JP2023522334A - Toy building blocks made from recycled ABS material - Google Patents

Abstract

The present invention relates to toy building elements made of recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing resins containing recycled ABS polymer. [Selection drawing] Fig. 1

Description

The present invention relates to toy building elements made of recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing resins containing recycled ABS polymer.

Toy construction elements have been manufactured and marketed for many years.

Traditionally, such toy building elements are made of petroleum-based polymers, such as ABS.

ABS is an engineering thermoplastic polymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. Proportions may vary from 15 to 35% acrylonitrile, 5 to 30% butadiene, and 40 to 60% styrene. ABS consists of an amorphous-continuous phase and a rubbery dispersed phase. Poly(styrene-co-acrylonitrile) (SAN) copolymers form a continuous phase and a secondary phase consisting of dispersed butadiene or butadiene copolymers. Butadiene particles have a layer of SAN grafted onto the surface, which makes the two phases compatible. The properties of ABS are derived from the composition, the properties of the thermoplastic and rubbery phases, and the interactions between them. Therefore, SAN content and molecular weight control properties such as processability, heat resistance, surface hardness and chemical resistance. Butadiene content primarily contributes to toughness.

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 high gloss surface of an ABS material can be obtained when the ABS is produced by emulsion polymerization, while a low surface gloss is usually obtained when the ABS material is produced by bulk polymerization.

Growing concerns about declining petroleum resources and the impact of global warming have prompted the development of technologies for recycling ABS and using biomass as a renewable resource to produce ABS polymers. encouraged.

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 bio-acrylic acid, bio-acrylonitrile and bio-1,4-butadiene using renewable carbon sources as raw materials. In the first stage, bio-1,3-propanediol is derived from renewable carbon sources via microbial fermentation, and in the second stage, bio-1,3-propanediol is derived from bio-acrylic acid, or bio-acrylonitrile. , or bio 1,4-butadiol.

ABS uses materials obtained using carbon capture technology, i.e. materials produced using carbon monoxide and/or carbon dioxide captured directly from the air or from gases by industrial processes. can also be generated by Such carbon capture technologies include, for example, absorption, adsorption, chemical looping and membrane separation technologies. The trapped carbon oxides can then be converted to hydrocarbons such as methanol or ethanol that can be used as a source to make new monomers or polymers.

ABS can also be obtained by mechanical or chemical recycling of ABS material.

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

One of the problems associated with the use of mechanically recycled ABS material is that the properties of recycled ABS material are usually inferior to virgin ABS material. This is due to decomposition phenomena that occur during the lifetime of ABS and during melt rework operations, which accelerate the decomposition effect. During rework, ABS materials are subjected to high temperatures and shear stresses, which induce different types of decomposition reactions. The degree of decomposition depends on the number of cycles and processing temperature. In post-consumer recycled ABS, exposure to light, elevated temperatures and chemicals during use is also expected to cause further degradation. ABS is believed to degrade due to chain scission and cross-linking, creating oligomeric products that can migrate to surfaces and fragile cross-linked polybutadiene particles. Chemical changes have a significant adverse effect on e.g. impact strength and it is necessary to improve the performance of the recycled polymer by adding suitable additives or by blending it with virgin polymer. .

Another problem with the use of mechanically recycled ABS material is the presence of hazardous and/or unacceptable additives and other undesirable substances in the waste ABS used for recycling. ABS waste is typically washed before it is recycled, but this washing step does not remove all additives and other undesirable substances present in the waste. Some types of additives can be harmful and therefore their presence in recycled ABS material is unacceptable when used to make toys, eg toy building elements. In particular, substances classified as Category 1A, 1B or 2 carcinogenic, mutagenic or toxic for reproduction (CMR) under Regulation (EC) No 1272/2008 are substances that are undesirable in recycled materials. . The presence of toxic metals should also be avoided. Flame retardants in waste from WEEE (waste electrical and electronic equipment) are further examples of unacceptable types of additives. Other types of additives that may be present in discarded ABS include pigments, such as iron oxide, which contribute to the continuous degradation of ABS material during the item's life before the item is discarded as waste. do. Other types of additives are impact modifiers that affect the impact strength of recycled ABS materials, lubricants that can affect material processing and friction properties, and color and mechanical properties of recycled ABS materials. It can be a colorant that can affect both. ABS waste can also contain undesirable 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 containing other monomers and solvents.

Yet 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 brightly colored toys made from recycled ABS materials, a suitable coloring process must be developed.

Chemical recycling of ABS refers to any process in which ABS waste material is chemically converted to its original monomers and/or oligomers, which produce new virgin-like polymers that can be used to create ABS items. . Chemical recycling processes of this type include pyrolysis and chemical depolymerization. Chemical recycling is an optional process in which the ABS waste can be dissolved using a suitable solvent and the dissolved ABS polymer then recovered, typically by precipitating the polymer or by evaporating the solvent. Also refers to the process of This type of chemical recycling process is typically referred to as "solvent dissolution."

Pyrolysis refers to the collapse of ABS materials at elevated temperatures in the absence of oxygen. Pyrolysis turns the plastic into pyrolysis oil, which can be further refined. New virgin-like polymers can then be made from the resulting oil by known polymerization processes.

Chemical depolymerization is the process of using chemicals to break down polymers into monomers, oligomers, or mixtures of monomers and/or oligomers and/or intermediates thereof. The process removes additives and colorants from the monomers/intermediates. New virgin-like polymers can be produced by polymerizing monomers. There is no commercial technology available today that is suitable for depolymerizing ABS waste. However, new virgin ABS polymers can be produced by polymerization of monomers recovered from the depolymerization of other types of plastic waste. For example, styrene monomer can be recovered by depolymerization of polystyrene, as described in WO2016/049782.

Solvent dissolution involves selective extraction of the polymer using a solvent. Any additives and colorants are removed and the resulting polymer recovered, typically by precipitating the polymer or by evaporating the solvent. Polymer chains and structures are not disrupted. Technologies for dissolution-based recycling of ABS have also been developed, and many solvents, such as acetone and tetrahydrofuran (THF), have been suggested to dissolve ABS.

