CN115943183A

CN115943183A - Toy building elements made of polymeric polyester material

Info

Publication number: CN115943183A
Application number: CN202180043260.5A
Authority: CN
Inventors: B.安德森; R.米克尔森
Original assignee: Lego AS
Current assignee: Lego AS
Priority date: 2020-06-16
Filing date: 2021-06-16
Publication date: 2023-04-07
Also published as: EP4165132A1; JP2023530350A; WO2021255098A1; MX2022016146A; KR20230023740A

Abstract

The present invention relates to a toy building element made of a polyester material and manufactured by processing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier. The invention further relates to a method of manufacturing such a toy building element.

Description

Toy building elements made of polymeric polyester material

Technical Field

Background

Polyesters are a class of polymers that contain ester functional groups in their backbone. They may be formed by the reaction of a diacid or anhydride with a diol with the removal of water, or by ring-opening polymerization of cyclic (di) esters. Polyesters are classified into aliphatic, semi-aromatic and aromatic according to the composition of their main chain. In general, aromatic acids and diols improve hardness, stiffness and heat resistance, while aliphatic acids and diols improve flexibility, lower melting or softening points, and improve processability.

Common aliphatic diols are ethylene glycol, 1, 4-butanediol and 1, 3-propanediol. They are often reacted with aromatic diacids, such as terephthalic acid, phthalic anhydride, and naphthalene dicarboxylic acid. Glycerin and unsaturated acids (anhydrides), such as maleic anhydride, are sometimes added to crosslink the polyester. In the case of unsaturated acids (anhydrides), crosslinking is achieved in the subsequent free radical chain polymerization. The double bonds in the polyester backbone also improve resistance to softening and deformation at high temperatures.

Poly (ethylene terephthalate) (also known as PET) is a common thermoplastic polymer resin. It can be produced by the reaction of ethylene glycol and terephthalic acid. Today, PET is widely used for manufacturing containers for food, water, carbonated water, soft drinks, and the like, due to its excellent combination of mechanical properties and gas barrier properties. Clear water bottles are made by blow molding of amorphous PET. Thus, amorphous PET can be considered a low cost raw material for the production of engineered compounds because it is widely available, for example from recycled beverage bottles.

PET was not originally considered an injection molding material because it has high humidity sensitivity, poor impact strength, and a slow crystallization rate, which slows the molding process.

The properties of PET can be modified and enhanced to the extent that it is useful for the industrial production of durable products. Very slow crystallization rates can be improved by the addition of nucleating agents, while poor impact strength can be improved by the addition of glass, fibers, inorganic or organic reinforcing materials (e.g., carbon nanotubes, graphene, and graphite), and/or impact modifiers.

Standard bottle grade PET typically has an intrinsic viscosity in the range of 0.75 to 0.85 deciliters/gram. Copolymer modification (acid or glycol modification) has been used to reduce the crystallization rate and the PET melting temperature, thereby reducing the energy requirements in the production process. Standard PET bottle polymers modified with copolymers are typically modified with 0 to 3 mole% isophthalic acid (IPA) to reduce the crystallization rate and allow the production of clear amorphous preforms weighing up to 100 grams.

Poly (ethylene furan dicarboxylate) (also known as PEF) is an aromatic thermoplastic polyester that is easily molded and thermoformed. It can be produced by polycondensation of ethylene glycol and 2, 5-furandicarboxylic acid (FDCA). PEF has many attractive properties, including high tensile strength and puncture toughness, good heat resistance, and outstanding gas barrier properties, all of which are superior to PET. PEF also has a lower melting point and a higher glass transition temperature than PET and therefore has more attractive thermal and mechanical properties. Information on impact strength is very little.

PEF is a known analog of PET and can replace PET because its chemical structure is very similar to that of PET. In particular, research in recent years has focused on the use of PEF as a food and beverage packaging material because it has better barrier properties, i.e., better resistance to the permeation of gases (oxygen and carbon dioxide), as compared to PET.

It has been demonstrated that PEF can be recycled in a manner very similar to PET recycling. Preliminary tests have shown that PEF has no substantial effect on the mechanical and physical properties (e.g., strength and impact) of PET. It is therefore suggested that it is possible to recover PEF in the PET recovery stream, at least during the transition period after the PEF product is placed on the market. It is believed that less than 2% PEF is compatible in existing PET recycling streams, and the upper limit of 2% PEF in PET recycling streams has in fact been approved by the european PET bottle platform.

Research has not focused on improving the impact strength and toughness of PEF. However, due to the chemical similarity of PEF to PET, it is believed that the impact strength of PEF can be improved in a similar manner to PET when the same type and amount of impact modifier is added.

Poly (ethylene glycol-co-1, 4-cyclohexanedimethanol terephthalate) (also known as glycol-modified polyethylene terephthalate or PETG) is prepared by partially substituting the ethylene glycol group of PET with a 1, 4-Cyclohexanedimethanol (CHDM) group. In contrast to semi-crystalline PET, ethylene glycol modified poly (ethylene terephthalate) copolyester is an amorphous thermoplastic that exhibits a glass transition temperature of about 80 ℃, which is similar to that of PET. In some studies, PETG is reported to have a higher glass transition temperature than PET.

The impact strength of PETG is dependent on the amount of ethylene glycol and 1, 4-cyclohexanedimethanol terephthalate, respectively. The higher the 1, 4-cyclohexanedimethanol terephthalate content, the higher the impact strength.

Impact modifiers are known to improve the durability and toughness of polymer resins. Impact modifiers for PET are generally elastomeric compounds that generally decrease modulus while increasing impact strength and elongation. An effective method of improving impact strength is to disperse a rubber phase in a PET matrix. The main role of the rubber particles is to induce a global deformation mechanism rather than a local phenomenon, thereby greatly increasing the dissipated fracture energy. The effectiveness of rubber modification depends on the type of rubber, rubber content, rubber particle size and inter-particle distance.

Impact modifiers may be characterized as reactive or non-reactive. Reactive impact modifiers are preferred for toughening of PET because they form a stable dispersed phase by grafting onto the PET matrix. The non-reactive elastomer can be dispersed into the PET by intensive compounding, but may coalesce downstream in the compounder.

The reactive impact modifier has functionalized end groups. Functionalization serves two purposes: first by binding the impact modifier to the polymer matrix and second by altering the interfacial energy between the polymer matrix and the impact modifier to enhance dispersion.

Non-reactive (unfunctionalized) elastomeric impact modifiers are not very effective in toughening polyesters because they do not interact well with the polyester matrix to achieve an optimally sized dispersed phase and strong interfacial bonding. Non-reactive impact modifiers may take on a unique core-shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and, since the structure is usually obtained by emulsion copolymerization, it provides a well-defined particle size which in turn leads to a well-controlled blend morphology. The soft rubber core may be a butadiene core or an acrylic core and the outer shell may be made of PMMA.

Polyester is an attractive material for the manufacture of toys such as toy building elements. However, in order to meet the requirements of product safety and play experience, it is necessary to vary the impact strength so that durable toy bricks can be produced, e.g. without breaking when the toy bricks are dropped on the floor or stepped on by adults. Improved impact strength needs to be focused on injection molded objects with complex geometries, such as conventional

Building block geometries, which have been marketed for many years, are produced from conventional materials such as ABS.

Disclosure of Invention

The inventors of the present invention have developed a new polyester resin for use in the manufacture of toy building elements, which polyester resin provides improved impact strength to the manufactured elements.

In particular, the inventors of the present invention have surprisingly found that when a resin comprising one or more polyesters, a reactive impact modifier and a non-reactive impact modifier is processed into a toy building element, a significantly improved impact strength is obtained. In fact, a synergistic effect is observed when processing such polyester resins, compared to polyester resins comprising only reactive or non-reactive impact modifiers.

In a first aspect, the present invention relates to a toy building element made of a polyester material and manufactured by processing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a poly (ethylene terephthalate) polyester (PET polyester) or a modified PET polyester which has been modified by the following substitutions:

-all or part of the terephthalic acid groups of the PET polyester are substituted with diacid monomers selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4' -biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and mixtures thereof; and/or

-all or a portion of the ethylene glycol groups of the PET polyester are substituted with a glycol monomer selected from the group consisting of isosorbide, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, diethylene glycol, 1, 2-propanediol, neopentyl glycol, 1, 3-propanediol, 1, 4-butanediol, and mixtures thereof,

provided that not all of the terephthalic acid groups and all of the ethylene glycol groups can be substituted simultaneously.

