, Surlyn® 1605, Surlyn® 8150, Surlyn® 8320, Surlyn® 8528, and Surlyn® 8660 (manufactured by DuPont).

[0083] In other embodiments, the impact modifier is an alkyl methacrylate-silicone / alkyl acrylate graft copolymer. The "alkyl methacrylate" in the graft copolymer may be selected from the group consisting of 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 a silicone monomer and an alkyl acrylate monomer. The silicone monomer may be selected from the group consisting of dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. The alkyl monomer may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, and butyl methacrylate. Graft copolymers are in the form of core-shell rubber and have a graft ratio of 5 to 90% (wt / wt), a core glass transition temperature of -150 to -20°C, and a shell glass transition temperature of 20 to 200°C. In one embodiment of the present invention, the graft copolymer is a methyl methacrylate-silicone / butyl acrylate graft copolymer. Specific examples include S-2001, S-2100, S-2200, and S-2501 manufactured by Mitsubishi Rayon Co., Ltd. of Japan.

[0084] Other suitable impact modifiers include siloxane polymers, as mentioned in US4,616,064, which contain siloxane units and at least one carbonate, urethane, or amide unit.

[0085] Suitable impact modifiers include those mentioned in paragraphs

[0043] to

[0072] of WO2018 / 089573.

[0086] Other suitable impact modifiers include core-shell impact modifiers, such as those mentioned in US 5,409,967.

[0087] Resins containing recycled ABS polymer may also contain fillers. Suitable examples of fillers include inorganic particulate materials, nanocomposite materials, or mixtures thereof.

[0088] Suitable examples of inorganic particulate materials include inorganic oxides, e.g., glass, MgO, SiO2, TiO2, and Sb2O3; hydroxides, e.g., Al(OH)3 and Mg(OH)2; salts, e.g., CaCO3, BaSO4, CaSO4, and phosphates; silicates, e.g., talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feldspar, and asbestos; metals, e.g., boron and steel; and carbon-graphite, e.g., 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, e.g., alumina surface-modified TiO2.

[0089] Suitable examples of nanocomposite materials 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, epoxy / clay nanocomposites, polypropylene (PP) / clay nanocomposites, poly(methyl methacrylate) (PMMA) / clay nanocomposites and polyvinyl chloride (PVC) / clay nanocomposites; alumina-filled polymers, such as epoxy / alumina nanocomposites, PMMA / alumina nanocomposites, PI / alumina nanocomposites, PP / alumina nanocomposites, LDPE / A Lumina nanocomposites and crosslinked 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, epoxy / 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, epoxy / zinc oxide nanocomposites and PMMA / zinc oxide nanocomposites.

[0090] Resins containing recycled ABS polymer may also contain antioxidants. Preferred examples of antioxidants include phosphites, phenols, amines, and mixtures thereof.

[0091] Resins containing recycled ABS polymer may also contain lubricants. The addition of lubricants can be extremely important in obtaining toy assembly elements with satisfactory surface properties, such as satisfactory surface friction. 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 mixtures thereof.

[0092] Resins containing recycled ABS polymer may also contain flame retardants. Suitable examples of flame retardants include inorganic flame retardants, such as magnesium hydroxide or aluminum, and organic flame retardants, such as carboxylic acid and organophosphorus flame retardants.

[0093] Resins containing recycled ABS polymer may also contain colorants. Suitable examples of colorants include organic pigments, inorganic pigments, oil-soluble dyes, zinc ferrite, carbon black, titanium dioxide, and aluminum oxide.

[0094] Resins containing recycled ABS polymer may also contain light stabilizers and / or UV absorbers. Suitable examples of light stabilizers / UV absorbers include benzoates, benzophenones, benzotriazoles, hindered amines, and triazines.

[0095] Resins containing recycled ABS polymer may also contain plasticizers. Suitable examples of plasticizers include hydrocarbon process oils, phosphate esters such as triphenyl phosphate and resorcinol bis(diphenyl phosphate) or oligomeric phosphates, long-chain fatty acids, and aromatic sulfonamides.

