Filament suitable for fiber and 3D printing

Abstract

The present invention relates to fibers made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, and to a method for preparing such fibers. The present invention also relates to a filament suitable for three-dimensional printing made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, and to a method for preparing such a filament.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to EP Patent Application No. 23162116.0, filed on 15 March 2023, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] [Technical Field] The present invention relates to fibers comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, methods for preparing such fibers, and the use of such fibers in yarns or fabrics. The present invention also relates to filaments suitable for three-dimensional printing comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, methods for preparing such filaments, and the use of such filaments for three-dimensional printing. [Background technology]

[0003] Sustainable textiles should be based on ecological, economic, and social sustainability. Sustainable products must consider these factors from raw materials to processing, finishing, sales, and recycling.

[0004] Today, fibers used in sustainable textiles include, for example, natural fibers such as cotton, wool, linen, and SeaCell® (cellulose fiber derived from algae, manufactured by Smartfiber); recycled fibers such as recycled polyester (e.g., derived from polyethylene terephthalate (PET) bottles) and Econyl® (recycled nylon fiber); or regenerated fibers such as lyocell (e.g., Tencel®, manufactured by Lenzing) or modal (a term for fibers prepared from natural materials such as wood through chemical processing). Examples include the following:

[0005] However, even though these fibers are used in sustainable textile products, they have various drawbacks. For example, cotton and wool production requires large amounts of water and land. Obtaining recycled fibers such as recycled PET typically requires large amounts of energy, water, and chemicals.

[0006] Sustainable textile products are even more desirable to be suitable for use under the concept of a circular economy. In particular, it is desirable that textile products and fibers exhibit appropriate biodegradability so that they can be used in a biological cycle, for example, under a cradle-to-cradle design, thereby avoiding non-degradable waste. Beneficial induction of textile products into the biological cycle is achieved when textile products are returned at the end of their life cycle and subjected to industrial composting. This generates biomass and biogas (CH4, CO2, water), which can be directly input into the biological cycle.

[0007] Therefore, there is a continuing need for fibers that meet particularly ecological requirements. Accordingly, providing such fibers is the objective of this invention.

[0008] Similar considerations apply to filaments and three-dimensional printed molded products that can be used in three-dimensional printing. Therefore, there is a need for filaments suitable for three-dimensional printing that address particularly ecological requirements. Similarly, there is a need for three-dimensional printed molded products that address particularly ecological requirements. Therefore, an object of the present invention is to provide such filaments suitable for three-dimensional printing. It is also an object of the present invention to provide such three-dimensional printed molded products. [Overview of the project]

[0009] This objective is achieved by fibers, yarns, garments, and methods having the features of the independent claims.

[0010] In a first aspect, the present invention relates to fibers made from a mixture comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate.

[0011] In a second aspect, the present invention relates to a yarn comprising the fibers of the present invention.

[0012] In a third aspect, the present invention relates to a fabric comprising the fibers or the yarn of the present invention.

[0013] In a fourth aspect, the present invention relates to a method for preparing fibers according to the present invention, comprising the following steps: - Spinning a melt comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate through a spinning nozzle to obtain precursor fibers; and - Cooling the precursor fibers to obtain fibers.

[0014] In a fifth aspect, the present invention relates to the use for the production of fibers of a melt comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate, wherein the fibers are as defined herein.

[0015] In a sixth aspect, the present invention relates to the use for the preparation of fibers of a melt comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate.

[0016] In a seventh aspect, the present invention relates to the use for the production of fibers of a mixture comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate, wherein the fibers are as defined herein.

[0017] In an eighth aspect, the present invention relates to the use for the production of fibers of a mixture comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate.

[0018] The object of the present invention can also be achieved by a filament suitable for three-dimensional printing, a roll containing the filament, a cartridge suitable for a three-dimensional printer, a three-dimensional printed molded product, and a method having the features of the independent claims.

[0019] In a ninth aspect, the present invention relates to a filament suitable for three-dimensional printing, made from a mixture comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate.

[0020] In a tenth aspect, the present invention relates to a roll containing a filament suitable for three-dimensional printing.

[0021] In an eleventh aspect, the present invention relates to a cartridge suitable for a three-dimensional printer, comprising a filament suitable for three-dimensional printing according to the present invention.

[0022] In a twelfth embodiment, the present invention relates to a three-dimensional printed molded article, which can or can be obtained by subjecting a filament suitable for three-dimensional printing of the present invention to three-dimensional printing.

[0023] In a thirteenth embodiment, the present invention relates to a method for preparing a filament suitable for three-dimensional printing, the preparation method comprising extruding a molten material containing an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate into a filament shape.

[0024] In a fourteenth aspect, the present invention relates to the use of melts comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, wherein the filaments are as defined herein.

[0025] In a fifteenth aspect, the present invention relates to the use of melts comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing.

[0026] In a fourteenth aspect, the present invention relates to the use of a mixture comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, wherein the filaments are as defined herein.

[0027] In a fifteenth aspect, the present invention relates to the use of a mixture comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing. [Brief explanation of the drawing]

[0028] The present invention will be better understood by considering the following non-limiting embodiments and drawings in conjunction with the detailed description: [Figure 1] Figure 1 is a schematic diagram of a melt spinning apparatus for preparing fibers according to an embodiment of the present invention. [Figure 2] Figure 2 schematically shows a fiber manufacturing process, including further processing of fibers in a fiber post-processing line, according to an embodiment of the present invention. [Figure 3] Figure 3 is a photograph showing granules of a mixture that can be used to prepare fibers or filaments suitable for injection molding according to the present invention, fibers according to embodiments of the present invention, yarn produced from the fibers, and a shirt (in particular, yarn produced from the fibers) produced using the fibers according to embodiments of the present invention. Figure 3 also shows a filament suitable for three-dimensional printing according to embodiments of the present invention. [Figure 4] Figure 4 is a photograph showing a shirt manufactured using the fibers according to an embodiment of the present invention, and in particular a further appearance of the yarn manufactured from the fibers. [Modes for carrying out the invention]

[0029] 〔fiber〕 As described above, in the first embodiment, the present invention relates to fibers made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate.

[0030] A mixture consisting of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate was found to be suitable for fiber preparation. In particular, fibers containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate can be obtained, or may be obtained, by melt spinning a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In this regard, a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate was found to exhibit good spinnability useful for melt spinning. Furthermore, fibers consisting of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate were found to exhibit good properties for use as woven fibers, such as good mechanical strength, elongation, flexibility, elasticity, and abrasion resistance. A further advantage is that the water and land consumption required for fiber preparation is far less than that of cotton (see Example 3). Another further advantage is that the fibers can be manufactured without the use of harmful substances such as antimony (see Example 2). Furthermore, by using aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, it is possible to obtain fibers that are biodegradable, conform to the European harmonized standard EN13432, and can be processed in industrial composting plants. The fibers of the present invention can be used, for example, as woven fibers for manufacturing clothing such as shirts (see Example 4 and Figures 3, 4). Such clothing fibers are biodegradable and have been shown to decompose / corrode completely in just 2-3 weeks after being placed in organic waste.In this context, it should be noted that various products, such as plates, foils, and fibers, consisting of one or more aliphatic polyesters, aliphatic-aromatic polyesters, and / or polyhydroxyalkanoates, are described, for example, in European Patent No. 3626767, International Publication No. 2010 / 034689, International Publication No. 2010 / 034711, International Publication No. 2015 / 169660, European Patent No. 1966419, European Patent No. 2984138, Chinese Patent No. 103668540, Chinese Patent No. 103668541, International Publication No. 2014 / 173055, and Chinese Patent No. 104120502.