In a second aspect, the invention relates to a method of manufacturing a toy building element, the method comprising the steps of:

a) Providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a poly (ethylene terephthalate) polyester (PET polyester) or a modified PET polyester that has been modified by substitution of:

-all or a portion of the ethylene glycol groups of the PET polyester are replaced with a glycol monomer selected from the group consisting of isosorbide, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, diethylene glycol, 1, 2-propanediol, neopentyl glycol, 1, 3-propanediol, 1, 4-butanediol, and mixtures thereof,

provided that not all terephthalic acid groups and all ethylene glycol groups can be substituted simultaneously,

and

b) Processing the resin.

Drawings

FIG. 1 shows a conventional box shape

2 x 4 blocks.

Detailed Description

The present invention relates to a toy building element made of a polyester material and manufactured by processing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.

The term "toy building element" as used herein comprises conventional toy building elements in the form of box-like bricks provided with knobs on their upper side and complementary tubes on their lower side. A conventional box-like toy block is shown in fig. 1. Conventional box-like toy bricks are disclosed for the first time in US 3,005,282 and are given the brand name

And &>

Is widely sold. The term also includes other similar box-shaped bricks, which are produced by companies other than lega and are therefore sold under other trademarks than LEGO.

The term "toy building element" also comprises other kinds of toy building elements forming part of a toy building set, which usually comprises a plurality of building elements that are compatible and thus interconnectable. Such toy building sets are also sold under the trade mark LEGO, for example

Building blocks, LEGO technical and->

Some of these toy building sets include toy building characters, e.g. </or>

Mini-characters (see for example US 05/877,800) having complementary tubes on the underside so that the characters can be connected to other toy building elements in the toy building set. Such toy building figures are also covered by the term "toy building element". The term also includes similar toy building elements produced by companies other than LEGO and sold under other trademarks than LEGO.

Toy building elements come in a wide variety of shapes, sizes and colours.

Building block and/or>

One difference of the building blocks is that the size, or the position, is/are>

All dimensions of the building blocks are->

Twice as many building blocks. Conventional box-shaped @, with 4 x2 knobs on the upper side>

The dimensions of the toy bricks are about 3.2 centimeters in length, about 1.6 centimeters in width, and about 0.96 centimeters in height (excluding the knobs), each knob having a diameter of about 0.48 centimeters. In contrast, [ 4X 2 knobs on the upper side [. Sup. ] is present [. Sup. ]>

The dimensions of the building blocks are about 6.4 cm in length and about 3.2 cm in widthAbout 1.92 cm in height (excluding the knobs), each knob having a diameter of about 0.96 cm.

The toy building element is manufactured by injection moulding or by additive manufacturing, or by a combination of injection moulding and additive manufacturing.

Injection moulding of toy building elements is a conventional way of manufacturing toy building blocks. Such manufacturing techniques have been used for many years and are well known to the skilled person. In some embodiments, the toy building element is manufactured by injection moulding of a polyester resin. In other embodiments, the toy building element is manufactured by two-component injection moulding, wherein one component is a polyester resin.

In recent years, new additive manufacturing techniques have been developed for building objects using polymeric materials and the like. As used herein, the term "additive manufacturing" or grammatical variations thereof refers to the construction of a building block in a manner that adds material, i.e., by adding new material on top of a substrate or on top of newly added material, by repeatedly curing a thin liquid layer or droplet on a substrate or previously cured liquid layer or droplet, or by repeatedly printing thermoplastic polymer material on a substrate or previously printed plastic material, or by repeatedly welding (e.g., with a laser) in a manner that adds plastic material.

In some embodiments, the toy building element is manufactured by injection moulding. In other embodiments, the toy building element is manufactured by additive manufacturing. In other embodiments, the toy building element is manufactured by a combination of injection moulding and additive manufacturing. Such a combined manufacturing technique is for example described in WO 2014/005591, where toy building elements with a high degree of design personalization are manufactured by adding material in a layer-by-layer manner on the surface of a traditional injection-molded box-like building block.

Thus, the toy building element is made of a polyester material and is manufactured by processing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.

The term "polyester" as used herein includes PET polyester and modified PET polyester and mixtures thereof. Modified PET polyesters have been modified by the following substitutions:

The term "polyester resin" as used herein refers to a resin comprising at least one polyester as defined above, at least one reactive impact modifier and at least one non-reactive impact modifier.

The PET polyester is produced by polymerization of the monomers ethylene glycol and terephthalic acid. The modified PET polyester can be produced in three different ways. First, the modified PET polyester can be produced by polymerization of the monomers ethylene glycol, terephthalic acid, and one or more other comonomers, which are diacid monomers and/or diol monomers, resulting in diacid modification, diol modification, or diacid/diol modification. Secondly, the modified PET polyester may be produced by polymerisation of the monomers ethylene glycol and one or more other comonomers, which are one or more diacid monomers and optionally one or more diol monomers. Third, the modified PET polyester may be produced by polymerization of the monomer terephthalic acid and one or more other comonomers, which are one or more diol monomers and optionally one or more diacid monomers. In all cases, the diacid monomer is selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4' -biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and mixtures thereof, and the diol monomer is selected from the group consisting of isosorbide, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, diethylene glycol, 1, 2-propanediol, neopentyl glycol, 1, 3-propanediol, 1, 4-butanediol, and mixtures thereof.

In some embodiments, the resin comprises PET polyester. The PET polyester is produced by the reaction of ethylene glycol and terephthalic acid. In a preferred embodiment, the polyester is a PET polyester.

In some embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol and terephthalic acid with the comonomer 1, 4-cyclohexanedimethanol. In other embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol and terephthalic acid and the comonomer isophthalic acid. In other embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol and terephthalic acid with the comonomer 2, 4-tetramethyl-1, 3-cyclobutanediol. In other embodiments, the resin comprises a modified PET polyester produced by the reaction of terephthalic acid and 1, 4-cyclohexanedimethanol. In other embodiments, the resin comprises a modified PET polyester produced by the reaction of terephthalic acid, isophthalic acid, and 1, 4-cyclohexanedimethanol. In other embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol, terephthalic acid, and 2, 5-furandicarboxylic acid.

In a preferred embodiment, the resin comprises a poly (ethylene terephthalate-co-isophthalate) polyester. The poly (ethylene terephthalate-co-isophthalate) polyester is produced by the reaction of ethylene glycol, terephthalic acid, and isophthalic acid. In a preferred embodiment, the polyester in the resin is a modified PET polyester which is a poly (ethylene terephthalate-co-isophthalate) polyester. The amount of isophthalic acid in the poly (ethylene terephthalate-co-isophthalate) polyester is generally 0.5 to 12 mole%, preferably 1 to 3 mole%.

The chemical composition of the poly (ethylene terephthalate-co-isophthalate) polyester (i.e., the amount of isophthalic acid in the poly (terephthalate-co-isophthalate) polyester) can be determined according to "martianez de Ilarduya, a.; kit, d.p.;

sequence Analysis of Poly (ethylene terephthalate-co-isophthalate) Copolymers by 13C NMR, of Guerra, S.A.Macromolecules 2000, 33, 4596-4598 "were characterized by 13C-nuclear magnetic resonance spectroscopy (C NMR). Accordingly, the amount of isophthalic acid can be measured using this C NMR method.

An important characteristic of PET is Intrinsic Viscosity (IV). Intrinsic viscosity measured in deciliters/gram is obtained by extrapolating the relative viscosity to zero concentration. Depending on the length of the PET polymer chain. The longer the polymer chains, the more entanglement between the chains and thus the higher the viscosity. During polymerization, the average length of a particular batch of PET resin can be controlled.

The PET Intrinsic Viscosity (IV) can be measured according to ASTM D4603.

High IV homopolymer and copolymer PET compositions are difficult to handle in injection molding because of their high viscosity.

In some embodiments, the IV of the PET polyester is from 0.6 to 1.1 deciliter per gram, for example from 0.7 to 0.9 deciliter per gram, preferably from 0.75 to 0.85 deciliter per gram.