WO2015/034948 A1 WO2016/049782 US 3,005,282 US05/877,800 WO2014/005591 US 4,616,064 WO2018/089573 paragraphs [0043] to [0072] US 5,409,967

One of the problems with using ABS polymer recovered from solvent dissolution recycling processes is that solvent extraction also removes all additives. This is because the recycled ABS material does not have the required properties such as viscosity, mold release, friction, fillers and flame retardants, and new protective additives such as heat stabilizers, antioxidants, UV stabilizers, etc. means that it may require

Another problem with the use of ABS polymer recovered from solvent dissolution recycling processes is that the solvent extraction contains a mixture of different SAN chains and butadiene spheres. Compensating for unpredictable mixtures of material components is a challenge. Therefore, it may be necessary to add short or long chain SANs to modify rheology or degree of cure, and to add butadiene spheres to improve impact properties. It may also be necessary to add different types of additives to compensate for additive loss during the solvent dissolution process.

A major problem with the use of recycled ABS, regardless of how it is manufactured, is the recovery of the polymer composition, which is not as uniform as the virgin polymer composition. The degree of variability is determined primarily by the waste material: the more uniform the waste material, the lower the degree of variability. Recycled ABS possesses high variability with respect to the ratio between styrene, butadiene and acrylonitrile, the chain length of SAN copolymers, the size and size distribution of butadiene spheres, and the extension of SAN grafts onto the surface of butadiene spheres. should be expected to A further serious challenge is therefore to make recycled ABS suitable and useful for manufacturing items such as toy building elements in order to obtain items with satisfactory properties such as satisfactory impact strength, surface friction and color. required for In particular, if the goal is to produce an item with a glossy surface, it should be noted that the ABS waste material was previously produced by emulsion polymerization, and the size of the butadiene spheres in the ABS material will affect the gloss of the finished item. It is important to include suitably sized butadiene spheres, as this has been found to be important for obtaining a surface.

The present invention relates to toy building elements made of recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing resins containing recycled ABS polymer. The inventors have surprisingly found that toy building elements can be manufactured by processing resins containing recycled ABS polymer.

In a first aspect, the present invention relates to toy building elements made from recycled ABS material.

In a second aspect, the invention relates to a method for manufacturing toy building elements made from recycled ABS material.

Fig. 2 shows a 2x4 block classic box LEGO®; FIG. 10 illustrates a method for manufacturing toy building elements by processing resin comprising mechanically recycled ABS polymer and/or chemically recycled ABS polymer recovered from a melt recycling process. FIG. 10 illustrates a method for manufacturing toy construction elements by processing resins containing mechanically recycled ABS polymer. FIG. 10 illustrates a method for manufacturing toy building elements by processing resins containing mechanically recycled ABS polymer, wherein waste ABS material is discarded toy building elements. FIG. 10 illustrates a method for manufacturing toy building elements by processing resins containing chemically recycled ABS polymer recovered from a melt recycling process. In this embodiment, both the SAN phase and butadiene spheres are recycled. FIG. 10 illustrates a method for manufacturing toy building elements by processing resins containing chemically recycled ABS polymer recovered from a melt recycling process. In this embodiment, only the SAN phase is recycled and mixed with additives and virgin butadiene and optionally additional ABS polymer. FIG. 10 illustrates a method for manufacturing toy building elements by processing resins containing chemically recycled ABS polymer recovered from a melt recycling process. In this embodiment, only the SAN phase is recycled and mixed with virgin ABS with high additive and butadiene content.

The present invention is directed to toy building elements made from recycled ABS materials.

The term "toy building element" as used herein includes traditional toy building elements in the form of box-shaped building blocks with protrusions on the upper surface and complementary tubes on the lower surface. . A traditional box toy building block is shown in FIG. Classical box toy building blocks were first disclosed in US 3,005,282 and are widely marketed under the trade names LEGO® and LEGO® DUPLO®. The term also includes other similar box-shaped building blocks produced by other companies not in the LEGO Group and therefore sold under other trademarks that are not the LEGO trademark.

The term "toy building element" also includes other types of toy building elements that form part of a toy building set, typically including a plurality of building elements that are compatible with each other and can therefore be interconnected. include. Such toy building sets are also marketed under the LEGO trademarks, such as LEGO(R) bricks, LEGO(R) Technic and LEGO(R) DUPLO(R). Some of these toy construction sets include toy construction figures, such as LEGO® Minifigures (see, e.g., US05/877,800), which have a complementary tubular portion on their underside, which As a result, the figure can be attached to other toy building elements in the toy building set. Such toy construction figures are also encompassed by the term "toy construction element". The term also includes similar toy building elements produced by other companies that are not part of the LEGO Group and therefore sold under other trademarks that are not the LEGO trademark.

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, with LEGO® DUPLO® bricks, in all dimensions, It is twice the size of a LEGO® brick. A traditional box-shaped LEGO® toy building block with 4×2 protrusions on the top measures approximately 3.2 cm long, 1.6 cm wide, and 0.96 cm high ( excluding the protrusions), and the diameter of each protrusion is about 0.48 cm. In contrast, a LEGO® DUPLO® brick with 4×2 protrusions on its top measures about 6.4 cm long, about 3.2 cm wide and about 1.92 cm high ( excluding the protrusions), and the diameter of each protrusion is approximately 0.96 cm.

The toy building elements are made of recycled ABS material, and the elements are manufactured by processing resins containing mechanically recycled ABS polymer and/or chemically recycled ABS polymer recovered from solvent dissolution recycling processes.