[0031] As used herein, the term “aliphatic polyester” generally refers to polyesters synthesized by condensation polymerization of an aliphatic diol with an aliphatic dicarboxylic acid or its anhydride. Exemplarily, as used herein, aliphatic polyesters are aliphatic C2-C2. 20 Dicarboxylic acids and aliphatic C2-C 12 Diols may be included. Preferably, the aliphatic diol is an aliphatic C2-C8 diol. More preferably, the aliphatic diol is an aliphatic C2-C6 diol. Even more preferably, the aliphatic diol is an aliphatic C3 diol or an aliphatic C4 diol. Examples of aliphatic diols used in aliphatic polyesters include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Preferably, the aliphatic diol is 1,3-propanediol or 1,4-butanediol. More preferably, the aliphatic diol is 1,4-butanediol. Preferably, the aliphatic dicarboxylic acid is an aliphatic C2-C 12It is a dicarboxylic acid. More preferably, the aliphatic dicarboxylic acid is an aliphatic C2-C8 dicarboxylic acid, and even more preferably an aliphatic C4 dicarboxylic acid. Examples of the aliphatic dicarboxylic acid used in the aliphatic polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, etc. Preferably, the aliphatic dicarboxylic acid is malonic acid or succinic acid. More preferably, the aliphatic dicarboxylic acid is succinic acid. Optionally, when the dicarboxylic acid is an aliphatic C2-C 12 dicarboxylic acid, the aliphatic polyester is C2-C 12 It may further contain an aliphatic C6-C 20 dicarboxylic acid different from the dicarboxylic acid. Examples of any aliphatic C6-C 12 dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, brassilic acid and arachidonic acid. Preferably, any aliphatic C6-C 12 dicarboxylic acid may contain adipic acid, suberic acid, azelaic acid, sebacic acid and brassilic acid. Any aliphatic C2-C 12Dicarboxylic acids may be present in the aliphatic polyester in a proportion of 0 to 10 mol% based on 100 mol% of the total amount of aliphatic dicarboxylic acids in the aliphatic polyester. Optionally, the aliphatic polyester may further contain chain extenders and / or branching agents. Examples of optional chain extenders and / or branching agents include polyfunctional isocyanates, isocyanurates, oxazolines, carboxylic acid anhydrides such as maleic anhydride, epoxides (especially epoxy-containing poly(meth)acrylates), at least trihydric alcohols, and at least tribasic carboxylic acids. Any chain extender and / or branching agent may be present in the aliphatic polyester in a proportion of 0 to 1% by weight based on 100% by weight of the total amount of aliphatic dicarboxylic acids and aliphatic diols. The term "aliphatic polyester" may also include mixtures of two or more different aliphatic polyesters. Aliphatic polyesters may have a number-average molecular weight (Mn) in the range of 2,500 to 150,000 g / mol, preferably 5,000 to 100,000 g / mol, more preferably 7,500 to 75,000 g / mol, even more preferably 10,000 to 65,000 g / mol, and even more preferably 12,000 to 60,000 g / mol. Aliphatic polyesters may have a weight-average molecular weight (Mw) in the range of 5,000 to 300,000 g / mol, preferably 10,000 to 250,000 g / mol, more preferably 20,000 to 220,000 g / mol, even more preferably 50,000 to 200,000 g / mol, and even more preferably 60,000 to 190,000 g / mol. Aliphatic polyesters can have a polydispersity index (i.e., the ratio of weight-average molecular weight to number-average molecular weight (Mw / Mn)) in the range of 1 to 6, preferably 1 to 4, more preferably 1.0 to 3.0, even more preferably 1.2 to 2.0, and even more preferably 1.4 to 1.8.

[0032] Examples of aliphatic polyesters that can be used in the present invention may include aliphatic polyesters selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasrate (PBSBr), and combinations thereof. The aliphatic polyester may preferably be selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasrate (PBSBr), and combinations thereof. In preferred embodiments, the aliphatic polyester is polybutylene succinate. The term "polybutylene succinate" as used specifically herein refers to the condensation product of succinic acid, an aliphatic dicarboxylic acid, and 1,4-butanediol, an aliphatic diol. Polybutylene succinate (PBS) and polybutylene succinate-co-adipate (PBSA), which are aliphatic polyesters, are commercially available, for example, as Blanche® from Showa Polymer Co., Ltd. and as GSPIa® from Mitsubishi Corporation. Aliphatic polyesters, particularly polybutylene succinate (PBS), can be obtained from renewable or fossil resources. Preferably, aliphatic polyesters derived from renewable resources are used. More preferably, bio-based polybutylene succinate (PBS) produced from bio-based succinic acid and 1,4-butanediol, such as that commercially available from Mitsubishi Chemical under the trade name BioPBS® FZ71, can be used. Preferably, the aliphatic polyester is biodegradable. In particular, polybutylene succinate (PBS) is a biodegradable aliphatic polyester.

[0033] Preferably, the fiber contains 30 to 70% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the fiber contains 35 to 65% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 40 to 60% by weight or 42 to 62% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 45 to 55% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges may apply when the aliphatic polyester is polybutylene succinate. In a preferred embodiment, the fiber comprises 52% by weight of polybutylene succinate, based on a total amount of 100% by weight of polybutylene succinate, aliphatic aromatic polyester, and polyhydroxyalkanoate.

[0034] As commonly used herein, the term “aliphatic-aromatic polyester” generally refers to polyesters synthesized from aliphatic diols, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids. For example, aliphatic-aromatic polyesters include aliphatic C2-C2 compounds. 20 Dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic C 2- C 12Diols may be included, preferably the aliphatic diol is an aliphatic C2-C8 diol. More preferably the aliphatic diol is an aliphatic C2-C6 diol. Even more preferably the aliphatic diol is an aliphatic C3 diol or an aliphatic C4 diol. Aliphatic diols used in aliphatic polyesters may include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Preferably the aliphatic diol is 1,3-propanediol or 1,4-butanediol. More preferably the aliphatic diol is 1,4-butanediol. Preferably the aliphatic dicarboxylic acid is an aliphatic C2-C 12 It is a dicarboxylic acid. More preferably, the aliphatic dicarboxylic acid is an aliphatic C4-C 10The aliphatic dicarboxylic acid is a dicarboxylic acid, and more preferably an aliphatic C6 dicarboxylic acid. Examples of aliphatic dicarboxylic acids used in aliphatic-aromatic polyesters include glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassic acid, suberic acid, and itaconic acid. Preferably, the aliphatic dicarboxylic acid is adipic acid, azelaic acid, or sebacic acid. More preferably, the aliphatic dicarboxylic acid is adipic acid. Preferably, the aromatic dicarboxylic acid is terephthalic acid. The aromatic dicarboxylic acid, particularly terephthalic acid, may be present in the aliphatic-aromatic polyester in amounts of, for example, 30 to 70 mol-%, preferably 40 to 60 mol-%, and more preferably 40 to 55 mol-%, based on a total amount of aliphatic dicarboxylic acid and aromatic dicarboxylic acid of 100 mol-%, respectively. Optionally, the aliphatic polyester may further contain chain extenders and / or branching agents. Optional chain extenders may include, for example, bifunctional or polyfunctional isocyanates, preferably hexamethylene diisocyanates. Optional branching agents may include, for example, trimethylolpropane, pentaerythritol, preferably glycerol. Any chain extenders and / or branching agents may be present in the aliphatic polyester in a proportion of 0 to 1% by weight, based on 100% by weight of the total amount of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic diols. The term "aliphatic-aromatic polyester" may include mixtures of two or more different aliphatic-aromatic polyesters. Aliphatic-aromatic polyesters may have a number-average molecular weight (Mn) in the range of 1,000 to 500,000 g / mol, preferably 5,000 to 300,000 g / mol, more preferably 5,000 to 100,000 g / mol, even more preferably 10,000 to 75,000 g / mol, and even more preferably 15,000 to 50,000 g / mol. Aliphatic-aromatic polyesters may have a weight-average molecular weight (Mw) in the range of 10,000 to 500,000 g / mol, preferably 20,000 to 400,000 g / mol, more preferably 30,000 to 300,000 g / mol, and even more preferably 60,000 to 200,000 g / mol.Aliphatic-aromatic polyesters can have a polydispersity index (i.e., the ratio of weight-average molecular weight to number-average molecular weight (Mw / Mn)) in the range of 1 to 6, preferably 2 to 4, more preferably 1.0 to 3.0, even more preferably 1.2 to 2.0, and even more preferably 1.4 to 1.8.

[0035] Aliphatic-aromatic polyesters usable in the present invention include, but are not limited to, aliphatic-aromatic polyesters selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof. In a preferred embodiment, the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). As used herein, the term "polybutylene adipate terephthalate" refers to an aliphatic-aromatic polyester containing adipic acid, an aliphatic dicarboxylic acid; terephthalic acid, an aromatic dicarboxylic acid; and 1,4-butanediol, an aliphatic diol. Aliphatic-aromatic polyesters, particularly polybutylene adipate terephthalate (PBAT), can be obtained from renewable or fossil resources. Preferably, aliphatic-aromatic polyesters derived from renewable resources are used. Polybutylene adipate terephthalate (PBAT) is commercially available, for example, from BASF as Ecoflex®, such as Ecoflex® F Blend C1200 or Ecoflex® FBX 7011, or from Showa Denko as Bionolle®. Preferably, the aliphatic-aromatic polyester is biodegradable. In particular, polybutylene adipate terephthalate (PBAT) is a biodegradable aliphatic-aromatic polyester.