In a preferred embodiment, the modified PET polyester is bottle grade PET. The term "bottle grade" is well known in the art and refers to a PET stock that is readily processed into bottles. In most embodiments, "bottle grade" PET is made from poly (ethylene terephthalate-co-isophthalate) polyester containing 1-3 mole% isophthalic acid. In bottle grade PET, the IV is typically in the range of 0.70 to 0.78 deciliters per gram for non-carbonated water and 0.78 to 0.85 deciliters per gram for carbonated water.

Suitable examples of PET grades that are also commercially available include bottle grade EASTLON PET CB-600, CB-602, and CB-608 provided by Far Eastern New Center (FENC), commercial grade post-consumer rPET CB-602R provided by FENC, part bio-based bottle grade PET CB-602AB provided by FENC, and homopolymer PET grade 6020 provided by Invista.

In some embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol and terephthalic acid with the comonomer 1, 4-cyclohexanedimethanol. In some embodiments, the resin comprises a poly (ethylene glycol-co-1, 4-cyclohexanedimethanol terephthalate) polyester, also known as glycol-modified polyethylene terephthalate or PETG. In a preferred embodiment, the polyester is a modified PET polyester which is PETG. The amount of 1, 4-cyclohexanedimethanol in PETG is typically from 0.1 to 25 mole%. In other embodiments, the resin comprises ethylene glycol modified poly (cyclohexanedimethylene terephthalate), which is also known as PCTG. In a preferred embodiment, the polyester is a modified PET polyester which is PETG. The amount of 1, 4-cyclohexanedimethanol in PETG is typically in the range of 25-49.99 mole%.

In other embodiments, the resin comprises a modified PET polyester produced by the reaction of ethylene glycol and terephthalic acid with the comonomer 2, 4-tetramethyl-1, 3-cyclobutanediol. In some embodiments, the resin comprises poly (ethylene glycol-co-2, 4-tetramethyl-1, 3-cyclobutanediol terephthalate), also known as PETT.

In other embodiments, the resin comprises a modified PET polyester produced by the reaction of terephthalic acid and 1, 4-cyclohexanedimethanol. In some embodiments, the resin comprises poly (cyclohexanedimethylene terephthalate), which is also known as PCT.

In other embodiments, the resin comprises a modified PET polyester produced by the reaction of terephthalic acid, isophthalic acid, and 1, 4-cyclohexanedimethanol. In some embodiments, the resin comprises isophthalic acid modified poly (cyclohexanedimethylene terephthalate), which is also known as PCTA. The amount of isophthalic acid is usually 0.1 to 50 mol%, more usually 0.1 to 5 mol%.

In some embodiments, the resin comprises a poly (ethylene furan dicarboxylate-co-ethylene terephthalate) polyester. The poly (ethylene furan dicarboxylate-co-ethylene terephthalate) polyester is produced by the reaction of ethylene glycol, terephthalic acid, and 2, 5-furandicarboxylic acid. The amount of 2, 5-furandicarboxylic acid in the modified PET polyester is usually 0.5 to 12 mol%, preferably 1 to 3 mol%.

In some embodiments, the resin comprises a poly (ethylene furan dicarboxylate) polyester, also known as PEF. The poly (ethylene furandicarboxylate) polyester is produced by the reaction of ethylene glycol and furandicarboxylic acid. In a preferred embodiment, the polyester is a modified PET polyester which is PEF.

In other embodiments, the resin comprises a mixture of poly (ethylene terephthalate) polyester and poly (ethylene furan dicarboxylate) polyester. In other embodiments, the resin comprises a mixture of poly (ethylene terephthalate-co-isophthalate) polyester and poly (ethylene furandicarboxylate) polyester. In other embodiments, the resin comprises a poly (ethylene terephthalate) polyester, a mixture of poly (ethylene terephthalate-co-isophthalate) polyester, and poly (ethylene furan dicarboxylate) polyester. In any of these mixtures, the amount of poly (ethylene furan dicarboxylate) polyester is typically 0.1 to 10% (w/w), for example 0.1 to 5% (w/w) or 0.1 to 2% (w/w), based on the total amount of polyester.

In some embodiments, the polyester resin is an unfilled polyester resin.

The term "unfilled polyester resin" as used herein refers to a polyester resin that does not contain reinforcing and filling materials such as glass, glass beads, fibers, mineral reinforcing materials (e.g., aluminum silicate, talc, asbestos, mica, and calcium carbonate), and organic reinforcing materials (e.g., aramid fibers, carbon nanotubes, graphene, and graphite).

In one embodiment, the polyester resin does not contain glass, glass beads and/or glass fibers. In one embodiment, the polyester resin is free of fibers. In one embodiment, the polyester resin is free of inorganic reinforcing materials such as aluminum silicate, asbestos, talc, mica, and calcium carbonate. In one embodiment, the polyester resin is free of organic reinforcing materials such as aramid fibers, carbon nanotubes, graphene, and graphite. In one embodiment, the polyester resin is free of glass and fibers.

In another preferred embodiment, the polyester resin further comprises one or more fillers in an amount of up to 5% (w/w), such as 0.1-5% (w/w), more preferably 0.2-4% (w/w), most preferably 0.5-3% (w/w), relative to the total weight of the resin. The one or more fillers may be an inorganic particulate material or a nanocomposite material, or a mixture thereof.

Suitable examples of inorganic particulate materials include inorganic oxides such as glass, mgO, siO ₂ 、TiO ₂ And Sb ₂ O ₃ (ii) a Hydroxides, such as Al (OH) ₃ And Mg (OH) ₂ (ii) a Salts, e.g. CaCO ₃ 、BaSO ₄ 、CaSO ₄ And a phosphate; silicates such as talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feldspar, and asbestos; metals, such as boron and steel; carbon-graphite, such as carbon fibers, graphite fibers and flakes, carbon nanotubes, and carbon black. Suitable examples of inorganic particulate materials also include surface treated and/or surface modified SiO ₂ And TiO 2 ₂ E.g. surface-modified TiO of alumina ₂ 。

Suitable examples of nanocomposites include clay-filled polymers such as clay/Low Density Polyethylene (LDPE) nanocomposites, clay/High Density Polyethylene (HDPE) nanocomposites, acrylonitrile-butadiene-styrene (ABS)/clay nanocomposites, polyimide (PI)/clay nanocomposites, epoxy/clay nanocomposites, polypropylene (PP)/clay nanocomposites, polymethyl 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, epoxy/zinc oxide nanocomposites, and PMMA/zinc oxide nanocomposites.

In one embodiment, the resin comprises an amount of polyester of at least 50% (weight/weight) relative to the total weight of the resin. In other embodiments, the resin comprises an amount of polyester of at least 60% or 70% or 80% (weight/weight) relative to the total weight of the resin. In a preferred embodiment, the resin comprises an amount of polyester of at least 85% relative to the total weight of the resin, such as at least 90% (w/w), more preferably at least 95% or 97% or 99% (w/w) relative to the total weight of the resin.

In another embodiment, the resin comprises an amount of polyester ranging from 50 to 99.5% (weight/weight) relative to the total weight of the resin. In other embodiments, the resin comprises a polyester amount of 60 to 97%, or 70 to 95% (weight/weight), relative to the total weight of the resin. In a preferred embodiment, the resin comprises an amount of polyester of 75-95%, more preferably 77-92%, even more preferably 80-90% (weight/weight) with respect to the total weight of the resin.

The polyester in the resin may be a bio-based polymer, a hybrid bio-based polymer, or a petroleum-based polymer, or a mixture thereof.

The term "bio-based polymer" as used herein refers to a polymer produced by chemical or biochemical polymerization of monomers derived from biomass. Bio-based polymers include polymers produced by the polymerization of one biomass-derived monomer, as well as polymers produced by the polymerization of at least two different biomass-derived monomers.

In a preferred embodiment, the bio-based polymer is produced by chemical or biochemical polymerization of monomers, both derived from biomass.

The bio-based polymer of the present invention comprises:

polymers produced by biochemical polymerization (i.e. for example by using microorganisms). The monomers are produced using biomass as a substrate.

Polymers produced by chemical polymerization (i.e. by chemical synthesis). The monomers are produced using biomass as a substrate.

In some embodiments, the bio-based polymer is produced by biochemical polymerization. In other embodiments, the bio-based polymer is produced by chemical polymerization. In other embodiments, the bio-based polymer is produced by biochemical or chemical polymerization. The bio-based polymer may also be produced by a combination of biochemical and chemical polymerization, for example where two monomers are combined into a dimer by a biochemical reaction pathway, and then the dimer is polymerized by a chemical reaction.