As used herein, the term "recycled ABS material" refers to ABS material obtained by processing resins containing recycled ABS polymer. Recycled ABS polymer is obtained from ABS waste. ABS scrap can be mechanically recycled ABS material or chemically recycled ABS material. The recycled ABS polymer in resin is mechanically recycled ABS polymer and/or chemically recycled ABS polymer recovered from a solvent dissolution recycling process. Additionally, the resin may further comprise virgin ABS polymer, and/or chemically recycled ABS polymer recovered from a pyrolytic recycling process, and/or recycled ABS polymer recovered from a chemical depolymerization recycling process.

"Mechanically recycled ABS material" refers to ABS material recovered by 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 scrap is collected and washed to remove foreign matter. The cleaned plastic is then crushed into flakes, which can be compounded and pelletized, or reprocessed into granules.

"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 process.

"Pyrolysis" refers to the decomposition of ABS materials into pyrolysis oils at elevated temperatures in the absence of oxygen. New virgin-like polymers can then be made from the resulting oil by known polymerization processes.

"Chemical depolymerization" refers to the process by which a polymer breaks down into a monomer, mixture of monomers, or intermediates thereof using chemical agents. New virgin-like polymers can be produced by polymerization of monomers.

"Solvent dissolution" refers to selective extraction of a polymer using a solvent. The extracted polymer is recovered by precipitating the polymer or by evaporating the solvent. Polymer chains and structures are not disrupted. Butadiene is present in ABS as discrete globules. Although solvent dissolution does not change the chemical bonds in the polymer chains, there is a risk of physical alteration of the shape and size of the butadiene spheres. Therefore, it may be necessary to dispose of the butadiene spheres during the solvent dissolution process.

The term "recycled ABS polymer" refers to ABS polymer contained in mechanically recycled ABS waste or polymer chemically recovered from ABS waste in a solvent dissolution process. The term also refers to virgin-like ABS polymers produced in pyrolytic recycling processes, or chemical depolymerization recycling processes. When the term refers to virgin-like ABS polymers, it also includes polymers in which only one or two of the monomers have been recycled by thermal decomposition or chemical depolymerization. For example, the term includes ABS polymers in which some or all of the styrene monomer is recycled by chemical depolymerization of polystyrene, while acrylonitrile and butadiene monomers are non-recycled monomers produced by traditional manufacturing methods. obtain.

In some embodiments, the recycled ABS material comprises recycled ABS polymer obtained from mechanically recycled ABS scrap. In other embodiments, the recycled ABS material comprises recycled ABS polymer obtained from chemically recycled ABS scrap, where the ABS polymer was recovered using a solvent dissolution recycling process. In still other embodiments, the recycled ABS material comprises a mixture of recycled ABS polymer obtained from mechanically recycled ABS scrap and chemically recycled ABS scrap, wherein the ABS polymer was recovered using a solvent dissolution recycling process. In further embodiments, the recycled ABS material may further comprise virgin ABS polymer and/or virgin-like ABS polymer, ie, recycled ABS polymer recovered from pyrolytic recycling processes and/or from chemical depolymerization recycling processes.

Toy building elements are manufactured by 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.

Injection molding of toy building elements is the traditional means of manufacturing toy building blocks. This manufacturing technique has been in use 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 another embodiment, the toy building element is manufactured by two-component injection molding, one of the components being a resin comprising recycled ABS polymer. In yet another embodiment, the toy building element is a multi-component injection molded product, at least one of the components being a resin comprising recycled ABS polymer.

In recent years, new additive manufacturing techniques have been developed for assembling objects, for example, from polymeric materials. The term "additively manufactured" or "additively manufactured" as used herein refers to adding new material in an additive manner, i.e., onto a substrate or onto newly added material. by repeatedly solidifying thin liquid layers or droplets on substrates or previously solidified liquid layers or droplets, or by repeatedly printing substrates or previously printed plastic materials with thermoplastic polymer materials or by repeatedly brazing the plastic material in an additive manner, for example by using a laser.

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 still other embodiments, the toy building elements are manufactured by a combination of injection molding and additive manufacturing. Such combined manufacturing techniques are described, for example, in WO 2014/005591, where advanced designs are achieved by adding material layer by layer to the surface of a conventional injection molded box building block. Toy building elements with individuality are produced.

In still other embodiments, the toy building elements are manufactured by extrusion. Optionally, the extrusion process is followed by shaping using thermoforming or similar techniques.

The size of the butadiene spheres in the ABS material is known to affect the surface gloss of items made from the ABS material. In the toy industry, glossy surfaces are very often targeted. Therefore, in preferred embodiments, the size of the butadiene spheres in the recycled ABS material is 0.5 micrometers or less.

One of the major problems in manufacturing new toy building elements using recycled ABS materials is the loss of mechanical properties, particularly impact strength. This problem may be at least partially solved by adding virgin ABS polymer to the resin before it is processed into toy building elements. Alternatively, this problem can be solved by adding a virgin-like ABS polymer or a mixture of virgin and virgin-like ABS polymers.

In one embodiment, the resin further comprises virgin ABS polymer. In some embodiments, the amount of virgin ABS polymer is at least 5 wt% of the total amount of polymer in the resin, such as 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 5 to 95 wt% of the total amount of polymer in the resin, such as 10-95 wt%, 30-95 wt%, 50-95 wt%, 70-95 wt% or 80-95 wt%. is in the range of In still other embodiments, the amount of virgin ABS polymer ranges from 5-50 wt%, such as 5-30 wt%, 5-20 wt%, or 5-10 wt% of the total amount of polymer in the resin.

In other embodiments, the resin comprises virgin-like ABS polymer. As used herein, the term "virgin-like ABS polymer" means chemically recycled ABS polymer recovered from a pyrolytic recycling process and/or from 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 polymer in the resin, such as 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 5 to 95 wt% of the total amount of polymer in the resin, such as 10-95 wt%, 30-95 wt%, 50-95 wt%, 70-95 wt% or 80-95 wt%. % range. In still other embodiments, the amount of virgin-like ABS polymer ranges from 5-50 wt%, such as 5-30 wt%, 5-20 wt%, or 5-10 wt% of the total amount of polymer in the resin.