[0096] The type and composition of the ABS waste material are important for the uniformity of the ABS polymer in the resin. The more uniform the waste material, the more uniform the resin will be. It is advantageous to use a resin having recycled ABS polymer with uniform length and crosslinking, as well as the size of the butadiene spheres. In one embodiment, the recycled ABS polymer is produced from ABS waste material from the toy industry.

[0097] In a preferred embodiment, the ABS waste material is discarded toy assembly elements. The main advantage of using toy assembly elements discarded from a manufacturer's own production plant is that their chemical composition is known, as is how the material is processed. If the waste material is color-sorted before recycling, it may be easier to produce recycled toy assembly elements with a uniform color. If the waste material is not color-sorted before recycling, it may be necessary to first remove the colorants and then add new colorants to obtain final toy assembly elements with a satisfactory color.

[0098] Some ABS waste materials contain harmful additives, and therefore their presence is unacceptable in recycled ABS material if used to manufacture toys, such as toy assembly 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 continuous decomposition of the ABS material during the service life of the item before the ABS item is disposed of as waste.

[0099] In general, recycled ABS material must meet the requirements specified, for example, in Regulation (EC) No 1907 / 2006 and the Toy Safety Directive (2009 / 48 / EC); otherwise, ABS waste material is not suitable for use in the manufacture of toy assembly elements.

[0100] More specifically, the amounts of substances classified as carcinogenic, mutagenic, or reproductively toxic (CMR) under Regulation (EC) No. 1272 / 2008, category 1A, 1B, or 2, must be below the specified limits. Therefore, the total content of carcinogenic substances in categories 1A and 1B must be no more than 1000 ppm, while the total content of carcinogenic substances in category 2 must be no more than 10000 ppm. The total content of mutagenic substances in categories 1A and 1B must be no more than 10000 ppm, while the total content of mutagenic substances in category 2 must be no more than 10000 ppm. The total content of reproductively toxic substances in categories 1A and 1B must be no more than 30000 ppm, while the total content of reproductively toxic substances in category 2 must be no more than 30000 ppm.

[0101] It is also important that the metal content in ABS waste is below the transition limits specified, for example, in the Toy Safety Directive (2009 / 48 / EC), otherwise the waste is not suitable for use in the manufacture of toy assembly elements. In detail, the following transition limits must not exceed: aluminum: 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, organotin: 12 mg / kg, and zinc: 46,000 mg / kg.

[0102] To achieve non-toxic ABS waste with uniform physical and chemical properties, screening the waste before recycling may be beneficial or even necessary. Such screening may include analytical methods for detecting and / or quantifying carcinogens, mutagenic substances, reproductively toxic substances, antioxidants, heavy metals, halides, lubricants, flame retardants, colorants, etc., in order to quantify the butadiene copolymer to SAN ratio. Preferred analytical methods may include attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) to determine the butadiene copolymer to SAN ratio, thermogravimetric analysis (TGA) and / or differential scanning calorimetry-oxidation induction time (DSC-OIT) to determine the thermal oxidation stability of the waste, and X-ray fluorescence spectroscopy (XRF) to determine the amount of heavy metals and / or halides, etc. It may also be necessary to screen the ABS waste for the size of butadiene spheres and to investigate whether the spheres are distributed within 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 the reformed elements.

[0103] The present invention also relates to a method for manufacturing toy assembly elements. This method is shown in Figure 2. This method is a) A step of preparing and screening ABS waste material, b) A step of recovering recycled ABS polymer from the screened ABS waste by subjecting the ABS waste from step a to a crushing and / or solvent dissolution recycling process, c) A step of obtaining a resin by mixing the recovered ABS polymer from 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. d) A step of manufacturing toy assembly elements by processing the resin from step c, Includes.

[0104] Suitable resins obtained in step c and processed in step d include those described above.

[0105] Recycled ABS polymers in resins are derived from ABS waste materials, which undergo one or more screening processes before being incorporated into the resin. As a result, only materials that are not harmful and / or contain acceptable additives are incorporated into the resin.