Bio-based polymers also include polymers having the same molecular structure as petroleum-based polymers, but which are produced by chemical and/or biochemical polymerization of biomass-derived monomers.

The term "petroleum-based polymer" as used herein refers to a polymer produced by chemical polymerization of monomers derived from petroleum, petroleum by-products, or petroleum-derived feedstocks.

The term "hybrid bio-based polymer" as used herein refers to a polymer produced by the polymerization of at least two different monomers, wherein at least one monomer is derived from biomass and at least one monomer is derived from petroleum, petroleum by-products, or petroleum-derived feedstocks. The polymerization process is typically a chemical polymerization process.

The hybrid bio-based polymers may also be characterized by their bio-based/total carbon content. The term "biobased carbon" as used herein refers to carbon atoms derived from biomass used as a substrate in the production of monomers, which carbon atoms form part of a biobased polymer and/or a hybrid biobased polymer. The content of biobased carbon in the mixed biobased polymer can be determined by carbon-14 isotope content or equivalent protocol as specified in ASTM D6866 or CEN/TS 16137.

In some embodiments, the content of biobased carbon in the mixed biobased polymer is at least 25%, such as at least 30% or at least 40%, based on the total carbon content of the mixed biobased polymer. In other embodiments, the content of bio-based carbon in the mixed bio-based polymer is at least 50%, such as at least 60%, such as at least 70%, such as at least 80%, based on the total carbon content of the mixed bio-based polymer.

In one embodiment, the ethylene glycol monomers and/or the diol monomers are bio-based monomers, while the terephthalic acid monomers and/or the diacid monomers are not bio-based monomers, such as petroleum-based monomers. In another embodiment, the terephthalic acid monomer and/or the diacid monomer are bio-based monomers and the ethylene glycol monomer and/or the diol monomer are not bio-based monomers. In another embodiment, the ethylene glycol monomers and/or the diol monomers and the terephthalic acid monomers and/or the diacid monomers are bio-based monomers. In another embodiment, none of the ethylene glycol monomers, the diol monomers, the terephthalic acid monomers, and the diacid monomers are biobased monomers.

In a preferred embodiment, the ethylene glycol monomers and/or the diol monomers are biomass-derived biobased monomers and have a biobased carbon content equal to 100% based on the total carbon content in the ethylene glycol monomers and/or the diol monomers. In other embodiments, the ethylene glycol monomer and/or the diol monomer has a biobased carbon content of at least 25%, for example at least 50%, preferably at least 70%, more preferably at least 90%, most preferably at least 95%, based on the total carbon content in the ethylene glycol monomer and/or the diol monomer.

In a preferred embodiment, the terephthalic acid monomer and/or the diacid monomer are biomass-derived biobased monomers and have a biobased carbon content equal to 100% based on the total carbon content in the terephthalic acid monomer and/or the diacid monomer. In other embodiments, the terephthalic acid monomer and/or the diacid monomer have a biobased carbon content of at least 25%, such as at least 50%, preferably at least 70%, more preferably at least 90%, and most preferably at least 95%, based on the total carbon content in the terephthalic acid monomer and/or the diacid monomer.

In some embodiments, the content of biobased carbon in the polyester is at least 25% based on the total carbon content in the polyester. In other embodiments, the biobased carbon content in the polyester is at least 50%, such as at least 60%, such as at least 70%, preferably at least 80%, more preferably at least 90%, and even more preferably at least 95% based on total carbon content. In a most preferred embodiment, the content of biobased carbon in the polyester is 100% based on the total carbon content in the polyester.

In some embodiments, the content of biobased carbon in the resin is at least 25% based on the total carbon content in the resin. In other embodiments, the content of biobased carbon in the resin is at least 50%, such as at least 60%, such as at least 70%, preferably at least 75%, more preferably at least 80%, even more preferably at least 85%, based on the total carbon content in the resin. In a most preferred embodiment, the content of biobased carbon in the resin is 90% based on the total carbon content in the resin.

The terms "bio-based polymer," mixed bio-based polymer, "and" petroleum-based polymer "also include recycled polymers and recycled materials comprising" bio-based polymer, "" mixed bio-based polymer, "and" petroleum-based polymer.

The term "recycled material" as used herein refers to a material obtained by treating a resin comprising recycled polymer. The recycled polymer is obtained from waste. The waste material may be mechanically recycled material or chemically recycled material.

"mechanically recycled material" refers to material that has been recovered by mechanically recycling the material. Mechanical recycling involves only mechanical processes such as grinding, washing, separating, drying, re-granulating and compounding. In a typical recycling process, waste material is collected and cleaned to remove contaminants. The cleaned plastic is then ground into flakes, which can be compounded and pelletized or reprocessed into pellets.

"chemically recovered material" includes material obtained by pyrolysis, chemical depolymerization, solvent dissolution, or any other suitable chemical recovery process.

"pyrolysis" refers to the decomposition of a material to crude oil at elevated temperatures in the absence of oxygen. The new virgin polymers can then be prepared from the resulting oils by known polymerization methods.

"chemical depolymerization" refers to the process of decomposing a polymer into monomers, monomer mixtures, or intermediates thereof using a chemical reagent. New virgin polymers can be produced by polymerization of the monomers.

"solvent dissolution" refers to the selective extraction of a polymer using a solvent. The extracted polymer is recovered by precipitation of the polymer or evaporation of the solvent. The polymer chains and structures do not decompose.

The term "recycled polymer" refers to a polymer contained in mechanically recycled waste or chemically recycled from waste during solvent dissolution. This term also refers to virgin polymers produced during pyrolytic recovery processes or chemical depolymerization recovery processes. Where the term refers to virgin polymers, it also includes polymers where only one or two monomers are recovered by pyrolysis or chemical depolymerization.

In some embodiments, the resin comprises a mechanically recycled polyester. In other embodiments, the resin comprises mechanically recycled polyester and bio-based polyester. In other embodiments, the resin comprises mechanically recycled polyester and mixed bio-based polyester. In other embodiments, the resin comprises mechanically recycled polyesters and petroleum-based polyesters. In other embodiments, the resin comprises mechanically recycled polyesters, bio-based polyesters, and petroleum-based polyesters. In other embodiments, the resin comprises mechanically recycled polyesters, hybrid bio-based polyesters, and petroleum-based polyesters. In other embodiments, the resin comprises mechanically recycled polyesters, biobased polyesters, and hybrid biobased polyesters. In other embodiments, the resin comprises mechanically recycled polyesters, biobased polyesters, mixed biobased polyesters, and petroleum based polyesters.

In some embodiments, the amount of mechanically recycled polyester in the resin is at least 10% (weight/weight) of the total weight of the resin, such as at least 20%, or such as at least 30%, such as at least 40%, or such as at least 50%. In other embodiments, the amount of mechanically recycled polyester in the resin is at least 60% (weight/weight), such as at least 70%, or such as at least 75%, such as at least 80%, or such as at least 85%, based on the total weight of the resin.

In some embodiments, the polyester comprises chemically recycled monomers. In other embodiments, the polyester comprises chemically recycled monomers and bio-based monomers. In other embodiments, the polyester comprises chemically recycled monomers and mixed bio-based monomers. In other embodiments, the polyester comprises chemically recycled monomers and petroleum-based monomers. In other embodiments, the polyester comprises chemically recycled monomers, bio-based monomers, and petroleum-based monomers. In other embodiments, the polyester comprises chemically recycled monomers, mixed bio-based monomers, and petroleum-based monomers. In other embodiments, the polyester comprises chemically recycled monomers, bio-based monomers, and mixed bio-based monomers. In other embodiments, the polyester comprises chemically recycled monomers, bio-based monomers, mixed bio-based monomers, and petroleum-based monomers.

In some embodiments, the amount of chemically recovered monomer in the polyester is at least 10% (weight/weight), such as at least 20%, or such as at least 30%, such as at least 40%, or such as at least 50%, based on the total weight of the polyester. In other embodiments, the amount of chemically recovered monomer in the polyester is at least 60% (weight/weight), such as at least 70%, or such as at least 80%, such as at least 90%, or such as at least 95%, based on the total weight of the polyester.