[0036] Preferably, the fiber contains 10 to 60% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the fiber contains 20 to 50% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 25 to 40% by weight or 26 to 46% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 30 to 40% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges are applicable when the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). In a preferred embodiment, the fiber comprises 36% by weight of polybutylene adipate terephthalate (PBAT), based on a total amount of aliphatic polyester, polybutylene adipate terephthalate (PBAT), and polyhydroxyalkanoate of 100% by weight.

[0037] As used herein, the term “polyhydroxyalkanoate” generally refers to polyesters obtained from hydroxyalkanecarboxylic acid monomers. Polyhydroxyalkanoates can be produced by many microorganisms, including bacterial fermentation of sugars or lipids. Preferably, the hydroxyalkanecarboxylic acid is C4-C 18 The hydroxyalkanecarboxylic acid is, preferably, a hydroxyalkanecarboxylic acid containing 4 to 18 carbon atoms. More preferably, the polyhydroxyalkanoate contains monomer units having the following formula (I):

[0038] [ka]

[0039] Here, R is given by equation C n H 2n+1 The alkyl group is such that n is an integer from 1 to 15, preferably from 1 to 6. In some embodiments, the polyhydroxyalkanoate is a homopolymer. In some preferred embodiments, the polyhydroxyalkanoate is a copolymer. When the polyhydroxyalkanoate is a copolymer, the copolymer may contain two different monomer units of formula (I). The term "polyhydroxyalkanoate" may also include a mixture of two or more different polyhydroxyalkanoates. The polyhydroxyalkanoate may have a weight-average molecular weight (Mw) in the range of 70,000 to 1,000,000 g / mol, preferably 100,000 to 1,000,000 g / mol, and more preferably 300,000 to 600,000 g / mol.

[0040] Examples of polyhydroxyalkanoates that may be used in this disclosure may include polyhydroxyalkanoates selected from the group consisting of polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, polyhydroxybutyrate-co-hydroxyhexanoate, and any combination thereof. Preferably, the polyhydroxyalkanoate is selected from the group consisting of poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), and any combination thereof. More preferably, the polyhydroxyalkanoate is [ka] The polyhydroxyalkanoate is selected from the group consisting of these combinations. More preferably, the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate. In a very preferred embodiment, the polyalkoxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH). Preferably, the molar ratio m:n in the above-described structural formula is 95:5 to 85:15, more preferably 90:10 to 88:12. Preferably, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH) having a molar ratio of 5 to 15 mol%, preferably 7 to 13 mol%, and more preferably 10 to 13 mol%, of 3-hydroxyhexanoate based on 100 mol% of the total amount of monomers in poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH) is used. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is sold, for example, by P&G and Kaneka. Polyhydroxyalkanoates, in particular poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) can be obtained from renewable or fossil resources. Preferably, polyhydroxyalkanoates derived from renewable resources are used. More preferably, bio-based poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) can be used, which is commercially available, for example, from Kaneka under the trade name AONILEX X 151 A. Preferably, the polyhydroxyalkanoate is biodegradable. In particular, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is a biodegradable polyhydroxyalkanoate.

[0041] Preferably, the fiber contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the fiber contains 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 3 to 20% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the fiber contains 3 to 18% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the fiber contains 5 to 15% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Preferably, when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), the fiber contains 20% by weight or less, more preferably 18% by weight or less of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH).If the proportion of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) exceeds 18% by weight, it may become difficult to achieve the EN 13432 standard for biodegradability without pre-composting or industrial composting, and it becomes even more difficult if it exceeds 20% by weight. In a preferred embodiment, the fiber contains 12% by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) based on a total amount of polybutylene succinate, polybutylene adipate terephthalate, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) of 100% by weight.

[0042] In a very preferred embodiment, the aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyalkoxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Therefore, in a very preferred embodiment, the fiber comprises polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0043] The ranges of amounts of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate can also be combined with each other. For example, a fiber may contain 42-62% by weight, preferably 45-55% by weight, of aliphatic polyester; a fiber may contain 26-46% by weight, preferably 30-40% by weight, of aliphatic-aromatic polyester; and a fiber may contain 2-22% by weight, preferably 3-20% by weight, more preferably 3-18% by weight, of polyhydroxyalkanoate, with each proportion based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. A person skilled in the art will readily select appropriate amounts of one or more polymers within the range provided herein so as not to exceed 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges apply when the aliphatic polyester is polybutylene succinate, the aliphatic aromatic polyester is polybutylene adipate terephthalate, and the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In a very preferred embodiment, the fiber comprises 52% by weight of polybutylene succinate, 36% by weight of polybutylene adipate terephthalate, and 12% by weight of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), where each proportion is based on 100% by weight of the total amount of polybutylene succinate, polybutylene adipate terephthalate, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0044] In some embodiments, the polyhydroxyalkanoate may be partially or completely substituted with polylactide (also known as PLA, or polylactic acid or poly(lactic acid)). Therefore, in some embodiments, when the polyhydroxyalkanoate is partially substituted with polylactide, the fiber comprises an aliphatic polyester, an aliphatic-aromatic polyester, the polyhydroxyalkanoate, and the polylactide. In some embodiments, when the polyhydroxyalkanoate is completely substituted with polylactide, the fiber comprises an aliphatic polyester, an aliphatic-aromatic polyester, and the polylactide. However, in embodiments where the polyhydroxyalkanoate is completely substituted with polylactide, the fiber does not contain the polyhydroxyalkanoate.

[0045] Preferably, the fibers are woven fibers. As used herein, the term “fiber” generally refers to fibers suitable for making textiles. In non-limiting examples, woven fibers may be suitable for preparing yarns, textiles, or textile surfaces.

[0046] Optionally, the fiber may further contain at least one additive (or one or more additives). For example, the fiber may contain at least one additive (or one or more additives) that are commonly known to be used in textile fibers. Optional additives may include, but are not limited to, flame retardants, matting agents, markers for certification (e.g., fluorescent markers), antimicrobial agents, colorants, plasticizers, fillers, and any combination thereof.

[0047] Preferably, the fiber further contains a flame retardant, such as a phosphate. The term "phosphate" as used herein refers to [H2PO4] - [HPO4] 2- and [PO4] 3- This refers to a salt containing an anion selected from the group consisting of the following. Preferably, the cation is ammonium [NH4]. +Therefore, in a preferred embodiment, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), and any combination thereof. More preferably, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), and any combination thereof. More preferably, the flame retardant is ammonium dihydrogen phosphate ([NH4][H2PO4]) or diammonium hydrogen phosphate ([NH4]2[HPO4]). Even more preferably, the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]). Alternatively, or in addition, the flame retardant may be a polyphosphate. A "polyphosphate" is a salt or ester of a polymer oxyanion formed from tetrahedral PO4 (phosphate) structural units linked by sharing oxygen atoms. Preferably, if the flame retardant is a polyphosphate, the flame retardant is ammonium polyphosphate.

[0048] The fibers may contain a flame retardant in an amount of 0.01% to 5% by weight, based on 100% by weight of the total weight of the fibers. Preferably, the fibers contain a flame retardant in an amount of 0.1% to 4% by weight, based on 100% by weight of the total weight of the fibers. More preferably, the fibers contain a flame retardant in an amount of 0.2% to 3% by weight, based on 100% by weight of the total weight of the fibers. Even more preferably, the fibers contain a flame retardant in an amount of 0.3% to 3% by weight, based on 100% by weight of the total weight of the fibers. Even more preferably, the fibers contain a flame retardant in an amount of 0.3% to 2% by weight, based on 100% by weight of the total weight of the fibers. In particular, the above ranges apply when the flame retardant is a phosphate or polyphosphate, preferably when the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]).

[0049] Optionally, the fibers may also contain a matting agent. Any matting agent known to those skilled in the art may be used, such as typical matting agents used in fibers. For example, the matting agent may be zinc sulfide.