In still other embodiments, the resin comprises a mixture of virgin and virgin-like ABS polymers. In some embodiments, the combined amount of virgin and virgin-like ABS polymer is at least 5 wt% of the total amount of polymer in the resin, such as at least 10 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt%, or at least 90 wt% is. In other embodiments, the combined amount of virgin and virgin-like ABS polymer is 5 to 95 wt% of the total amount of polymer in the resin, such as 10-95 wt%, 30-95 wt%, 50-95 wt%, 70-95 wt%. Or in the range of 80 to 95 wt%. In still other embodiments, the combined amount of virgin and virgin-like ABS polymer ranges from 5-50 wt%, such as 5-30 wt%, 5-20 wt% or 5-10 wt% of the total amount of polymer in the resin. .

In a preferred embodiment, the recycled ABS scrap material is discarded toy building elements, thus the recycled material is the same as virgin material, except that the recycled material has been processed into toy building elements and then ground into pellets or flakes. Exactly the same. In such cases, toy building elements made exclusively of mechanically recycled toy building elements have satisfactory mechanical properties, i.e. impact strength, and new additions to improve mechanical properties. It has surprisingly been found that it can be produced without even incorporating agents such as impact modifiers.

In some embodiments, the resin does not contain any virgin ABS polymer. In other embodiments, the amount of virgin ABS polymer ranges from 0 to 95 wt%, such as 0-50 wt%, 0-25 wt%, 0-10 wt%, or 0-5 wt% of the total amount of polymer in the resin.

The weight ratio between mechanically recycled ABS polymer and virgin ABS polymer is 100:0 to 1:99, such as 100:0 to 10:90, 90:10 to 50:50 or 50:50 to 90:10. can be a range.

In some embodiments, recycled ABS scrap is subjected to a solvent dissolution recycling process. In this process, ABS polymer from waste material is dissolved in a solvent and then the dissolved ABS polymer is typically recovered by precipitating the polymer or by evaporating the solvent. In solution, the polymer can separate into two phases; one phase contains poly(styrene-co-acrylonitrile) chains, also called SAN phase, and the other phase contains butadiene copolymer. , also called butadiene spheres.

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 suitably recycled, the recycled SAN copolymer can be blended with butadiene, which can be virgin butadiene or recycled butadiene, or mixtures thereof. In other cases where only the SAN phase is suitably recycled, the recycled SAN copolymer can be blended with ABS having a high content of butadiene. The ABS with high butadiene content can be virgin ABS or recycled ABS, or mixtures thereof.

As used herein, the term "ABS with high butadiene content" means ABS with at least 20 wt% butadiene.

In still other embodiments, the resin comprises mechanically recycled ABS polymer and chemically recycled ABS polymer recovered from solvent dissolution recycling processes. In some embodiments, the resin further comprises virgin ABS polymer.

Alternatively, the resin includes mechanically recycled ABS polymer, recycled SAN copolymer, and even ABS with a high content of butadiene. The ABS with high butadiene content can be virgin ABS or recycled ABS, or mixtures thereof.

In other embodiments, the resin comprises a mechanically recycled ABS polymer and a SAN phase recovered from ABS waste that has undergone a solvent dissolution recycling process. In this embodiment, it may be preferable to additionally add butadiene or ABS with a high content of butadiene, or mixtures thereof. Butadiene and ABS with a high content of butadiene can be of virgin or recycled origin, or mixtures thereof.

In a practical injection molding system, the amount of recycled ABS is determined by the volumetric ratio of the mold and mold runner system. When starting a new production, the mold is supplied with virgin material in the first run. Material left in the runner system, and therefore not forming part of the final injection molded element, is re-ground into pellets or flakes etc. and used as recycled material to be mixed with virgin material and injected into the mold once more. supplied. This recycling continues until a steady state situation is achieved, the amount of recycled material representing a certain percentage of the input material, the remainder of the material being virgin material. This constant percentage of recycled material is referred to as "% post-steady state recycled material".

The inventors have surprisingly found that a significant improvement in the Charpy v-notch for the molded element produced in the mold is observed with a low % post-steady state recycled material flow. A detailed example described in Example 2 is a mold with 42% post-steady-state recycled material flow (Mold 1), which produced molded specimens with a relative Charpy v-notch value of 108%. be done. Another mold (Mold 2) running 90% post-steady-state recycled material showed no decrease in relative Charpy v-notch values. These findings were highly unexpected since a reduction in relative Charpy v-notch values was expected when ABS material was recycled.

Thus, in a particular preferred embodiment of the invention, the toy building elements are produced by injection molding using a mold with a post-steady state recycled material flow of 20-95 wt%, for example 30-90 wt%.

Resins that are processed into toy building elements can include bio-based ABS polymers and/or hybrid bio-based ABS polymers.

As used herein, the term "bio-based ABS polymer" means an ABS polymer produced by chemical or biochemical polymerization of monomers derived from biomass. In some embodiments, bio-based polymers are produced by chemical polymerization of monomers that are all derived from biomass. In other embodiments, bio-based polymers are produced by biochemical polymerization of monomers that are all derived from biomass.

As used herein, the term "hybrid bio-based ABS polymer" means that at least one of the ABS monomers is derived from biomass and at least one of the ABS monomers is derived from petroleum, petroleum by-products or petroleum-derived feedstocks. It means an ABS polymer produced by polymerization. ABS monomers can be virgin monomers, chemically recycled monomers or mixtures of virgin and recycled monomers. The polymerization process is typically a chemical polymerization process.

In some embodiments, at least a portion of the recycled ABS polymer is bio-based ABS polymer and/or 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 still other embodiments, 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.

In still other embodiments, toy construction elements may include ABS polymers produced using carbon capture technology. As used herein, the term "ABS polymer produced using carbon capture technology" refers to carbon monoxide and/or carbon dioxide captured directly from air or from gases by industrial processes. means a polymer containing carbon atoms of

In one embodiment, the total amount of ABS polymer in the resin is at least 50 wt% based on 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% of 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%, based on the total weight of the resin.