In some embodiments, the resin comprises a mixture of recycled poly (ethylene terephthalate) polyester and recycled poly (ethylene furan dicarboxylate) polyester. In other embodiments, the resin comprises a mixture of recycled poly (ethylene terephthalate-co-isophthalate) polyester and recycled poly (ethylene furan dicarboxylate) polyester. In other embodiments, the resin comprises a mixture of recycled poly (ethylene terephthalate) polyester, recycled poly (ethylene terephthalate-co-isophthalate) polyester, and recycled poly (ethylene furandicarboxylate) polyester.

The polyester resin comprises at least one reactive impact modifier and at least one non-reactive impact modifier.

The term "impact modifier" as used herein refers to an agent that increases the impact strength of the produced toy building element. The impact strength was measured using the charpy V notch test defined below.

The term "reactive impact modifier" as used herein refers to an impact modifier having functionalized end groups. These functionalized end groups serve two purposes: 1) Binding the impact modifier to the polymer matrix, and 2) altering the interfacial energy between the polymer matrix and the impact modifier to enhance dispersion. Preferred examples of such functionalized end groups include glycidyl methacrylate, maleic anhydride and carboxylic acids.

In a preferred embodiment, the reactive impact modifier is a copolymer represented by the formula X/Y/Z, wherein X is an aliphatic or aromatic hydrocarbon polymer having 2 to 8 carbon atoms, Y is a moiety comprising an acrylate or methacrylate ester having 3 to 6 and 4 to 8 carbon atoms, respectively, and Z is a moiety comprising methacrylic acid, glycidyl methacrylate, maleic anhydride or a carboxylic acid.

In a preferred embodiment, the reactive impact modifier may be described by the following formula:

wherein:

n is an integer of 1 to 4,

m is an integer of 0 to 5,

k is an integer of 0 to 5, and

r is an alkyl group of 1 to 5 carbon atoms or 1 hydrogen atom.

X represents 40 to 90% (w/w) of the impact modifier, Y represents 0 to 50% (w/w) of the impact modifier, for example 10 to 40% (w/w), preferably 15 to 35% (w/w), most preferably 20 to 35% (w/w), and Z represents 0.5 to 20% (w/w), preferably 2 to 10% (w/w), most preferably 3 to 8% (w/w) of the reactive impact modifier.

In other embodiments, X comprises from 70 to 99.5% (w/w), preferably from 80 to 95% (w/w), most preferably from 92 to 97% (w/w), Y comprises 0% (w/w) of the impact modifier, and Z comprises from 0.5 to 30% (w/w), preferably from 5 to 20% (w/w), most preferably from 3 to 8% (w/w) of the reactive impact modifier.

Suitable examples of specific reactive impact modifiers that can be used in the resins of the present invention include ethylene-ethylene acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate. Commercially available impact modifiers include Paraloid ^TM EXM-2314 (an acrylic copolymer produced by Dow Chemical Company),

AX8700、/>

AX8900、/>

AX8750、/>

AX8950 and +>

AX8840 (produced by Arkema) and +>

PTW (manufactured by DuPont).

Other suitable examples of specific reactive impact modifiers that may be used in the resins of the present invention include anhydride-modified ethylene acrylates. Commercially available impact modifiers include

3210、/>

3410、/>

4210、/>

3430、/>

4402、/>

4503、/>

4613、/>

4700、

5500、/>

6200、/>

8200、/>

HX8210、/>

HX8290、

LX4110、/>

TX8030 (produced by Arkema), ` based on `>

21E533、/>

21E781、

21E810 and +>

21E830 (manufactured by DuPont).

In other embodiments, the reactive impact modifier is a modified ethylene vinyl acetate, for example

1123 or->

1124 (manufactured by DuPont); acid-modified ethylene acrylates, e.g. < >>

2002 or +>

2022 (manufactured by DuPont); modified ethylene acrylates, e.g. </or>

22E757、/>

22E780 or->

22E804 (manufactured by DuPont); anhydride-modified ethylene vinyl acetates, e.g. </or >, in>

30E670、/>

30E671、/>

30E753 or->

30E783 (manufactured by DuPont); and acid/acrylate-modified ethylene vinyl acetates, for example->

3101 or->

3126 (manufactured by DuPont); anhydride-modified ethylene vinyl acetates, e.g. </or >, in>

E418、/>

3810、/>

3859、/>

3860 or

3861 (manufactured by DuPont); anhydride-modified ethylene vinyl acetates, e.g. </or >, in>

3930 or->

39E660 (manufactured by DuPont); and anhydride-modified high-density polyethylene, e.g. < >>

4033 or +>

40E529 (manufactured by DuPont); anhydride-modified linear low density polyethylene, e.g. [ in>

4104、/>

4105、

4109、/>

4125、/>

4140、/>

4157、/>

4164、/>

41E556、

41E687、/>

41E710、/>

41E754、/>

41E755、/>

41E762、

41E766、/>

41E850、/>

41E865 or +>

41E871 (manufactured by DuPont); anhydride-modified low-density polyethylene, e.g.. Based on->

4206、/>

4208、/>

4288 or>

42E703 (manufactured by DuPont); or anhydride-modified polypropylene, e.g. </>>

50E571、/>

50E662、/>

50E725、/>

50E739、/>

50E803 or->

50E806 (manufactured by DuPont).

Other suitable reactive impact modifiers include maleic anhydride grafted impact modifiers. Specific examples of such reactive impact modifiers include chemically modified ethylene acrylate copolymers, for example

A560 (manufactured by DuPont); anhydride-modified polyethylene, e.g.. Dbr>

E158 (manufactured by DuPont); anhydride-modified polyethylene resins, e.g. </or>

E564 or->

E589 or->

E226 or +>

E528 (manufactured by DuPont); anhydride-modified high-density polyethylene, e.g.. Based on->

E100 or->

E265 (manufactured by DuPont); anhydride-modified ethylene copolymers, e.g. <' >>

N525 (produced by DuPont); or chemically modified propylene copolymers, e.g. </or>

E353 (manufactured by DuPont).

Other suitable reactive 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 the ethylene-methacrylic acid based copolymer impact modifier include

403、/>

407HS、/>

411HS、/>

0609HSA、

0903、/>

0903HC、/>

908HS、/>

910、/>

910HS、/>

1202HC、/>

599、/>

699、/>

925 and->

960 (manufactured by DuPont). Specific examples of ethylene-acrylic acid based copolymers include->

30707、/>

30907、/>

31001、

3990 and->

AE (manufactured by DuPont). Other specific examples of ethylene of the ethylene-acrylic acid (EAA) -based copolymer include Escor ^TM 5000、Escor ^TM 5020、Escor ^TM 5050、Escor ^TM 5080、Escor ^TM 5100、Escor ^TM 5200 and Escor ^TM 6000 (manufactured by Exon Mobile Chemical).

Other suitable reactive impact modifiers include ionomers of ethylene-acid copolymers. Specific examples of such impact modifiers include

1601、/>

1601-2、/>

1601-2LM、/>

1605、

8150、/>

8320、/>

8528 and +>

8660 (manufactured by DuPont).

In other embodiments, the reactive impact modifier is an alkyl methacrylate-siloxane/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 siloxane 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. The graft copolymer is in the form of a core-shell rubber and has a grafting ratio of 5 to 90% (weight/weight), the glass transition temperature of the core is-150 to-20 ℃, and the glass transition temperature of the shell is 20 to 200 ℃. In one embodiment of the invention, the graft copolymer is a methyl methacrylate-siloxane/butyl acrylate graft copolymer. Specific examples include S-2001, S-2100, S-2200, S-2501 manufactured by Mitsubishi Rayon Co., ltd.

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

Suitable reactive and non-reactive impact modifiers also include the impact modifiers mentioned in paragraphs [0043] - [0072] of WO 2018/089573.

The term "non-reactive impact modifier" as used herein refers to an impact modifier that does not have functionalized end groups and thus is not capable of forming covalent chemical bonds with the polymer matrix. Non-reactive impact modifiers are typically dispersed in the polymer matrix by intensive compounding, but may coalesce downstream in the compounder.

Non-reactive impact modifiers may take on a unique core-shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and, since the structure is usually obtained by emulsion copolymerization, it provides a well-defined particle size which in turn leads to a well-controlled blend morphology.