[0050] Optionally, the fibers may also contain markers suitable for certification. As an exemplary, non-limiting example, the markers suitable for certification may be fluorescent markers. The fluorescence of the fibers can be detected by appropriate equipment and collected for certification. For example, fluorescent markers available from Polysecure (Freiburg im Breisgau, Germany) can be used. Markers suitable for certification are generally used in small amounts and do not alter the properties of the fibers. Typically, the amount of markers suitable for certification in the fibers is in the range of ppb (parts per billion).

[0051] Optionally, the fibers may also contain an antimicrobial agent. Any antimicrobial agent known to those skilled in the art and suitable for use in fibers may be used. In an exemplary, non-limiting example, the antimicrobial agent may be zinc encapsulated in polyethylene terephthalate. Such an antimicrobial agent is commercially available, for example, under the product name SMARTZINC 213 PET Hot Melt from Smartpolymer GmbH in Rudhlstadt, Germany.

[0052] Optionally, the fibers may also contain a plasticizer. Any plasticizer known to the industry and suitable for use in fibers may be used. For example, the plasticizer may be polycaprolactone. In particular, polycaprolactone is biodegradable. In some embodiments, the fibers may contain polycaprolactone in an amount of 1% by weight or less based on 100% by weight of the total weight of the fibers. Fibers containing 1% by weight or less of polycaprolactone have been found to exhibit satisfactory softness and flexibility. However, it should be noted that the fibers of the present invention, including aliphatic polyesters, aliphatic-aromatic polyesters and polyhydroxyalkanoates, can usually exhibit satisfactory softness and flexibility without the addition of polycaprolactone or other plasticizers.

[0053] Optionally, the fibers may also contain colorants. Any colorant that provides the desired color and is suitable for use with the fibers may be used. For example, the colorant may be an inorganic pigment or an organic pigment.

[0054] Optionally, the fibers may also contain fillers. Any filler known to those skilled in the art and suitable for use with fibers may be used, and biodegradable fillers are preferred. For example, the (biodegradable) filler may be lignin or contain lignin. Preferably, the lignin is oxygen-bleached lignin. Oxygen bleaching of lignin is an environmentally friendly process compared to conventional chlorine bleaching.

[0055] Those skilled in the art will be able to easily select an appropriate amount of additive to be blended into the fiber. For example, the fiber may contain an additive in a total amount of 15% by weight or less, based on 100% by weight of the total fiber weight. The fiber may contain an additive in a total amount of 10% by weight or less, based on 100% by weight of the total fiber weight. Preferably, the fiber may contain an additive in a total amount of 7% by weight or less, based on 100% by weight of the total fiber weight. More preferably, the fiber may contain an additive in a total amount of 5% by weight or less, based on 100% by weight of the total fiber weight. Even more preferably, the fiber may contain an additive in a total amount of 4% by weight or less, based on 100% by weight of the total fiber weight. Even more preferably, the fiber may contain an additive in a total amount of 3% to 4% by weight, based on 100% by weight of the total fiber weight. To achieve the stiffness of a fiber useful as a woven fiber, it is preferable that the fiber contains an additive in a total amount of 7% by weight or less, and more preferably 3 to 4% by weight, based on 100% by weight of the total fiber weight.

[0056] The fiber titer is not particularly limited. For example, any fiber titer commonly used in the textile industry can be applied. For example, the fiber titer may be 0.5 to 8 den. Preferably, the fiber titer is 0.8 to 6 den. More preferably, the fiber titer is 0.9 to 3 den. Even more preferably, the fiber titer is 1.0 to 2 den. Even more preferably, the fiber titer is 1.0 to 1.5 den. Even more preferably, the fiber titer is 1.1 to 1.2 den.

[0057] The fibers may be staple fibers. As used herein, the term “staple fiber” generally refers to fibers of discontinuous length. The length of the staple is not particularly limited. For example, any stable length commonly used in the textile industry can be applied. Thus, as an example, the fibers may have a staple length of 2 to 80 mm. Preferably, the fibers have a staple length of 5 to 70 mm. More preferably, the fibers have a staple length of 10 to 60 mm. Even more preferably, the fibers have a staple length of 15 to 50 mm. Even more preferably, the fibers have a staple length of 20 to 40 mm. Even more preferably, the fibers have a staple length of 22 to 35 mm. Even more preferably, the fibers have a staple length of 25 to 32 mm. Generally, the term “staple length” refers to the average length of the fibers in the sample.

[0058] Fibers may be filaments. Generally, the terms “filament” or “filament fiber” refer to fibers with virtually no length limitations. Therefore, generally, the terms “filament” or “filament fiber” refer to continuous fibers.

[0059] Preferably, the fibers are biodegradable. More preferably, the fibers are biodegradable in accordance with EN13432. Thus, if the fibers have a degree of biodegradation equal to at least 90% of the DIN EN13432 percentage after a predetermined period, the fibers can be considered biodegradable in accordance with EN13432. The general effect of biodegradability is that the fibers decompose within a suitable and verifiable period. Decomposition may occur enzymatically, hydrolytically, oxidatively, and / or by electromagnetic radiation, such as ultraviolet radiation, and may be mainly by the action of microorganisms such as bacteria, yeasts, fungi, and algae. Biodegradability can be quantified, for example, by mixing the fibers with compost and storing them for a certain period of time. For example, CO2-free air can be flowed into the mature compost during composting, and the mature compost can be subjected to a predetermined temperature program. Biodegradability can be defined, for example, as the ratio of the net CO2 released by the sample (after subtracting the CO2 released by compost without the sample) to the maximum amount of CO2 that the sample can release (calculated from the carbon content of the sample), which is the percentage of biodegradation. Biodegradable fibers usually show clear signs of decomposition, such as fungal growth, cracking, and punctures, within just a few days after composting. Other methods for measuring biodegradability are described, for example, in ASTM D 5338 and ASTM D 6400.

[0060] Preferably, the fibers are crimped fibers.

[0061] Optionally, the fibers described herein may be subjected to post-processing, for example, using a post-processing line for fibers. The post-processing may include processes conventionally used for processing fibers, such as reeding, suction construction, immersion, drafting, stretching, steaming, reviving, crimping, drying, and / or staple cutting.

[0062] In some embodiments, the fibers are not hollow fibers. As used herein and as known in the art, the term “hollow fiber” generally refers to any fiber having one or more cavities in cross-section. As used herein, the term “cavity” generally refers to the hollow space present within the cross-section of the fiber. The cavities may be filled with a gas, such as air. Exemplarily, a hollow fiber may have one continuous cavity in cross-section. However, a hollow fiber may also contain two or more cavities (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or more cavities). In addition to one or more cavities, a hollow fiber may further contain one or more portions having a dense structure. As used herein, the term “dense structure” may also be called “condensed structure” and generally refers to the fiber material existing in a substantially dense or condensed form, particularly compared to the cavities of a hollow fiber. The terms “dense structure” or “condensed structure” may also encompass the presence of pores, which are generally considerably smaller than the cavities in hollow fibers. Hollow fibers containing both cavities and dense (or condensed) structures are sometimes also referred to as segmented fibers or segmented hollow fibers. As an illustrative example, a hollow fiber may consist of alternating cavities and dense structures along the longitudinal direction of the fiber.

[0063] In particular, in some embodiments, the fibers are not the same as those described in international application PCT / EP2022 / 075084. The fibers described in international application PCT / EP2022 / 075084 are also described below. Therefore, in some embodiments, the fibers are not the following fibers: Fibers that can be obtained or obtained by a method including the following steps: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fibers are cooled under a temperature gradient to obtain the fibers. The fibers that can be obtained by this method, or that can be obtained, comprise two types of parts, one of which is a thick part and the other of which is a thin part, and have the structure described below herein. Therefore, in some embodiments, the fibers are not the following fibers: A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, The fiber comprises two types of portions in the longitudinal direction, one of which is a thick portion and the other is a thin portion, the thick portion and the thin portion extending perpendicular to the longitudinal direction of the fiber, and the extension of the thick portion in the perpendicular direction being greater than the extension of the thin portion in the perpendicular direction; A fiber in which at least a portion of the thicker part has a cavity, and at least a portion of the thinner part has a dense structure. In some embodiments, the fibers are not hollow fibers made from a mixture of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. In some embodiments, the fibers are not split fibers or split hollow fibers.

[0064] In some embodiments, the fibers are solid fibers. In some embodiments, the fibers are non-hollow fibers. The terms used herein, and as known in the art, also referred to as “solid fiber” or “non-hollow fiber,” generally refer to any fiber whose material exists in a substantially dense or condensed form and does not have cavities as described herein for hollow fibers. However, the terms “solid fiber” or “non-hollow fiber” do not preclude the fiber from containing several pores which are generally significantly smaller than the cavities of hollow fibers.