[0106] In step a, the ABS waste material is: - The amount of a substance classified as carcinogenic, mutagenic, or reproductively toxic (CMR) of category 1A, 1B, or 2 under Regulation (EC) No 1272 / 2008, - Transition limits for 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. - The amount of oxide, - Amount of phthalate, - Amount of flame retardant, - Ratio of butadiene copolymer to SAN, - Size and size distribution of butadiene spheres, and - The butadiene spheres are screened for at least one property selected from the group consisting of the level of crosslinking.

[0107] It is of paramount importance that the amounts of substances classified as carcinogenic, mutagenic, or reproductively toxic (CMR) in categories 1A, 1B, or 2 under Regulation (EC) No. 1272 / 2008 be below the prescribed limits; otherwise, the waste material is unsuitable for use in the manufacture of toys. Therefore, the total content of carcinogenic substances in categories 1A and 1B must not exceed 1,000 ppm, while the total content of carcinogenic substances in category 2 must not exceed 10,000 ppm. The total content of mutagenic substances in categories 1A and 1B must not exceed 1,000 ppm, while the total content of mutagenic substances in category 2 must not exceed 10,000 ppm. The total content of reproductively toxic substances in categories 1A and 1B must not exceed 3,000 ppm, while the total content of reproductively toxic substances in category 2 must not exceed 30,000 ppm.

[0108] It is also important that the metal content in ABS waste is below the transition limits specified, for example, in the Toy Safety Directive (2009 / 48 / EC), otherwise the waste is not suitable for use in the manufacture of toy assembly elements. In detail, the following transition limits must not be exceeded: aluminum: 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, organotin: 12 mg / kg, and zinc: 46,000 mg / kg.

[0109] This amount of iron oxide must also be kept at an extremely low level to avoid the chemical degradation of the ABS polymer over time, specifically to avoid the formation of ABS monomers that would impair the mechanical properties of the toy assembly elements produced and thus pose a safety issue for the product. When ABS waste is used in the manufacture of toys, this amount of toxic compounds, such as phthalates and flame retardants, must also be avoided.

[0110] It is also important that waste ABS material is screened for the butadiene copolymer to SAN ratio and the size of the butadiene spheres. The butadiene content in the ABS material is preferably in the range of 15-22 wt% relative to the total ABS polymer. To obtain a glossy surface for the toy assembly elements produced, the size of the butadiene spheres is preferably 0.5 micrometers or less.

[0111] In some cases, waste ABS material can be extremely heterogeneous, and in such cases, it may be necessary to sort the waste ABS material before screening it for the properties mentioned above.

[0112] In step b, the screened ABS waste is subjected to a crushing and / or solvent dissolution recycling process to recover recycled ABS polymer.

[0113] A method for manufacturing toy assembly elements by processing resin containing mechanically recycled ABS polymer is shown in Figures 3 and 4. In this method, screened ABS waste is crushed. In the crushing step, the recycled material is broken / cut into small pieces of material. This step is important to obtain a homogeneous mixture of material that is readily mixed with additives and optionally other ABS polymers and readily melted during the manufacture of toy assembly elements, i.e., during injection molding, extrusion or additive manufacturing processes.

[0114] A method for manufacturing toy assembly elements by processing resin containing chemically recycled ABS polymer is shown in Figures 5, 6, and 7. In this method, screened ABS waste is subjected to a solvent dissolution recycling process. Typically, the waste ABS material is pulverized before dissolution to facilitate dissolution, but the pulverization step is not mandatory. During the dissolution step, the ABS waste is dissolved and the ABS polymer is separated into two phases: one phase contains poly(styrene-co-acrylonitrile) chains and is also called the SAN phase, and the other phase contains butadiene copolymer and is also called 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 recycled (Figures 6 and 7).