In another embodiment, the total amount of ABS polymer in the resin is 50-99 wt% based on 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% of 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% of the total weight of the resin.

As used herein, the term "total amount of ABS polymer in the resin" means that the ABS polymer contains recycled ABS polymer, virgin ABS polymer, bio-based ABS polymer, hybrid bio-based ABS polymer and/or carbon capture technology. It means the total amount of ABS polymer in the resin, regardless of whether it is the ABS polymer that was used to produce it.

It can be beneficial to add additives to resins containing recycled ABS polymers to improve the properties of toy building elements produced by processing the resins. In some embodiments, resins comprising recycled ABS polymers are added with one or more additives such as impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers/UV Contains absorbents and plasticizers.

The impact modifier can be a reactive impact modifier or can be a non-reactive impact modifier. In some embodiments, the recycled ABS polymer resin may contain both reactive and non-reactive impact modifiers. In preferred embodiments, the resin includes a reactive impact modifier.

As used herein, the term "impact modifier" means an agent that, when added to a resin, enhances the impact strength of an injection molded ABS element.

Reactive impact modifiers have functionalized end groups. Functionalization serves 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 improve dispersion. do what you do Preferred examples of such functionalized end groups include glycidyl methacrylate, maleic anhydride and carboxylic acid.

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

In one preferred embodiment, the impact modifier has the formula:
[Chemical 1]
(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 is alkyl of 1 to 5 carbons or 1 hydrogen atom).

X constitutes 40-90% (wt/wt) of the impact modifier and Y constitutes 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 is 0.5-20% (wt/wt) of the impact modifier. , preferably 2-10% (wt/wt), most preferably 3-8% (wt/wt).

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

Suitable examples of specific impact modifiers that may 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 Paraloid™ EXM-2314 (an acrylic copolymer from The Dow Chemical Company), Lotader® AX8700, Lotader® AX8900, Lotader® AX8750®, Lotader ® AX8950 and Lotader ® AX8840 (manufactured by Arkema), and Elvaloy ® PTW (manufactured by DuPont).

Other suitable examples of specific impact modifiers that may be used in the resins of this invention include anhydride-modified ethylene acrylates. 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, Lotader® 8200, Lotader® HX8210, Lotader® HX8290, Lotader® LX4110, Lotader® TX8030 (manufactured by Arkema), Bynel® 21E533, Bynel® 21E781, Bynel® 21E810 and Bynel® 21E830 (manufactured by DuPont).

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

Other suitable impact modifiers include maleic anhydride grafted impact modifiers. Specific examples of such impact modifiers are chemically modified ethylene acrylate copolymers such as Fusabond® A560 (manufactured by DuPont), anhydride modified polyethylenes such as Fusabond® E158 (DuPont anhydride modified polyethylene resins such as Fusabond® E564 or Fusabond® E589 or Fusabond® E226 or Fusabond® E528 (manufactured by DuPont), anhydride Modified high density polyethylene such as Fusabond® E100 or Fusabond® E265 (manufactured by DuPont), anhydride modified ethylene copolymers such as Fusabond® N525 (manufactured by DuPont), or chemical Modified propylene copolymers such as Fusabond® E353 (manufactured by DuPont).

Still other 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 are 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 based copolymers, 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 are Escor™ 5000, Escor™ 5020, Escor™ 5050, Escor™ 5080, Escor™ 5100, Escor 5200 and Escor 6000 (manufactured by ExonMobile Chemical).

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

In another embodiment, the impact modifier is an alkyl methacrylate-silicone/alkyl acrylate graft copolymer. The "alkyl methacrylate" of the graft copolymer can be selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate. "Silicone/alkyl acrylate" in graft copolymer refers to a polymer obtained by polymerizing a mixture of silicone monomers and alkyl acrylate monomers. Silicone monomers include dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. It may be selected from the group consisting of siloxanes. Alkyl monomers may be selected from the group consisting of 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 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 invention, the graft copolymer is a methyl methacrylate-silicone/butyl acrylate graft copolymer. A specific example is manufactured by Mitsubishi Rayon Co. of Japan. , Ltd. including S-2001, S-2100, S-2200 and S-2501 manufactured by

Other suitable impact modifiers include the siloxane polymers mentioned in US Pat. No. 4,616,064, which contain siloxane units and at least one carbonate, urethane or amide unit.

Suitable impact modifiers also include those mentioned in WO2018/089573 paragraphs [0043] to [0072].

Other suitable impact modifiers include core-shell impact modifiers such as those mentioned in US Pat. No. 5,409,967.

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

Suitable examples of inorganic particulate materials are 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, nanoclays, feldspars and asbestos; metals such as boron and steel; carbon-graphites 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 alumina surface-modified TiO2.

Suitable examples of nanocomposites are 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/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, 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. , including epoxy/zinc oxide nanocomposites and PMMA/zinc oxide nanocomposites.

Resins containing recycled ABS polymer may also contain antioxidants. Suitable examples of antioxidants include phosphites, phenols, amines and mixtures of any thereof.

Resins containing recycled ABS polymer may also contain a lubricant. The addition of lubricants can be very important to obtain toy building elements with satisfactory surface properties, such as satisfactory surface friction. Suitable examples of lubricants are 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 their including any mixture of

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

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.

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.

Resins containing recycled ABS polymer may also contain a plasticizer. 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.

The type and assortment of ABS waste is critical to the uniformity of the ABS polymer in the resin. The more uniform the waste material, the more uniform resin can be obtained. It is advantageous to use a resin with uniform length and crosslinks and recycled ABS polymer of butadiene sphere size. In one embodiment, the recycled ABS polymer is produced from ABS scrap from the toy industry.