[0065] The present invention also relates to yarns made from the fibers described herein. Any type of yarn is conceivable. In non-illustrated examples, the yarns may be spun yarns, carded or combed yarns, knitted yarns, open-end yarns, novelty yarns, filament yarns, or textured yarns. The yarns can be prepared from the fibers described herein by any method suitable for preparing yarns. Methods for preparing yarns are generally known and can be easily selected by those skilled in the art.

[0066] The present invention also relates to a woven surface containing the fibers described herein. The present invention also relates to a woven surface containing yarn, wherein the yarn contains the fibers described herein. In non-limiting examples, the woven surface may be selected from the group consisting of fabrics, knitted fabrics, and nonwoven fabrics. The fibers or yarns containing the fibers can also be used in the preparation of fleece.

[0067] The present invention also relates to textiles comprising fibers as described herein. The present invention also relates to textiles comprising yarn, wherein the yarn comprises fibers as described herein. The textile may be clothing. In non-limiting examples, clothing may be selected from the group consisting of shirts, polo shirts, trousers, jackets, underwear, socks, coats, shoes, and shoelaces. In particular, clothing may be polo shirts, and preferably shirts. The textile may be household textiles. In non-limiting examples, household textiles may be selected from the group consisting of curtains, rugs, blankets, bed sheets, quilts, duvet covers, cushion covers, and towels.

[0068] The present invention also relates to a method for preparing fibers according to the present invention, comprising the following: - A molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate is spun through a spinning nozzle to obtain precursor fibers; and, - Cooling the precursor fibers to obtain the fibers. Fibers can be further defined for any fiber as described herein.

[0069] As used herein, the term “precursor fiber” generally refers to a fiber that is produced as an intermediate in the manufacturing process of the present invention after exiting the spinning nozzle and during cooling. The (final) fiber of the present invention that can be obtained by the method of the present invention, particularly after cooling, or that is obtained, is generally simply referred to as “fiber.”

[0070] A molten material for spinning fibers can be prepared using any method for producing molten materials for spinning fibers that is known to those skilled in the art. For example, aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates can be mixed in a non-molten state, for example, by mixing in polymer granules, with the optional addition of one or more further additives. Optionally, the polymer and any additives may be dried before mixing and preparation of the molten material. The mixture can then be heated above the melting point of the polymer to prepare the molten material. For example, mixing and heating may be carried out in an extruder. In some embodiments, the molten material may have a temperature in the range of 200°C to 260°C, preferably 220°C to 250°C, more preferably 230°C to 250°C, and even more preferably 230°C to 240°C, particularly before spinning through a spinning nozzle. For example, the molten material may be heated to a temperature of 235°C. The molten material is then passed through a spinning nozzle. For example, an extruder may be used to pass the molten material through a hollow fiber spinning nozzle. Any spinning nozzle commonly known in the art can be used. A molten material containing an aliphatic polyester, an aliphatic aromatic polyester, and a polyhydroxyalkanoate is spun through a spinning nozzle to obtain a hot precursor fiber. The hot precursor fiber obtained by spinning the molten material through the spinning nozzle is then cooled to obtain the fiber.

[0071] Cooling of precursor fibers can be carried out by using any suitable means / apparatus for cooling. Suitable means / apparatus for cooling can be easily selected by those skilled in the art. For example, one or more temperature control elements can be used for cooling. Exemplarily, temperature control elements can be placed and / or operated in or near a spinning apparatus. Apparatus for melt spinning is generally known to those skilled in the art. Temperature control elements can be heating and / or cooling elements that can actively or passively impart a heating or cooling effect to the precursor fibers. A non-limiting example of a temperature control element that is a cooling element is an air cooling aggregate that can provide an airflow over the precursor fibers. For example, an air cooling aggregate can be placed on the sides of the precursor fibers and can provide an airflow substantially perpendicular to the longitudinal direction of the precursor fibers; see, for example, Figure 1, precursor fiber 3 and airflow 7. By placing cooling aggregates on both sides of the precursor fibers, the cooling of the precursor fibers can be carried out under a substantially uniform temperature distribution through the fibers. The air used for air cooling can have a temperature of ambient temperature, preferably room temperature, more preferably +20°C ± 5°C. However, although Figure 1 shows air cooling using cooling aggregates, it is also possible to perform air cooling by simply exposing the precursor fibers to ambient air, that is, without supplying an airflow onto the precursor fibers from a cooling device. Furthermore, other suitable cooling methods such as water cooling can also be used.

[0072] In some embodiments, cooling is preferably performed by air cooling.

[0073] Preferably, the molten material contains 30 to 70% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 35 to 65% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 40 to 60% by weight or 42 to 62% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 45 to 55% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges may apply when the aliphatic polyester is polybutylene succinate. In a preferred embodiment, the molten material contains 52% by weight of polybutylene succinate, based on a total amount of 100% by weight of polybutylene succinate, aliphatic aromatic polyester, and polyhydroxyalkanoate.

[0074] Preferably, the molten material contains 10 to 60% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 20 to 50% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 25 to 40% by weight or 26 to 46% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 30 to 40% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges are applicable when the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). In a preferred embodiment, the molten material contains 36% by weight of polybutylene adipate terephthalate (PBAT), based on a total amount of aliphatic polyester, polybutylene adipate terephthalate (PBAT), and polyhydroxyalkanoate of 100% by weight.

[0075] Preferably, the molten material contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 3 to 20% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 3 to 18% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 5 to 15% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Preferably, when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), the melt contains 20% by weight or less, more preferably 18% by weight or less of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH).

[0076] The ranges of amounts of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates can also be combined with each other. For example, the molten material may contain 42-62% by weight, preferably 45-55% by weight, of aliphatic polyesters; the molten material may contain 26-46% by weight, preferably 30-40% by weight, of aliphatic-aromatic polyesters; and the molten material may contain 2-22% by weight, preferably 3-20% by weight, more preferably 3-18% by weight, of polyhydroxybutyrate, with each proportion based on 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. A person skilled in the art will readily select appropriate amounts of one or more polymers within the range provided herein, so as not to exceed 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. In particular, these ranges apply when the aliphatic polyester is polybutylene succinate, the aliphatic aromatic polyester is polybutylene adipate terephthalate, and the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In a very preferred embodiment, the molten material comprises 52% by weight of polybutylene succinate, 36% by weight of polybutylene adipate terephthalate, and 12% by weight of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), where each proportion is based on 100% by weight of the total amount of polybutylene succinate, polybutylene adipate terephthalate, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0077] In some embodiments, the polyhydroxyalkanoate may be partially or completely substituted with polylactide (also known as PLA, or polylactic acid or poly(lactic acid)). Therefore, in some embodiments, when the polyhydroxyalkanoate is partially substituted with polylactide, the melt comprises an aliphatic polyester, an aliphatic-aromatic polyester, the polyhydroxyalkanoate, and the polylactide. In some embodiments, when the polyhydroxyalkanoate is completely substituted with polylactide, the melt comprises an aliphatic polyester, an aliphatic-aromatic polyester, and the polylactide. However, in embodiments where the polyhydroxyalkanoate is completely substituted with polylactide, the melt does not contain the polyhydroxyalkanoate.

[0078] Optionally, the molten material may further contain at least one additive. For example, the molten material may contain at least one additive that is commonly known to be used in textile fibers. Optional additives may include, but are not limited to, additives selected from the group consisting of flame retardants, matting agents, markers for certification (e.g., fluorescent markers), antimicrobial agents, plasticizers, colorants, fillers, and any combination thereof.

[0079] Preferably, the molten material contains a flame retardant. More preferably, the flame retardant is a phosphate. In a preferred embodiment, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), and any combination thereof. More preferably, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), and any combination thereof. More preferably, the flame retardant is ammonium dihydrogen phosphate ([NH4][H2PO4]) or diammonium hydrogen phosphate ([NH4]2[HPO4]). Even more preferably, the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]). Alternatively, or in addition, the flame retardant may be a polyphosphate. Preferably, if the flame retardant is a polyphosphate, the flame retardant is ammonium polyphosphate.