[0115] In step c, the recycled ABS polymer is mixed with other compounds to form a resin. Preferably, the mixing step is a compounding step. During mixing, the recycled ABS polymer, as well as one or more additives that are optionally mixed with the virgin and / or virgin-like ABS polymer, may also be mixed into the resin. Preferred additives include impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers, and / or plasticizers. The virgin and / or virgin-like ABS polymer may be a bio-based ABS polymer and / or a hybrid bio-based polymer. Furthermore, the virgin-like ABS polymer may be an ABS polymer recovered from a chemical pyrolysis recycling process or a chemical depolymerization recycling process.

[0116] In a detailed preferred embodiment, the waste ABS material is a discarded toy assembly element, as shown in Figure 4. In these embodiments, the addition of additives may not be necessary because the discarded toy assembly element may already possess the mechanical properties necessary to manufacture a toy assembly element with the required properties.

[0117] In step d, the toy assembly elements are manufactured by processing the resin obtained in step c. In some embodiments, the toy assembly elements are manufactured by injection molding. In such embodiments, the recycled ABS polymer may be mixed with additives and / or colorants, and optionally with further virgin or virgin-like ABS polymer, before the resin is fed into the injection molding machine. In some embodiments, the mixing may be carried out as a dry mixing step or a compounding step. In other embodiments, the mixing may be carried out by using a compounding step in an extruder before the injection molding step. In yet another embodiment, the additives may be mixed into a masterbatch, which is then mixed with the remainder of the ABS resin during feeding into the injection molding machine. Alternatively, the mixing may be carried out during the feeding of the resin into the injection molding machine.

[0118] In yet another embodiment, the toy assembly elements are manufactured by extrusion, followed optionally by thermoforming or molding using a similar technique.

[0119] In some embodiments, toy assembly elements are manufactured by additive manufacturing. A preferred example of additive manufacturing techniques is when toy assembly elements are assembled by photopolymerization additive manufacturing or thermoplastic additive manufacturing, such as liquid-based additive manufacturing, toner-based additive manufacturing, powder-based additive manufacturing, or granule-based additive manufacturing.

[0120] Preferably, this method also includes a step in step d in which the resin obtained in step c is subjected to quality control, and then the resin is manufactured into toy assembly elements. Quality control mainly involves verifying the important mechanical properties necessary to obtain the final toy assembly elements having the required properties. Examples of mechanical properties that are typically measured include one or more of impact strength, surface friction, surface gloss, and color.

[0121] Examples The following embodiments describe how ABS is recycled by crushing and recycling molded elements and runners, and then using this crushed and recycled material to generate new elements by injection molding. In Example 1, all ABS material is recycled, and in Example 2, the recycled ABS is mixed with virgin ABS before new elements are injection molded. The impact strength of the injection molded elements is tested by the Charpy v-notch test.

[0122] Charpy v-notch test Dimensions: 6.0 x 4.0 x 50.0 mm 3 Molded plastic rods of the relevant material to be tested, with dimensions B×W×H, were cut with a notch cutter (ZNO, Zwick, Germany) with a notch tip diameter of 0.5 mm, according to ISO 179-1 / 1 eA. The notched test specimens were placed with the v-notch opposite the pendulum and tested on a pendulum impact tester (HOT, Zwick, Germany) according to the principle described in ISO 179-1:2010. [Examples]

[0123] Properties of ABS from Mechanical Recycling - Complete Recycling of ABS Virgin ABS Terluran® GP35 (supplied by INEOS Styrolution) was dried at 80°C for 4 hours. The ABS was processed into impact test specimens and runners via injection molding (Arburg, Allrounder 470E 1000-400, 30mm screw, Germany). Ten impact test specimens were tested using a Charpy v-notch test, and the results are recorded as 0 crushing and regeneration cycles in the table below.

[0124] The remaining runners and impact test specimens were again ground into pellets using a plastic grinder. The ground ABS pellets were then processed again into impact test specimens and runners, and 10 impact test specimens were used for a Charpy v-notch test, with the results recorded as one grinding-regeneration cycle. The remaining impact test specimens and runners were ground and reprocessed in a similar manner for up to 10 grinding-regeneration cycles.