Suitable examples of non-reactive core-shell impact modifiers include the impact modifiers mentioned in US 5,409,967, i.e. core-shell impact modifiers wherein the core consists essentially of a rubbery core polymer (e.g. comprising a diene, preferably a 1,3-diene) copolymer and the shell polymer consists essentially of a vinyl aromatic monomer (e.g. styrene and hydroxyalkyl (meth) acrylate, or another functional monomer which functions in a similar manner to hydroxyalkyl (meth) acrylate). Other suitable examples include impact modifiers having a soft rubber core (e.g., a butadiene core, an acrylic core, or a silicone-acrylic core) and a shell made of polymethyl methacrylate (PMMA).

In some embodiments, the reactive impact modifier has a functionalized end group selected from the group consisting of glycidyl methacrylate, maleic anhydride, and carboxylic acid. In a preferred embodiment, the functional group of the reactive impact modifier is glycidyl methacrylate.

In some embodiments, the reactive impact modifier has a functionalized end group selected from the group consisting of glycidyl methacrylate, maleic anhydride, and carboxylic acid, and the non-reactive impact modifier is a core-shell impact modifier. In a preferred embodiment, the reactive impact modifier has a functionalized end group that is glycidyl methacrylate and the non-reactive impact modifier is a core-shell impact modifier.

In some embodiments, the non-reactive impact modifier is a core-shell impact modifier. In a preferred embodiment, the non-reactive impact modifier is a core-shell impact modifier having a butadiene core, an acrylic or silicone-acrylic core, and a shell made of polymethyl methacrylate (PMMA).

In some embodiments, the reactive impact modifier has a functionalized end group selected from the group consisting of glycidyl methacrylate, maleic anhydride, and carboxylic acid, and the non-reactive impact modifier is an ethylene-acrylate copolymer. In a preferred embodiment, the reactive impact modifier has a functionalized end group that is glycidyl methacrylate and the non-reactive impact modifier is an ethylene-acrylate copolymer.

In some embodiments, the amount of reactive impact modifier in the polyester resin is from 0.25 to 10% (weight/weight), based on the total weight of the resin. In a preferred embodiment, the amount of reactive impact modifier in the polyester resin is from 0.5 to 5% (w/w), for example from 1 to 3% (w/w), based on the total weight of the resin.

In some embodiments, the amount of non-reactive impact modifier in the polyester resin is from 0.25 to 15% (weight/weight), based on the total weight of the resin. In a preferred embodiment, the amount of non-reactive impact modifier in the polyester resin is from 0.5 to 10% (w/w), for example from 1 to 3% (w/w), based on the total weight of the resin.

In some embodiments, the total amount of impact modifier in the polyester resin is from 0.5 to 25% (weight/weight), based on the total weight of the resin. In some embodiments, the total amount of impact modifier is from 2 to 15% (w/w), for example from 2 to 5% (w/w) or from 5 to 8% (w/w) or from 8 to 12% (w/w), based on the total weight of the resin.

The resin may contain a lubricant in addition to the filler and impact modifier. Lubricants are generally added to resins to improve processability and mold release properties of the resins by reducing friction (external lubricants) and by reducing viscosity and heat dissipation (internal lubricants), and to prevent damage to injection molding equipment. The external lubricant migrates to the interface between the molten resin and the surface of the processing equipment and reduces friction during processing, reduces adhesion of the resin to the mold surface, and prevents melt fracture. In addition, external lubricants reduce the coefficient of friction, generally increasing the scratch resistance of the molded parts. The internal lubricant promotes the flow of the resin and aids in mold filling.

Suitable lubricants for the resins useful in the present invention include fatty alcohols having chain lengths of C12 to C22 produced by hydrogenation of fatty acids or from ethylene by the ziegler process. These fatty alcohols can also be esterified using dicarboxylic acids. These lubricants are effective internal lubricants. Suitable lubricants include those sold under the names Abrilube and Abrilflo (produced by Abril Industrial fuels), interlite (produced by Akros Chemical), baerolub (produced by Baerlocher GmBH), naftolub (produced by Chemson Polymer-Additive Ges. MbH), loxiol (produced by Cognis Deutchland GmbH), ligallub (produced by Peter Green Fettchemie), atmer (produced by Uniqema), and Marklube (produced by Witco Vinyl Additives GmbH).

Other suitable lubricants include fatty acid esters of short chain alcohols, such as fatty acid glycerides. Suitable examples include liquid glycerol monooleate and solid glycerol monostearate and also triglycerides of 12-hydroxystearic acid (hydrogenated castor oil). Other suitable examples include the stearates of trimethylolpropane and pentaerythritol, as well as n-butyl stearate and isobutyl stearate. These lubricants are considered internal lubricants. Suitable lubricants include those sold under the brand names interbite (produced by Akros Chemical), baerolub (produced by baerocher GmBH), naftolb (produced by Chemson Polymer-Additive ges. Mbh), loxiol (produced by Cognis Deutchland GmBH), lubriol (produced by Comiel (Morton International Group)), syncrolube (produced by Croda Oleochemicals), petrac waters (produced by Ferro Corporation), teger 9xx (produced by th. Goldscht AG), glycolub, glycostat and polyaldol (produced by Lonza Benelux b.v.,), radia and Radiasurf (produced by finas n.v., r.), ligalub (produced by febux, r), lubricant (produced by reaction, r), lubricant (produced by company, r.g), and water (produced by water).

Fatty acids (e.g., stearic acid) may also be suitable lubricants in the resins of the present invention. These lubricants are known to have good release effects. Suitable lubricants include lubricants sold under the brand name internite (produced by Akros Chemical), baerolub (produced by Baerlocher GmBH), naftozin (produced by Chemson Polymer-Additive ges. Mbh), loxiol (produced by Cognis deutschland GmBH), lubriol (produced by Comiel (Morton International Group)), crodacid (produced by Croda olefins), stavinor (produced by Ceca), pentrac waters (produced by Ferro truck), radiacid (produced by fine Chemicals n.v.), ligalub (produced by pet greenpaper Chemicals), waxso (produced by so.

Fatty acid amides are another example of suitable lubricants for use in the resins of the present invention. Examples include oleamide and erucamide, and bis (stearyl) ethylenediamine (commonly referred to as amide wax). These lubricants exhibit a significant sliding effect. Suitable lubricants include lubricants sold under the brand names Abrilube and Abrillo (manufactured by Abril Industrial fuels), armoslip (manufactured by Akzo Nobel Chemicals), licowax (manufactured by Clariant GmbH), loxamid (manufactured by Cognis Deutchland GmbH), lubriol (manufactured by Commel (Morton International Group)), crodamid (manufactured by Croda Oleochemics), stavinor (manufactured by Ceca), acrawax and Glycolub (manufactured by Lonza Bennelux B.V.), ligalubb (manufactured by Peter Green Fettice), realub (manufactured by reagent Societa Azinini industri Industria), waxso (manufactured by SO.J.S.J.S.S.S.S.S.S.S.A), and Uniqetaether Australi lubricants (manufactured by Unikway).

Metal soaps, especially alkaline earth metal soaps, are also suitable for use as lubricants in the resins of the invention. These lubricants are known to stabilize plastics and also act as mold release agents. Suitable lubricants include lubricants manufactured under the trade name Haro Chem (manufactured by Akros Chemical), baerolub (manufactured by baerocher GmBH), lstab (manufactured by Chemson Polymer-Additive ges. Mbh), licowax (manufactured by Clariant GmBH), loxiol (manufactured by Cognis Deutchland GmBH), lubriol (manufactured by commercial (Morton International Group), stavinor (manufactured by Ceca), glycolub, glycopersise, lonzest, and Pegosperse (manufactured by Lonza Benelux b.v.), radiar (manufactured by Fina Chemicals n.v.), ligalub (manufactured by petri fe), realia soap (manufactured by realia soap a), wai, and lubricant g.g.r.

One important group of lubricants is montan wax. Coarse montan wax is a by-product of some (but not all) lignite coals. The chemical properties of montan wax are similar to those of fatty acids. Esters of long chain alcohols, esters of monofunctional and multifunctional short chain alcohols, and oligo (complex) esters are synthesized from montan wax acid. In addition, saponified products and various metal soaps can also be used as lubricants. Montan waxes are known to act as mold release agents and to reduce viscosity. Suitable lubricants include those sold under the brand names interbite (manufactured by Akros Chemical), luwax (manufactured by BASF AG), licowax (manufactured by Clariant GmbH), and Stavinor (manufactured by Ceca).