[0080] The molten material may contain a flame retardant in an amount of 0.01% to 5% by weight, based on 100% by weight of the total weight of the molten material. Preferably, the molten material contains a flame retardant in an amount of 0.1% to 4% by weight, based on 100% by weight of the total weight of the molten material. More preferably, the molten material contains a flame retardant in an amount of 0.2% to 3% by weight, based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material contains a flame retardant in an amount of 0.3% to 3% by weight, based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material contains a flame retardant in an amount of 0.3% to 2% by weight, based on 100% by weight of the total weight of the molten material. In particular, the above ranges apply when the flame retardant is a phosphate or polyphosphate, preferably when the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]).

[0081] Those skilled in the art will be able to easily select an appropriate amount of additive to be blended into the molten material. For example, the molten material may contain an amount of additive of 15% by weight or less based on 100% by weight of the total weight of the molten material. The molten material may contain an amount of additive of 10% by weight or less based on 100% by weight of the total weight of the molten material. Preferably, the molten material may contain an amount of additive of 7% by weight or less based on 100% by weight of the total weight of the molten material. More preferably, the molten material may contain an amount of additive of 5% by weight or less based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material may contain an amount of additive of 4% by weight or less based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material may contain an amount of additive of 3% to 4% by weight based on 100% by weight of the total weight of the molten material. To achieve the stiffness of fibers useful as textile fibers, it is preferable that the molten material contains a total amount of additives of 7% by weight or less, based on 100% by weight of the total weight of the molten material, and more preferably 3-4% by weight of additives.

[0082] The fibers may be staple fibers.

[0083] The fibers may also be filaments.

[0084] In some embodiments, the spinning nozzle is not a hollow fiber spinning nozzle. As used herein, the term “hollow fiber spinning nozzle” refers to any hollow fiber spinning nozzle commonly known in the art. A merely exemplary example of a hollow fiber spinning nozzle is described, for example, in European Patent No. 2112256, the entire contents of which are incorporated herein by reference.

[0085] In some embodiments, this method is not a method for preparing fibers as described in international application PCT / EP2022 / 075084. In particular, in some embodiments, the method is not a method for preparing fibers that includes the following steps: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fibers are cooled under a temperature gradient to obtain the fibers.

[0086] The present invention relates to fibers that can be obtained or obtained by the method for preparing fibers of the present invention.

[0087] The present invention relates to the use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of fibers, where the fibers are as defined herein.

[0088] The present invention relates to the use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of fibers.

[0089] [Filament suitable for 3D printing] The present invention also relates to a filament suitable for three-dimensional printing, made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate.

[0090] A mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate has been found to be suitable for preparing filaments suitable for three-dimensional printing. In particular, filaments containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate can be obtained, or may be obtained, by extruding a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate into the shape of a filament. In this regard, a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate has been found to exhibit good extrudeability, particularly suitable for extrusion into filaments. A further advantage is that, as shown with respect to the fibers of the present invention (see Example 2), the production of filaments suitable for three-dimensional printing can be carried out without using harmful substances such as antimony. Furthermore, by using aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, it is possible to obtain filaments suitable for three-dimensional printing that are biodegradable, conform to the European harmonized standard EN13432, and can be processed in industrial composting plants. Furthermore, the filaments of the present invention, which include aliphatic-aromatic polyesters and polyhydroxyalkanoates, have been found to be suitable for preparing three-dimensional printed molded articles using conventional three-dimensional printers (3D printers), such as those operating under material extrusion technology. Therefore, three-dimensional printed molded articles that are biodegradable and conform to the European harmonized standard EN13432 can be prepared from the filaments suitable for three-dimensional printing according to the present invention.In this context, it should be noted that various products, such as plates and foils as well as fibers, comprising one or more aliphatic polyesters, aliphatic-aromatic polyesters, and / or polyhydroxyalkanoates, are described, for example, in European Patent No. 3626767, International Publication No. 2010 / 034689, International Publication No. 2010 / 034711, International Publication No. 2015 / 169660, European Patent No. 1966419, European Patent No. 2984138, Chinese Patent No. 103668540, Chinese Patent No. 103668541, International Publication No. 2014 / 173055 and Chinese Patent No. 104120502.

[0091] The term "3D printing," also known as "additive manufacturing," as used in this technical field, generally refers to the creation of three-dimensional objects from, for example, CAD models or digital 3D models. This can be done through various processes of depositing, bonding, and solidifying materials under computer control, where materials (such as plastics, liquids, or powder particles being fused together) are added together, usually layer by layer. Currently, three-dimensional printers (hereinafter sometimes referred to as "3D printers") using various additive manufacturing technologies (e.g., binder jetting, material extrusion, vat photopolymerization) are commercially available. Among these, 3D printer systems based on material extrusion technology (e.g., systems from Stratasys, Inc., USA) are used to create three-dimensional objects layer by layer by extruding fluid raw materials from a nozzle on an extrusion head, based on a computer-aided design (CAD) model. This system exemplifies a simple system in which a filament containing a thermoplastic resin raw material is inserted into an extrusion head, heated and melted, and continuously extruded from a nozzle on the extrusion head onto an XY plane platen in a chamber, depositing and fusing the extruded resin onto an already formed resin deposit, and solidifying and integrating it as the extruded resin cools. In material extrusion technology, the extrusion process is usually repeated while the nozzle position relative to the platen rises in the Z axis direction perpendicular to the XY plane, thereby creating a three-dimensional object such as a CAD model. The filament suitable for three-dimensional printing according to the present invention can be used, for example, to produce three-dimensional printed molded products by applying material extrusion technology.

[0092] The filaments suitable for three-dimensional printing according to the present invention can be further defined with respect to any fiber of the present invention as described herein.

[0093] As used herein, the term “aliphatic polyester” generally refers to polyesters synthesized by condensation polymerization of an aliphatic diol with an aliphatic dicarboxylic acid or its anhydride. Exemplarily, as used herein, aliphatic polyesters are aliphatic C2-C2. 20Dicarboxylic acids and aliphatic C2-C 12 Diols may be included. Preferably, the aliphatic diol is an aliphatic C2-C8 diol. More preferably, the aliphatic diol is an aliphatic C2-C6 diol. Even more preferably, the aliphatic diol is an aliphatic C3 diol or an aliphatic C4 diol. Examples of aliphatic diols used in aliphatic polyesters include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Preferably, the aliphatic diol is 1,3-propanediol or 1,4-butanediol. More preferably, the aliphatic diol is 1,4-butanediol. Preferably, the aliphatic dicarboxylic acid is an aliphatic C2-C 12 It is a dicarboxylic acid. More preferably, the aliphatic dicarboxylic acid is an aliphatic C2-C8 dicarboxylic acid, and even more preferably, an aliphatic C4 dicarboxylic acid. Examples of aliphatic dicarboxylic acids used in aliphatic polyesters include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Preferably, the aliphatic dicarboxylic acid is malonic acid or succinic acid. More preferably, the aliphatic dicarboxylic acid is succinic acid. Optionally, the dicarboxylic acid may be aliphatic C2-C 12 If it is a dicarboxylic acid, the aliphatic polyester is C2-C 12 Aliphatic C6-C groups different from dicarboxylic acids 20 It may further contain dicarboxylic acids. Any aliphatic C6-C 12 Examples of dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, and arachidonic acid. Preferably, any aliphatic C6-C 12 The dicarboxylic acid may include adipic acid, suberic acid, azelaic acid, sebacic acid, and brassic acid. Any aliphatic C2-C 12Dicarboxylic acids may be present in the aliphatic polyester in a proportion of 0 to 10 mol% based on 100 mol% of the total amount of aliphatic dicarboxylic acids in the aliphatic polyester. Optionally, the aliphatic polyester may further contain chain extenders and / or branching agents. Examples of optional chain extenders and / or branching agents include polyfunctional isocyanates, isocyanurates, oxazolines, carboxylic acid anhydrides such as maleic anhydride, epoxides (especially epoxy-containing poly(meth)acrylates), at least trihydric alcohols, and at least tribasic carboxylic acids. Any chain extender and / or branching agent may be present in the aliphatic polyester in a proportion of 0 to 1% by weight based on 100% by weight of the total amount of aliphatic dicarboxylic acids and aliphatic diols. The term "aliphatic polyester" may also include mixtures of two or more different aliphatic polyesters. Aliphatic polyesters may have a number-average molecular weight (Mn) in the range of 2,500 to 150,000 g / mol, preferably 5,000 to 100,000 g / mol, more preferably 7,500 to 75,000 g / mol, even more preferably 10,000 to 65,000 g / mol, and even more preferably 12,000 to 60,000 g / mol. Aliphatic polyesters may have a weight-average molecular weight (Mw) in the range of 5,000 to 300,000 g / mol, preferably 10,000 to 250,000 g / mol, more preferably 20,000 to 220,000 g / mol, even more preferably 50,000 to 200,000 g / mol, and even more preferably 60,000 to 190,000 g / mol. Aliphatic polyesters can have a polydispersity index (i.e., the ratio of weight-average molecular weight to number-average molecular weight (Mw / Mn)) in the range of 1 to 6, preferably 1 to 4, more preferably 1.0 to 3.0, even more preferably 1.2 to 2.0, and even more preferably 1.4 to 1.8.