[0125] The injection molding parameters were as follows: Melting temperature: 240℃ Mold temperature: 30℃

[0126] The results are shown in the table below. [Table 1]

[0127] The results suggest that one shredding and regeneration cycle does not appear to have any effect on the Charpy v-notch, but five shredding and regeneration cycles reduce the relative Charpy v-notch value from 100 to 95. Such a reduction would still be acceptable in cases where toy assembly elements are produced. A further reduction to 88 in the relative Charpy v-notch is observed after 10 shredding and regeneration cycles. This indicates that toy assembly elements made from ABS recycled 10 times are very likely to possess unacceptable mechanical properties due to insufficient impact strength. Therefore, new or additional impact-resistant modifiers need to be mixed into the recycled material to improve impact strength to an acceptable level. [Examples]

[0128] Properties of ABS from mechanical recycling - Partial recycling of ABS Two molds producing elements of different sizes were used to test the effect of applying varying amounts of mechanically recycled ABS in the molding process. In this study, the amount of mechanically recycled ABS was expressed as the percentage of the mechanically crushed and recycled runner system that was reintroduced into the ABS molding process. The two molds applied to the test were constructed so that 42% and 90% crushed and recycled material flowed through the runners during the molding process. These two molds were used to investigate whether supplementing virgin ABS with crushed and recycled ABS at varying levels could help maintain the good overall impact properties of the molded elements. The above two molds were used to generate input material for three additional molds, each with 37%, 51%, and 85% crushed and recycled material flowing through it, respectively.

[0129] Virgin ABS Terluran® GP35 (supplied by INEOS Styrolution) was dried at 80°C for 4 hours. The ABS was processed into LEGO elements via injection molding (Arburg, Allrounder 470 E 1000-400, 30mm screw, Germany) using molds no. 1 and 2. Crushed recycled and virgin ABS were supplied to the molds according to the table below. Due to the level of crushed recycled material introduced into the process, the molds need to generate several shots before the entire process stabilizes, i.e., before a steady state is achieved. The number of shots required to ensure a stable process is indicated in the table below. [Table 2]

[0130] Once stable processing was achieved, blend material samples ready for molding were collected and processed into impact test specimens via injection molding. The molded impact test specimens were used for Charpy v-notch analysis, and the results are shown in the table below.

[0131] The stable processing material produced in molds 1 and 2 was further used as input material for processing in molds 3, 4, and 5. Once stable processing was achieved, material samples were collected and used to produce impact test specimens to be tested by Charpy v-notch analysis. The results are shown in the table below. [Table 3]

[0132] The results show that adding a certain amount of mechanically recycled ABS to virgin ABS in the molding process unexpectedly increases the relative Charpy v-notch value. Specifically, mold 1 through which 42% pulverized recycled material flows shows an increase to 108% of the relative Charpy v-notch value. Furthermore, when the steady-state material from mold 1 is used as the input material for mold 3, the relative Charpy v-notch value increases further to 112% compared to the use of virgin material. The inventors have observed such increases in the relative Charpy v-notch value several times, which may indicate that an improved dispersion of polybutadiene spheres can be obtained when recycled ABS material is mixed with virgin ABS.

[0133] The results also show that as the number of ABS recycling cycles increases, the relative Charpy v-notch value decreases, resulting in molded elements with reduced impact strength. The exact Charpy v-notch value that is acceptable when recycled ABS is used to produce toy assembly elements depends on the type of element produced; for example, traditional LEGO® bricks require a higher impact strength than LEGO® DUPLO® bricks. However, ultimately, regardless of the type of element, recycled ABS material can no longer produce toy assembly blocks with satisfactory mechanical properties, and new or additional impact-resistant modifiers or virgin ABS must be mixed with the recycled ABS to produce toy assembly elements with acceptable impact strength.

[0134] The experimental results above indicate that while ABS can be mechanically recycled to some extent, ultimately, improvements in its mechanical properties are necessary to produce toy assembly elements with acceptable mechanical properties, such as acceptable impact strength.