In a preferred embodiment, the ABS scrap is discarded toy building elements. A major advantage of using discarded toy construction elements from the manufacturer's own production plant is that the chemical composition is known, as is how the material is processed. If the scrap material is color coded prior to recycling, it may help produce recycled toy building elements with uniform colors. If the scrap material is not color coded prior to recycling, it may be necessary to first remove the colorant and then add new colorant to obtain a final toy building element with a satisfactory color. .

Some ABS scrap contains harmful additives and therefore its presence in recycled ABS material is unacceptable when used to make toys, eg toy building elements. Examples of such hazardous additives include hazardous flame retardants such as halogenated flame retardants, plasticizers such as phthalates and bisphenol A, hazardous lubricants such as fluoropolymers, and inorganic materials such as cadmium and manganese. . Other types of additives that may be present in discarded ABS include pigments, such as iron oxide, which contribute to the continuous degradation of ABS material during the item's life before the item is discarded as waste. do.

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 can be used in toy assembly Not suitable for use in the manufacture of elements.

In particular, the amount of substances classified as Category 1A, 1B or 2 carcinogenic, mutagenic or toxic for reproduction (CMR) under Regulation (EC) No 1272/2008 shall be below the prescribed limits. must. Therefore, the total content of Category 1A and 1B carcinogens must be 1000 ppm or less, while the total content of Category 2 carcinogens must be 10000 ppm or less. The total content of Category 1A and 1B mutagens must be 1000 ppm or less, while the total content of Category 2 mutagens must be 10000 ppm or less. The total content of substances that are Category 1A and 1B reproductive toxic shall not exceed 3000 ppm, while the total content of substances which are Category 2 reproductive toxic shall not exceed 30000 ppm.

It is also important that the metal content in the ABS scrap is below the migration limits specified, for example, in the Toy Safety Directive (2009/48/EC), otherwise the scrap cannot be used in the manufacture of toy building elements. not suitable for Specifically, the migration limits are: Aluminum: 70000 mg/kg, Antimony: 560 mg/kg, Arsenic: 47 mg/kg, Barium: 18750 mg/kg, Boron: 15000 mg/kg, Cadmium: 17 mg/kg, Chromium (III): 460 mg/kg, chromium (IV): 0.053 mg/kg, cobalt: 130 mg/kg, copper: 7700 mg/kg, lead: 160 mg/kg, manganese: 15000 mg/kg, mercury: 94 mg/kg, nickel: 930 mg/kg , selenium: 460 mg/kg, strontium: 56000 mg/kg, tin: 180000 mg/kg, organotin: 12 mg/kg, and zinc: 46000 mg/kg.

In order to achieve non-hazardous ABS waste of uniform physical and chemical properties, it may be beneficial or even necessary to screen the waste prior to recycling. Such screens include carcinogens, mutagens, substances that are reproductively toxic, antioxidants, heavy metals, halides, lubricants, flame retardants, coloring agents, to quantify the ratio of butadiene copolymer to SAN. Analytical methods for detecting and/or quantifying agents and the like may be included. Suitable analytical methods include Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) to determine the ratio of butadiene copolymer to SAN, Thermogravimetric Analysis (TGA) to determine the thermooxidative stability of waste materials and/or Differential scanning calorimetry-oxidation induction time (DSC-OIT), X-ray fluorescence spectroscopy (XRF) to determine amounts of heavy metals and/or halides and the like may be included. It may also be necessary to screen the ABS scrap for the size of the 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 techniques include measuring the gloss of reshaped elements. .

The invention also relates to a method for manufacturing toy building elements. This method is illustrated in FIG. This method
a) providing and screening ABS scrap;
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 recycling process;
c) the recovered ABS polymer of step b is combined with one or more additives and optionally virgin ABS polymer, chemically recycled ABS polymer recovered from pyrolysis and chemically recycled ABS polymer recovered from chemical depolymerization obtaining a resin by mixing with one or more ABS polymers selected from the group consisting of ABS polymers;
d) manufacturing toy building elements by processing the resin of step c;
including.

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

Recycled ABS polymers in resins originate from ABS waste material and are subjected to one or more screening processes before being incorporated into the resin so that only materials containing non-hazardous and/or acceptable additives are included in the resin. incorporated into.

In step a, the ABS scrap is:
- amounts of substances classified under Regulation (EC) No 1272/2008 as Category 1A, 1B or 2 carcinogenic, mutagenic or toxic to reproduction (CMR),
- 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 migration limits for one or more metals;
- the amount of oxide,
- the amount of phthalates,
- the amount of flame retardant,
- the ratio of butadiene copolymer to SAN,
- the size and size distribution of the butadiene spheres; and - the level of cross-linking of the butadiene spheres.

It is very important that the amount of substances classified as Category 1A, 1B or 2 carcinogenic, mutagenic or toxic for reproduction (CMR) under Regulation (EC) No 1272/2008 is below the prescribed limits , otherwise the scrap material is not suitable for use in making toys. Therefore, the total content of Category 1A and 1B carcinogens must be 1000 ppm or less, while the total content of Category 2 carcinogens must be 10000 ppm or less. The total content of Category 1A and 1B mutagens must be 1000 ppm or less, while the total content of Category 2 mutagens must be 10000 ppm or less. The total content of substances that are Category 1A and 1B reproductive toxic shall not exceed 3000 ppm, while the total content of substances which are Category 2 reproductive toxic shall not exceed 30000 ppm.

It is also important that the metal content in the ABS scrap is below the migration limits specified, for example, in the Toy Safety Directive (2009/48/EC), otherwise the scrap cannot be used in the manufacture of toy building elements. not suitable for Specifically, the following migration limits: aluminum: 70000 mg/kg, antimony: 560 mg/kg, arsenic: 47 mg/kg, barium: 18750 mg/kg, boron: 15000 mg/kg, cadmium: 17 mg/kg, chromium(III): 460 mg. /kg, Chromium (IV): 0.053 mg/kg, Cobalt: 130 mg/kg, Copper: 7700 mg/kg, Lead: 160 mg/kg, Manganese: 15000 mg/kg, Mercury: 94 mg/kg, Nickel: 930 mg/kg, Selenium: 460 mg/kg, Strontium: 56000 mg/kg, Tin: 180000 mg/kg, Organotin: 12 mg/kg and Zinc: 46000 mg/kg.