Polar PE and PP waxes are also examples of suitable lubricants for use in the resins of the present invention. Polar PE waxes are typically produced by introducing oxygen-containing polar groups into hydrocarbons by oxidation in air. Polar PP waxes are typically produced by grafting using maleic anhydride. Suitable lubricants include those sold under the brand names Interlite (manufactured by Akros Chemical), baeroluub (manufactured by Baerlocher GmbH), luwax (manufactured by BASF AG), naftoluub (manufactured by Chemson Polymer-Additive Ges. MbH), licowax (manufactured by Clariant GmbH), loxiol (manufactured by Cognis Deutchland GmbH), vestowa (manufactured by Creanova), epolene (manufactured by Eastman Chemicals International AG), petrac Waxes (manufactured by Ferro Carposition), A-CPolyethylene, aclyn Iomers, and Acumwell (manufactured by Honeywell), LE-Wachs (manufactured by Leuna Polymer GmbH), and Marklube (manufactured by Extingui AddijWith).

Fluoropolymer (i.e., polytetrafluoroethylene or of the general structure- (F) ₂ C-CF ₂ ) _n -oligomers) is another example of a suitable lubricant suitable for use in the resin of the present invention. Fluoropolymers improve friction characteristics. Suitable lubricants include those sold under the trade name Dyneon PTFE Mikropulver (manufactured by Dyneon GmbH).

Other suitable examples of lubricants include silicon-based lubricants, i.e., polysiloxanes. These lubricants are based on a lubricant having the general structure (-R) ₂ Si-O-SiR ₂ ) _n -wherein R represents an organic group, typically methyl or phenyl or a mixture thereof, and n represents the number of repeating units. Silicon-based lubricants, particularly Polydimethylsiloxane (PDMS), are known to improve mold filling, surface appearance, mold release, surface lubricity, and wear resistance. Suitable lubricants include those sold under the tradenames Tegopren (manufactured by Th. Goldsmith AG) and Genioplast (manufactured by Wacker Chemical Corporation).

Specific examples of commercially available lubricants suitable for use in the resin of the present invention include, but are not limited to, crodamide ER, crodamide VRX, crodamide OR, crodamide ORX, crodamide 212, crodamide EBS, and Crodamide EBSV (produced by Croda), incroMold K, incroMold T (produced by Croda), and IncroMax PET 100 (produced by Croda),

PELLET P PLUS、/>

PELLET S、

FLUID 110 and +>

PELLET 345 (manufactured by Wacker Chemical Corporation), kemamide E-180 (stearyl erucamide),. Sup.>

P-181 (oleyl palmitamide) and Kemamide W-20 (manufactured by PMC Biogenix Inc.).

In some embodiments, the total amount of lubricant in the polyester resin is 0.1 to 5% (weight/weight) based on the total weight of the resin. In some embodiments, the total amount of lubricant is 0.2 to 5% (w/w), for example 0.5 to 4% (w/w), more preferably 1 to 3.5% (w/w), and still more preferably 2 to 3% (w/w), based on the total weight of the resin.

The resin may contain other additives such as nucleating agents, hydrolysis resistance additives, mold release agents, ultraviolet stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants, and colorants or pigments, in addition to the filler, impact modifier, and lubricant.

The inventors of the present invention have also surprisingly found that in some cases, beneficial effects are obtained when a non-reactive impact modifier is used alone without the presence of a reactive impact modifier.

Thus, in an alternative embodiment, the invention relates to a toy building element made of a polyester material and manufactured by processing a resin comprising at least one polyester and at least one non-reactive impact modifier, wherein the polyester is a poly (ethylene terephthalate) polyester (PET polyester) or a modified PET polyester which has been modified by substitution of:

with the proviso that not all terephthalic acid groups and all ethylene glycol groups can be substituted simultaneously, and

provided that the resin does not contain any reactive impact modifier.

The inventors of the present invention have surprisingly found that better flow characteristics can be obtained when only a non-reactive impact modifier is used, compared to using a combination of reactive and non-reactive impact modifiers. It has been shown that it is easier to control the compounding of non-reactive impact modifiers than to carry out the reactive compounding process with reactive impact modifiers.

The invention also relates to a method of manufacturing a toy building element, the method comprising the steps of:

a) Providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a PET polyester or a modified PET polyester that has been modified by substitution of:

and

b) Processing the resin.

Suitable resins provided and processed in the method include the resins described above. Suitable examples of the PET polyester, the modified PET polyester, the reactive impact modifier and the non-reactive impact modifier include the corresponding substances described above.

The total amount of impact modifier is generally up to 25% (weight/weight) based on the total weight of the resin. In some embodiments, the total amount of impact modifiers is from 2 to 15% (w/w), such as from 2 to 5% (w/w), or from 5 to 8% (w/w), or from 8 to 12% (w/w), based on the total weight of the resin. In some embodiments, the amount of the reactive impact modifier is in the range of 0.25 to 10% (weight/weight) based on the total weight of the resin. In other embodiments, the total amount of the non-reactive impact modifier is from 0.25 to 15% (weight/weight), based on the total weight of the resin.

In some embodiments, the toy building element is manufactured by injection moulding.

In some embodiments, the impact modifier is mixed with the polyester during the feeding of the injection molding machine. In such embodiments, the total amount of impact modifier is preferably at most 3% (weight/weight) based on the total weight of the resin to obtain a suitable dispersion of the impact modifier in the resin.

In a preferred embodiment, at least the reactive impact modifier is mixed with the polyester during the feeding of the injection molding machine. In such embodiments, the amount of the reactive impact modifier is preferably up to 3% (weight/weight) based on the total weight of the resin to obtain a suitable dispersion of the reactive impact modifier in the resin. In other embodiments, the amount of the reactive impact modifier is up to 9% (weight/weight), for example up to 6% (weight/weight), based on the total weight of the resin.

In other embodiments, the impact modifier is mixed with the polyester prior to feeding the mixture to the injection molding machine. The mixing may be performed by dry blending or compounding.

In some embodiments, the impact modifier and the polyester are dry blended prior to feeding to the injection molding machine. In such embodiments, the total amount of impact modifier is preferably up to 5% (weight/weight) based on the total weight of the resin to obtain a suitable dispersion of the impact modifier in the resin.

In other embodiments, the impact modifier and the polyester are mixed by compounding prior to feeding to the injection molding machine. In this case, the resin is brought to a molten state and then mixed thoroughly to ensure adequate dispersion of the impact modifier in the polyester, then the mixture is cooled and converted into pellets, which are then fed into an injection molding machine.

In embodiments where the impact modifier and polyester are mixed by compounding, the total amount of impact modifier is typically up to 25% (weight/weight) based on the total weight of the resin. In some embodiments, the total amount of impact modifiers is from 2 to 15% (w/w), such as from 2 to 5% (w/w), or from 5 to 8% (w/w), or from 8 to 12% (w/w), based on the total weight of the resin.

In some embodiments, the impact modifier and the polyester are compounded by thorough mixing to ensure adequate dispersion and then fed directly into an injection molding machine.

In other embodiments, the polyester and the impact modifier may be mixed into a masterbatch, which is then mixed with the rest of the resin during the feed of the injection molding machine.

Additives such as fillers, nucleating agents, anti-hydrolysis additives, mold release agents, lubricants, uv stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants, and colorants or pigments may be added before or during feeding to the injection molding machine and mixed with the impact modifier and polyester.

In some embodiments, the toy building element is manufactured by additive manufacturing. A suitable example of an additive manufacturing technique is a technique of constructing a toy building element by photo-polymeric additive manufacturing or thermoplastic additive manufacturing, such as liquid-based additive manufacturing, toner-based additive manufacturing, powder-based additive manufacturing or particle-based additive manufacturing.

Examples of the invention

In the following examples it is described how toy bricks can be manufactured by injection moulding. The blocks produced were then tested by the Charpy V notch test.

Charpy V notch test

Molded plastic rods with dimensions of 6.0 × 4.0 × 50.0 (length × width × height) cubic centimeters and the associated materials to be tested were cut according to ISO 179-1/1eA using a notch cutter (ZNO of zwitter, germany) with a notch tip diameter of 0.5 mm. Notch samples were placed against the pendulum with a V-notch according to the principles described in ISO 179-1.