Claims

1. Toy building elements made from recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing a resin that includes mechanically recycled ABS polymer and / or chemically recycled ABS polymer recovered from a solvent dissolution recycling process.

2. 10. The toy building element of claim 1, wherein the resin further comprises virgin ABS polymer, or chemically recycled ABS polymer recovered from a pyrolysis recycling process, or chemically recycled ABS polymer recovered from a chemical depolymerization recycling process, or any combination thereof.

3. 3. The toy building element of claim 1, wherein the toy building element is manufactured by injection molding, extrusion or additive manufacturing techniques, or by a combination of injection molding and additive manufacturing techniques.

4. 4. The toy building element of claim 1, wherein the size of the butadiene spheres in the recycled ABS polymer is 0.5 micrometers or less.

5. 6. A toy building element according to any one of claims 2 to 5, wherein the weight ratio between the mechanically recycled ABS polymer and the virgin ABS polymer ranges from 100:0 to 5:

95.

6. 6. The toy building element of claim 1, 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.

7. 7. A toy building element according to any one of claims 1 to 6, wherein the total amount of ABS polymer in the resin is at least 50 wt% relative to the total weight of the resin.

8. 8. The toy building element of claim 1, wherein the resin further comprises one or more additives selected from the group consisting of impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers and plasticizers.

9. 9. The toy building element of any one of claims 1 to 8, wherein the recycled ABS polymer is produced from ABS waste material from the toy industry.

10. 10. The toy building element of claim 9, wherein the ABS waste material is a discarded toy building element.

11. 11. A toy building element according to any one of claims 1 to 10, produced by injection moulding using a mould through which 20 to 95 wt%, for example 30 to 90 wt%, of recycled material after steady state flows.

12. a) providing and screening ABS waste material; b) subjecting the ABS waste material of step a to a crushing and / or solvent dissolution recycling process to recover recycled ABS polymer from the screened ABS waste material; 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 polymers, chemically recycled ABS polymers recovered from pyrolysis and chemically recycled ABS polymers recovered from chemical depolymerization; d) manufacturing toy building elements by processing the resin of step c; 1. A method for manufacturing a toy building element, comprising:

13. ABS waste: - the amount of substances classified as carcinogenic, mutagenic or toxic for reproduction (CMR) in category 1A, 1B or 2 under Regulation (EC) No 1272 / 2008, - 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; - amount of oxide, - amount of phthalates, - amount of flame retardant, - butadiene copolymer to SAN ratio, - butadiene sphere size and size distribution, and - the level of crosslinking of the butadiene spheres.

14. 14. The method according to claim 12 or 13, wherein the screened ABS waste material is subjected to crushing, and the recovered ABS polymer is recycled as a mechanically recycled ABS polymer.

15. 14. The method according to claim 12 or 13, wherein the screened ABS waste material is subjected to a solvent dissolution recycling process, thereby obtaining a SAN phase containing poly(styrene-co-acrylonitrile) chains and a butadiene phase containing a copolymer of butadiene, and at least the SAN phase is recycled as a chemically recycled ABS polymer.

16. 16. The method of any one of claims 12 to 15, wherein the recovered ABS polymer is compounded with one or more additives selected from the group consisting of impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers / UV absorbers, and plasticizers.

17. 17. The method according to any one of claims 12 to 16, wherein the toy building elements are manufactured by injection molding, extrusion or additive manufacturing of the resin obtained in step c), or by a combination of injection molding and additive manufacturing.

18. 18. A method according to any one of claims 12 to 17, wherein the resin obtained in step c is subjected to quality control before the resin is manufactured into toy building elements in step d.

19. The quality control includes measuring one or more mechanical properties of the resin, said mechanical properties being: - impact strength, - surface friction, - surface gloss, and - color.

20. 20. The method of any one of claims 12 to 19, wherein the ABS waste material is discarded toy building elements, and in step c, blending the recovered ABS polymer with one or more additives is optional.

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