This amount of iron oxide also results in poor mechanical properties of the manufactured toy building elements, in particular to avoid chemical degradation of the ABS polymer over time, and thus becomes a product safety issue. It must be kept at a very low level to avoid the formation of ABS monomers. This amount of toxic compounds such as phthalates and flame retardants should also be avoided if ABS scrap is used to make toys.

It is also important that the waste ABS material is screened for butadiene copolymer to SAN ratio and butadiene sphere size. The butadiene content in the ABS material is preferably in the range of 15-22 wt% with respect to the total ABS polymer. The size of the butadiene spheres is preferably 0.5 micrometers or less in order to obtain a glossy surface for the toy building elements to be produced.

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

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

A method of manufacturing toy building elements by processing a resin containing mechanically recycled ABS polymer is illustrated in FIGS. In this method, screened ABS waste is subjected to grinding. In the crushing step, the recycled material is crushed/cut into small pieces of material. This step produces a homogeneous mixture of materials that are easily mixed with additives and optionally other ABS polymers and melted during the manufacture of toy construction elements, i.e. injection molding, extrusion or additive manufacturing processes. important to get.

A method of manufacturing toy building elements by processing a resin containing chemically recycled ABS polymer is shown in FIGS. In this method, screened ABS waste is subjected to a solvent dissolution recycling process. Typically, the waste ABS material is subjected to grinding prior to melting to facilitate the dissolution of the waste material, although the grinding step is not required. During the dissolution step, the ABS waste material is dissolved and the ABS polymer is separated into two phases: one phase contains poly(styrene-co-acrylonitrile) chains, also called SAN phase, and the other phase is , containing butadiene copolymers, also called butadiene spheres. In some embodiments, both the SAN phase and butadiene spheres are recycled (Figure 5), while in other embodiments only the SAN phase is recycled (Figures 6 and 7).

In step c, the recycled ABS polymer is mixed with other compounds and formed into a resin. Preferably, the mixing step is a compounding step. During mixing, the recycled ABS polymer, and optionally one or more additives mixed with the virgin and/or virgin-like ABS polymer, may 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-like ABS polymers can be bio-based ABS polymers and/or hybrid bio-based polymers. Additionally, the virgin-like ABS polymer can be ABS polymer recovered from a chemical pyrolysis recycling process or a chemical depolymerization recycling process.

In a detailed preferred embodiment, the waste ABS material is discarded toy building elements, as shown in FIG. In these embodiments, the addition of additives may not be necessary because the discarded toy building elements have the necessary mechanical properties to produce toy building elements with the required properties. because you may already own

In step d, toy building 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, mixing the recycled ABS polymer with additives and/or colorants and optionally additional virgin or virgin-like ABS polymer may be performed prior to feeding the resin to the injection molding machine. In some embodiments, mixing may be performed as a dry mixing step or a compounding step. In other embodiments, mixing can be done by using a compounding step in an extruder prior to the injection molding step. In still other embodiments, the additives may be mixed into a masterbatch, which is then mixed with the remainder of the ABS resin during the injection molding machine feed. Alternatively, mixing can occur while the resin is being fed to the injection molding machine.

In still other embodiments, the toy construction elements are manufactured by extrusion, optionally followed by molding using thermoforming or similar techniques.

In some embodiments, toy building elements are manufactured by additive manufacturing. Suitable examples of additive manufacturing techniques are those in which the toy building elements are manufactured using photopolymeric 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. It is assembled by additive manufacturing of the base.

Preferably, the method also includes subjecting the resin obtained in step c to quality control prior to manufacturing the resin into toy building elements in step d. Quality control is primarily about ascertaining the critical mechanical properties necessary to obtain a final toy building element with the required properties. Examples of mechanical properties that are typically measured include one or more of impact strength, surface friction, surface gloss and color.

EXAMPLES The following examples show how ABS is recycled by regrinding molded elements and runners and then using this regrind material to produce new elements by injection molding. It is described about In Example 1, all ABS material is recycled, and in Example 2, recycled ABS is mixed with virgin ABS before a new component is injection molded. The impact strength of injection molded elements is tested by the "Charpy v-notch test".

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

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. ABS was processed into impact bars and runners via injection molding (Arburg, Allrounder 470E 1000-400, 30 mm screw, Germany). Ten impact bars were tested in the Charpy v-notch test and the results are recorded in the table below as 0 regrind cycles.

The remaining runner and impact specimens were re-ground into pellets with a plastic grinder. The ground ABS pellets were reprocessed into impact bars and runners, 10 impact bars were used for the Charpy v-notch test, and the results were recorded as one grind reclaim cycle. In a similar manner, the remaining impact specimens and runners were ground and reworked for up to 10 grinding regeneration cycles.

Injection molding parameters were as follows:
Melting temperature: 240°C
Mold temperature: 30°C

The results are shown in the table below.

From the results, 1 regrind cycle does not appear to have any effect on the Charpy v-notch, whereas 5 regrind cycles reduce the relative Charpy v-notch value from 100 to 95. is shown. Such a reduction would still be acceptable in cases where toy building elements are produced. A further drop in relative Charpy v-notch to 88 is seen after 10 regrind cycles. This indicates that toy building elements made of 10 times recycled ABS can very likely possess unacceptable mechanical properties due to insufficient impact strength. Therefore, new or additional impact modifiers need to be blended into the recycled material in order to improve the impact strength to acceptable levels.