Example 1: using Paraloid ^TM EXL-3691J and ELVALOY ^TM Modification of PET by PTW

Post-consumer bottle grade PET having an IV of 0.80 deciliters/gram was dried at 150 ℃ to a moisture content of 50-100ppm. Reacting the PET with an impact modifier Paraloid when the dried PET material is cooled to below 50 ℃ in the environment ^TM EXL-3691J (non-reactive impact modifier, produced by Dow Chemical Company) and ELVALOY ^TM PTW (a reactive random terpolymer composed of ethylene, butyl acrylate and glycidyl methacrylate (epoxy functional), produced by Dow/Dupont Chemical Company) was dry blended. The amounts of each impact modifier are set forth in the table below. The blend was processed into pellets by twin screw extrusion and then into tensile and impact bars by injection molding. The obtained impact bars were tested by the charpy V-notch test as described above. The results are shown in the following table.

The injection molding parameters were as follows:

melting temperature: 295 ℃ C

Temperature of hot runner: 300 deg.C

Temperature of the die: 20 deg.C

The extrusion processing parameters were as follows:

barrel temperature: 290 deg.C

Melting temperature: 295-300 deg.C

As can be seen in the comparative tests 1-3, 1-8 and 1-5, the impact modifier used was 4% (w/w) ELVALOY ^TM The resin-made molded plastic rods of PTW had Charpy V-notch values of 15 kJ/m and contained 5% (weight/weight) Paraloid as the sole impact modifier ^TM The resin EXL-3691J had a Charpy V notch value of 8 kJ/m. Very surprisingly, the results show that the impact modifier is made of two impact modifiers comprising the same amount (i.e., 4% (w/w) ELVALOY) ^TM PTW and 5% (weight/weight) Paraloid ^TM EXL-3691J) has a charpy V-notch value of 65 kilojoules per square meter. In other words, the results show that when a reactive impact modifier and a non-reactive impact modifier are used in combination, a synergistic effect is obtained.

Similar synergistic effects can also be seen when comparing runs 1-2, 1-9 and 1-6.

In summary, the results clearly show that the reactive impact modifier (ELVALOY) is being modified ^TM PTW) with non-reactive impact modifier (Paraloid) ^TM EXL-3691J) in combination, a synergistic effect on the Charpy V-notch value is obtained.

Example 2: using Paraloid ^TM EXL-3330 and ELVALOY ^TM PTW modification of PETG and PETT

Two different types of copolyesters were tested in a compounding test with different types of impact modifiers. One common type of copolyester is SkyGreen produced by SK Chemicals ^TM KN100 which is poly (ethylene glycol-co-1, 4-cyclohexanedimethanol terephthalate) (PETG). Another type of copolyester is Eastman, produced by Eastman ^TM GMX201 Natural, which is poly (ethylene glycol-co-2, 4-tetramethyl-1, 3-cyclobutanediol terephthalate) (PETT). Samples of PETG and PETT were dried at 70 ℃ to moisture contentIs 50-100ppm. When the dried material was cooled to below 50 ℃ in the ambient, samples of the material were combined with an impact modifier Paraloid according to the following table ^TM EXL-3330 (non-reactive impact modifier, produced by Dow Chemical Company) and ELVALOY ^TM PTW (a reactive random terpolymer consisting of ethylene, butyl acrylate and glycidyl methacrylate (epoxy functional) manufactured by Dow/Dupont Chemical Company) was dry blended. The blend was processed into pellets by twin screw extrusion and then into tensile and impact bars by injection molding. The obtained impact bars were tested by the charpy V-notch test as described above. The results are shown in the following table.

The injection molding parameters were as follows:

melting temperature: 290 deg.C

Temperature of hot runner: 295 deg.C

Temperature of the die: 30 deg.C

The extrusion processing parameters were as follows:

barrel temperature: 290 deg.C

Melting temperature: 295-300 deg.C

As can be seen when comparing tests 2-1, 2-3, 2-4 and 2-5, molded plastic bars made from resin containing PETG but no impact modifier had a Charpy V notch value of 9.4 kJ/m. After addition of 2.5% (w/w) ELVALOY ^TM PTW as the sole impact modifier, the PETG-containing resin had a Charpy V-notch value of 11.0 kJ/m with the addition of 5% (w/w) Paraloid ^TM EXL-3330 as the sole impact modifier, the PETG-containing resin had a Charpy V-notch value of 12.9 kJ/m. Very surprisingly, the results show that the PETG is comprised of 2.5% (w/w) ELVALOY ^TM PTW and 5% (weight/weight) Paraloid ^TM A molded plastic bar of EXL-3330 resin had a Charpy V notch value of 21.6 kJ/m. In other words, the results show that the reactivity is reducedWhen an impact modifier and a non-reactive impact modifier are used in combination, a synergistic effect is obtained.

As can be seen when comparing tests 2-2, 2-6, 2-7 and 2-8, molded plastic bars made from resin containing PETT but no impact modifier had a Charpy V notch value of 4.5 kilojoules per square meter. After addition of 2.5% (w/w) ELVALOY ^TM PTW as the sole impact modifier, the PETT-containing resin had a Charpy V notch value of 7.5 kJ/m with 5% (weight/weight) Paraloid added ^TM EXL-3330 as the sole impact modifier, the PETG-containing resin had a Charpy V-notch value of 7.6 kJ/m. Very surprisingly, the results show that the composition is made up of PETG and 2.5% (w/w) ELVALOY ^TM PTW and 5% (weight/weight) Paraloid ^TM The resin molded plastic rod of EXL-3330 had a charpy V-notch value of 106.4 kilojoules per square meter. In other words, the results show that when a reactive impact modifier and a non-reactive impact modifier are used in combination, a synergistic effect is obtained.

To sum up: the results clearly show that in the case of PETG-containing resins or PETT-containing resins with reactive impact modifiers (ELVALOY) ^TM PTW) and a non-reactive impact modifier Paraloid ^TM When EXL-3330 was mixed, a significant synergistic effect on charpy V-notch values was obtained.

Claims

1. A toy building element made of a polyester material and manufactured by processing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a poly (ethylene terephthalate) polyester (PET polyester) or a modified PET polyester which has been modified by substitution of:

2. The toy building element of claim 1, wherein said polyester is a PET polyester or a modified PET polyester modified by substituting isophthalic acid for all or part of the terephthalic groups of the PET polyester.

3. The toy building element of claim 1 wherein said polyester is a modified PET polyester modified by substituting furan dicarboxylic acid groups for all terephthalic acid groups of the PET polyester.

4. The toy building element of claim 1, wherein said polyester is a mixture of:

PET polyester or modified PET polyester modified by substitution of all or part of the terephthalic acid groups of the PET polyester with isophthalic acid, and

-a modified PET polyester modified by replacing all the terephthalic acid groups of the PET polyester with furandicarboxylic acid groups.

5. The toy building element of claim 1, wherein said polyester is a modified PET polyester modified by substituting 1, 4-cyclohexanedimethanol for a portion of the ethylene glycol groups of the PET polyester.

6. The toy building block of any one of the preceding claims, wherein the amount of the PET polyester or modified PET polyester is in the range of 75-95% (weight/weight) based on the total weight of the resin.

7. Toy block according to any one of the preceding claims, wherein the amount of reactive impact modifier is in the range of 0.25-10% (w/w) based on the total weight of the resin.

8. The toy block of any one of the preceding claims, wherein the amount of the non-reactive impact modifier is in the range of 0.25-15% (w/w), based on the total weight of the resin.

9. The toy block of any one of the preceding claims, wherein the resin further comprises an additive selected from the group consisting of fillers, nucleating agents, hydrolysis resistance additives, mold release agents, lubricants, uv stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants, and colorants and/or pigments, and mixtures thereof.

10. A method of manufacturing a toy building element comprising the steps of:

and

b) Processing the resin.

11. The method of claim 10, wherein the toy building element is manufactured by injection molding and/or additive manufacturing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.

12. The method of any one of claims 10 or 11, wherein the resin further comprises an additive selected from the group consisting of fillers, nucleating agents, anti-hydrolysis additives, mold release agents, lubricants, uv stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants, and colorants and/or pigments, and mixtures thereof.

13. The process of any one of claims 10 to 12, wherein the impact modifier is mixed with the polyester during feeding of an injection molding machine.

14. The process of any one of claims 10 to 13, wherein the impact modifier is mixed with the polyester prior to feeding the mixture to an injection molding machine.