[0094] Examples of aliphatic polyesters that can be used in the present invention may include aliphatic polyesters selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasrate (PBSBr), and combinations thereof. The aliphatic polyester may preferably be selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasrate (PBSBr), and combinations thereof. In preferred embodiments, the aliphatic polyester is polybutylene succinate. The term "polybutylene succinate" as used specifically herein refers to the condensation product of succinic acid, an aliphatic dicarboxylic acid, and 1,4-butanediol, an aliphatic diol. Polybutylene succinate (PBS) and polybutylene succinate-co-adipate (PBSA), which are aliphatic polyesters, are commercially available, for example, as Blanche® from Showa Polymer Co., Ltd. and as GSPIa® from Mitsubishi Corporation. Aliphatic polyesters, particularly polybutylene succinate (PBS), can be obtained from renewable or fossil resources. Preferably, aliphatic polyesters derived from renewable resources are used. More preferably, bio-based polybutylene succinate (PBS) produced from bio-based succinic acid and 1,4-butanediol, such as that commercially available from Mitsubishi Chemical under the trade name BioPBS® FZ71, can be used. Preferably, the aliphatic polyester is biodegradable. In particular, polybutylene succinate (PBS) is a biodegradable aliphatic polyester.

[0095] Preferably, a filament suitable for three-dimensional printing contains 30 to 70% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the filament contains 35 to 65% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 40 to 60% by weight or 42 to 62% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 45 to 55% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the aliphatic polyester is polybutylene succinate. In a preferred embodiment, the filament comprises 52% by weight of polybutylene succinate, based on a total amount of 100% by weight of polybutylene succinate, aliphatic aromatic polyester, and polyhydroxyalkanoate.

[0096] As commonly used herein, the term “aliphatic-aromatic polyester” generally refers to polyesters synthesized from aliphatic diols, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids. For example, aliphatic-aromatic polyesters include aliphatic C2-C2 compounds. 20 Dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic C 2- C 12Diols may be included, preferably the aliphatic diol is an aliphatic C2-C8 diol. More preferably the aliphatic diol is an aliphatic C2-C6 diol. Even more preferably the aliphatic diol is an aliphatic C3 diol or an aliphatic C4 diol. Aliphatic diols used in aliphatic polyesters may include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Preferably the aliphatic diol is 1,3-propanediol or 1,4-butanediol. More preferably the aliphatic diol is 1,4-butanediol. Preferably the aliphatic dicarboxylic acid is an aliphatic C2-C 12 It is a dicarboxylic acid. More preferably, the aliphatic dicarboxylic acid is an aliphatic C4-C 10The aliphatic dicarboxylic acid is a dicarboxylic acid, and more preferably an aliphatic C6 dicarboxylic acid. Examples of aliphatic dicarboxylic acids used in aliphatic-aromatic polyesters include glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassic acid, suberic acid, and itaconic acid. Preferably, the aliphatic dicarboxylic acid is adipic acid, azelaic acid, or sebacic acid. More preferably, the aliphatic dicarboxylic acid is adipic acid. Preferably, the aromatic dicarboxylic acid is terephthalic acid. The aromatic dicarboxylic acid, particularly terephthalic acid, may be present in the aliphatic-aromatic polyester in amounts of, for example, 30 to 70 mol-%, preferably 40 to 60 mol-%, and more preferably 40 to 55 mol-%, based on a total amount of aliphatic dicarboxylic acid and aromatic dicarboxylic acid of 100 mol-%, respectively. Optionally, the aliphatic polyester may further contain chain extenders and / or branching agents. Optional chain extenders may include, for example, bifunctional or polyfunctional isocyanates, preferably hexamethylene diisocyanates. Optional branching agents may include, for example, trimethylolpropane, pentaerythritol, preferably glycerol. Any chain extenders and / or branching agents may be present in the aliphatic polyester in a proportion of 0 to 1% by weight, based on 100% by weight of the total amount of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic diols. The term "aliphatic-aromatic polyester" may include mixtures of two or more different aliphatic-aromatic polyesters. Aliphatic-aromatic polyesters may have a number-average molecular weight (Mn) in the range of 1,000 to 500,000 g / mol, preferably 5,000 to 300,000 g / mol, more preferably 5,000 to 100,000 g / mol, even more preferably 10,000 to 75,000 g / mol, and even more preferably 15,000 to 50,000 g / mol. Aliphatic-aromatic polyesters may have a weight-average molecular weight (Mw) in the range of 10,000 to 500,000 g / mol, preferably 20,000 to 400,000 g / mol, more preferably 30,000 to 300,000 g / mol, and even more preferably 60,000 to 200,000 g / mol.Aliphatic-aromatic polyesters can have a polydispersity index (i.e., the ratio of weight-average molecular weight to number-average molecular weight (Mw / Mn)) in the range of 1 to 6, preferably 2 to 4, more preferably 1.0 to 3.0, even more preferably 1.2 to 2.0, and even more preferably 1.4 to 1.8.

[0097] Aliphatic-aromatic polyesters usable in the present invention include, but are not limited to, aliphatic-aromatic polyesters selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof. In a preferred embodiment, the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). As used herein, the term "polybutylene adipate terephthalate" refers to an aliphatic-aromatic polyester containing adipic acid, an aliphatic dicarboxylic acid; terephthalic acid, an aromatic dicarboxylic acid; and 1,4-butanediol, an aliphatic diol. Aliphatic-aromatic polyesters, particularly polybutylene adipate terephthalate (PBAT), can be obtained from renewable or fossil resources. Preferably, aliphatic-aromatic polyesters derived from renewable resources are used. Polybutylene adipate terephthalate (PBAT) is commercially available, for example, from BASF as Ecoflex®, e.g., Ecoflex® F Blend C1200 or Ecoflex® FBX 7011, or from Showa Denko as Bionolle®. Preferably, aliphatic-aromatic polyesters are biodegradable. In particular, polybutylene adipate terephthalate (PBAT) is a biodegradable aliphatic-aromatic polyester.

[0098] Preferably, a filament suitable for three-dimensional printing contains 10 to 60% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the filament contains 20 to 50% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 25 to 40% by weight or 26 to 46% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 30 to 40% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). In a preferred embodiment, the filament contains 36% by weight of polybutylene adipate terephthalate (PBAT) based on 100% by weight of the total amount of aliphatic polyester, polybutylene adipate terephthalate (PBAT), and polyhydroxyalkanoate.

[0099] As used herein, the term “polyhydroxyalkanoate” generally refers to polyesters obtained from hydroxyalkanecarboxylic acid monomers. Polyhydroxyalkanoates can be produced by many microorganisms, including bacterial fermentation of sugars or lipids. Preferably, the hydroxyalkanecarboxylic acid is C4-C 18 The hydroxyalkanecarboxylic acid is, preferably, a hydroxyalkanecarboxylic acid containing 4 to 18 carbon atoms. More preferably, the polyhydroxyalkanoate contains monomer units having the following formula (I):

[0100] [ka] Here, R is given by equation C n H 2n+1 The alkyl group is such that n is an integer from 1 to 15, preferably from 1 to 6. In some embodiments, the polyhydroxyalkanoate is a homopolymer. In some preferred embodiments, the polyhydroxyalkanoate is a copolymer. When the polyhydroxyalkanoate is a copolymer, the copolymer may contain two different monomer units of formula (I). The term "polyhydroxyalkanoate" may also include a mixture of two or more different polyhydroxyalkanoates. The polyhydroxyalkanoate may have a weight-average molecular weight (Mw) in the range of 70,000 to 1,000,000 g / mol, preferably 100,000 to 1,000,000 g / mol, and more preferably 300,000 to 600,000 g / mol.