Properties of ABS from Mechanical Recycling - Partial Recycling of ABS Two molds producing different sized elements test the effect of applying varying amounts of mechanically recycled ABS on the molding process. used for In this study, the amount of mechanically recycled ABS was expressed in terms of the percentage of mechanically reclaimed runner system that was reintroduced into the ABS molding process. The two molds applied for testing had runners constructed to flow 42% and 90% regrind material during the molding process. These two molds were used to investigate whether supplementing various levels of virgin ABS with regrind ABS could help maintain good overall impact properties of the molded element. The two molds described above were used to produce input material for three additional molds with respectively 37%, 51% and 85% regrind material flows.

Virgin ABS Terluran® GP35 (supplied by INEOS Styrolution) was dried at 80° C. for 4 hours. The ABS is manufactured via injection molding (Arburg, Allrounder 470 E 1000-400, 30mm screw, Germany) using mold no. 1 and 2 were used to fabricate LEGO elements. The mold was fed with regrind and virgin ABS according to the table below. Due to the level of regrind material introduced into the process, the mold needs to produce several shots before the overall process stabilizes, i.e. before a steady state situation is achieved. The number of shots to ensure a stable process is indicated in the table below.

Once stable processing was achieved, molding-ready blend material samples were collected and these samples were 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.

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 generate impact specimens that were tested by Charpy v-notch analysis. The results are shown in the table below.

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 values. Specifically, Mold 1 with 42% regrind material flow shows up to 108% increase in relative Charpy v-notch values. Also, if steady-state material from Mold 1 is used as input material for Mold 3, the relative Charpy v-notch value further increases to 112% compared to using virgin material. We have observed several such increases in relative Charpy v-notch values, indicating that improved dispersion of polybutadiene spheres is obtained when recycled ABS material is mixed with virgin ABS. can be pointed out.

The results also show that as the number of ABS recirculation cycles increases, the relative Charpy v-notch values decrease, resulting in molded elements with decreased impact strength. The exact Charpy v-notch value that can be accepted when using recycled ABS to produce toy construction elements depends on the type of element produced, e.g. ® DUPLO ® brick requires higher impact strength. Ultimately, however, independent of element type, recycled ABS materials can no longer produce toy building blocks with satisfactory mechanical properties, but produce toy building elements with acceptable impact strength. To do so, new or additional impact modifiers or virgin ABS must be mixed with the recycled ABS.

From the above experimental results, ABS can be mechanically recycled to some extent, but ultimately, in order to produce toy construction elements with acceptable mechanical properties, e.g. It indicates that improvement is needed.

Claims (20)

Toy building elements made of recycled ABS (acrylonitrile butadiene styrene) material and manufactured by processing a resin containing mechanically recycled ABS polymer and/or chemically recycled ABS polymer recovered from a solvent dissolution recycling process. . 4. The claim 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. 2. Toy building element according to claim 1. 3. A toy building element according to any one of claims 1 or 2, 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. Toy building element according to any one of claims 1 to 3, wherein the size of the butadiene spheres in the recycled ABS polymer is 0.5 micrometers or less. A toy building element according to any one of claims 2 to 5, wherein the weight ratio between mechanically recycled ABS polymer and virgin ABS polymer ranges from 100:0 to 5:95. 6. Any one of claims 1-5, 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. Toy construction elements as described in . A toy building element according to any preceding claim, wherein the total amount of ABS polymer in the resin is at least 50 wt% relative to the total weight of the resin. 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. 8. A toy building element as claimed in any one of claims 1 to 7 comprising. 9. A toy building element according to any preceding claim, wherein the recycled ABS polymer is produced from ABS scrap from the toy industry. 10. The toy building elements of claim 9, wherein the ABS scrap is discarded toy building elements. A toy construction according to any one of the preceding claims, produced by injection molding using a mold through which 20-95 wt%, such as 30-90 wt% post-steady-state recycled material flows. element. a) providing and screening ABS scrap;
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 recycling process;
c) the recovered ABS polymer of step b is combined with one or more additives and optionally virgin ABS polymer, chemically recycled ABS polymer recovered from pyrolysis and chemically recycled ABS polymer recovered from chemical depolymerization obtaining a resin by mixing with one or more ABS polymers selected from the group consisting of ABS polymers;
d) manufacturing toy building elements by processing the resin of step c;
A method for manufacturing a toy construction element comprising: ABS scrap is:
- amounts of substances classified under Regulation (EC) No 1272/2008 as Category 1A, 1B or 2 carcinogenic, mutagenic or toxic to reproduction (CMR),
- 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 migration limits for one or more metals;
- the amount of oxide,
- the amount of phthalates,
- the amount of flame retardant,
- the ratio of butadiene copolymer to SAN,
13. The method of claim 12, wherein the screen is screened for at least one property selected from the group consisting of - size and size distribution of the butadiene spheres, and - level of cross-linking of the butadiene spheres. 14. A method according to any one of claims 12 or 13, wherein the screened ABS waste is subjected to grinding and the recovered ABS polymer is recycled as mechanically recycled ABS polymer. The screened ABS scrap is subjected to a solvent dissolution recycling process resulting in a SAN phase containing poly(styrene-co-acrylonitrile) chains and a butadiene phase containing copolymers of butadiene, at least the SAN phase being chemically recycled. 14. A method according to any one of claims 12 or 13, wherein the ABS polymer is recycled. The recovered ABS polymer contains one or more selected from the group consisting of impact modifiers, fillers, antioxidants, lubricants, flame retardants, colorants, light stabilizers/UV absorbers and plasticizers. 16. The method of any one of claims 12-15, combined with an additive. 17. A toy building element as claimed in any one of claims 12 to 16, wherein the toy building element is produced from the resin obtained in step c by injection molding, extrusion or additive manufacturing, or by a combination of injection molding and additive manufacturing. the method of. 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. Quality control comprises measuring one or more mechanical properties of the resin, said mechanical properties comprising:
- impact strength,
- surface friction,
19. The method of claim 18, selected from the group consisting of - surface gloss, and - color. 20. Any one of claims 12 to 19, wherein the ABS scrap is discarded toy building elements and in step c, mixing the recovered ABS polymer with one or more additives is optional. The method described in .

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