[0101] Examples of polyhydroxyalkanoates that may be used in this disclosure may include polyhydroxyalkanoates selected from the group consisting of polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, polyhydroxybutyrate-co-hydroxyhexanoate, and any combination thereof. Preferably, the polyhydroxyalkanoate is selected from the group consisting of poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), and any combination thereof. More preferably, the polyhydroxyalkanoate is [ka] The polyhydroxyalkanoate is selected from the group consisting of these combinations. More preferably, the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate. In a very preferred embodiment, the polyalkoxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH). Preferably, the molar ratio m:n in the above-described structural formula is 95:5 to 85:15, more preferably 90:10 to 88:12. Preferably, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH) having a molar ratio of 5 to 15 mol%, preferably 7 to 13 mol%, and more preferably 10 to 13 mol%, of 3-hydroxyhexanoate based on 100 mol% of the total amount of monomers in poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH) is used. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is sold, for example, by P&G and Kaneka. Polyhydroxyalkanoates, in particular poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) can be obtained from renewable or fossil resources. Preferably, polyhydroxyalkanoates derived from renewable resources are used. More preferably, bio-based poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) can be used, which is commercially available, for example, from Kaneka under the trade name AONILEX X 151 A. Preferably, the polyhydroxyalkanoate is biodegradable. In particular, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is a biodegradable polyhydroxyalkanoate.

[0102] Preferably, a filament suitable for three-dimensional printing contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the filament contains 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 3 to 20% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the filament contains 3 to 18% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the filament contains 5 to 15% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Preferably, when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), the filament contains 20% by weight or less, more preferably 18% by weight or less of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH).If the proportion of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) exceeds 18% by weight, it may become difficult to achieve the EN 13432 standard for biodegradability without pre-composting or industrial composting, and it becomes even more difficult if it exceeds 20% by weight. In a preferred embodiment, the filament contains 12% by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) based on a total amount of polybutylene succinate, polybutylene adipate terephthalate, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) of 100% by weight.

[0103] In a very preferred embodiment, the aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyalkoxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Therefore, in a very preferred embodiment, a filament suitable for three-dimensional printing comprises polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0104] The ranges of amounts of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate can also be combined with each other. For example, a filament suitable for three-dimensional printing may contain 42-62% by weight, preferably 45-55% by weight, of aliphatic polyester; a filament may contain 26-46% by weight, preferably 30-40% by weight, of aliphatic-aromatic polyester; and a filament may contain 2-22% by weight, preferably 3-20% by weight, more preferably 3-18% by weight, of polyhydroxyalkanoate, with each proportion based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. A person skilled in the art will readily select appropriate amounts of one or more polymers within the range provided herein, so as not to exceed 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges apply when the aliphatic polyester is polybutylene succinate, the aliphatic aromatic polyester is polybutylene adipate terephthalate, and the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In a very preferred embodiment, the filament comprises 52% by weight of polybutylene succinate, 36% by weight of polybutylene adipate terephthalate, and 12% by weight of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), where each proportion is based on 100% by weight of the total amount of polybutylene succinate, polybutylene adipate terephthalate, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0105] In some embodiments, the polyhydroxyalkanoate may be partially or completely substituted with polylactide (also known as PLA, or polylactic acid or poly(lactic acid)). Therefore, in some embodiments, when the polyhydroxyalkanoate is partially substituted with polylactide, the filament suitable for three-dimensional printing comprises an aliphatic polyester, an aliphatic-aromatic polyester, the polyhydroxyalkanoate, and the polylactide. In some embodiments, when the polyhydroxyalkanoate is completely substituted with polylactide, the filament comprises an aliphatic polyester, an aliphatic-aromatic polyester, and the polylactide. However, in embodiments where the polyhydroxyalkanoate is completely substituted with polylactide, the filament does not contain the polyhydroxyalkanoate.

[0106] Optionally, a filament suitable for three-dimensional printing may further contain at least one additive (or more additives). For example, a filament may contain at least one additive (or more additives) that are commonly known to be used in filaments for three-dimensional printing. Optional additives may include, but are not limited to, flame retardants, matting agents, markers for certification (e.g., fluorescent markers), antimicrobial agents, colorants, plasticizers, fillers, and any combination thereof.

[0107] Preferably, a filament suitable for three-dimensional printing further contains a flame retardant, such as a phosphate. The term "phosphate" as used herein refers to [H2PO4] - [HPO4] 2- and [PO4] 3- This refers to a salt containing an anion selected from the group consisting of the following. Preferably, the cation is ammonium [NH4]. +Therefore, in a preferred embodiment, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), and any combination thereof. More preferably, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), and any combination thereof. More preferably, the flame retardant is ammonium dihydrogen phosphate ([NH4][H2PO4]) or diammonium hydrogen phosphate ([NH4]2[HPO4]). Even more preferably, the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]). Alternatively, or in addition, the flame retardant may be a polyphosphate. A "polyphosphate" is a salt or ester of a polymer oxyanion formed from tetrahedral PO4 (phosphate) structural units linked by sharing oxygen atoms. Preferably, if the flame retardant is a polyphosphate, the flame retardant is ammonium polyphosphate.

[0108] A filament suitable for three-dimensional printing may contain a flame retardant in an amount of 0.01% to 5% by weight, based on 100% by weight of the total weight of the filament. Preferably, the filament contains a flame retardant in an amount of 0.1% to 4% by weight, based on 100% by weight of the total weight of the filament. More preferably, the filament contains a flame retardant in an amount of 0.2% to 3% by weight, based on 100% by weight of the total weight of the filament. Even more preferably, the filament contains a flame retardant in an amount of 0.3% to 3% by weight, based on 100% by weight of the total weight of the filament. Even more preferably, the filament contains a flame retardant in an amount of 0.3% to 2% by weight, based on 100% by weight of the total weight of the filament fibers. In particular, the above ranges apply when the flame retardant is a phosphate or polyphosphate, preferably when the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]).

[0109] Optionally, filaments suitable for 3D printing may also contain a matting agent. Any matting agent known to those skilled in the art may be used, such as typical matting agents used in filaments suitable for 3D printing. For example, the matting agent may be zinc sulfide.

[0110] Optionally, a filament suitable for 3D printing may also contain a marker suitable for certification. As an exemplary, non-limiting example, the marker suitable for certification may be a fluorescent marker. The fluorescence of the filament and the molded product 3D printed with the filament can be detected by appropriate equipment and sampled for certification. For example, fluorescent markers available from Polysecure (Freiburg im Breisgau, Germany) can be used. The marker suitable for certification is generally used in small amounts and does not alter the properties of the filament. Typically, the amount of the marker suitable for certification in the filament is in the range of ppb (parts per billion).

[0111] Optionally, filaments suitable for three-dimensional printing may also contain an antimicrobial agent. Any antimicrobial agent known to those skilled in the art and suitable for use in three-dimensional printing filaments may be used. In an exemplary, non-limiting example, the antimicrobial agent may be zinc encapsulated in polyethylene terephthalate. Such an antimicrobial agent is commercially available, for example, from Smartpolymer GmbH in Rudhlstadt, Germany, under the product name SMARTZINC 213 PET Hot Melt.

[0112] Optionally, filaments suitable for 3D printing may also contain a plasticizer. Any plasticizer known to the industry and suitable for use in 3D printing filaments may be used. For example, the plasticizer may be polycaprolactone. In particular, polycaprolactone is biodegradable. In some embodiments, the filament may contain polycaprolactone in an amount of 1% by weight or less based on 100% by weight of the total weight of the filament. Filaments containing 1% by weight or less of polycaprolactone have been found to exhibit satisfactory softness and flexibility. However, it should be noted that the 3D printing filaments of the present invention, comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, can usually exhibit satisfactory softness and flexibility without the addition of polycaprolactone or other plasticizers.

[0113] Optionally, the filament may also contain a colorant. Any colorant that provides the desired color and is suitable for use with filaments suitable for three-dimensional printing may be used. For example, the colorant may be an inorganic pigment or an organic pigment.

[0114] Optionally, filament printing may also include a filler. Any filler known to those skilled in the art and suitable for use in three-dimensional printing filaments may be used, and biodegradable fillers are preferred. For example, the (biodegradable) filler may be lignin or contain lignin. Preferably, the lignin is oxygen-bleached lignin. Oxygen bleaching of lignin is an environmentally friendly process compared to conventional chlorine bleaching.

[0115] Those skilled in the art will be able to easily select an appropriate amount of additives to be incorporated into the filament. For example, a filament suitable for three-dimensional printing may contain a total amount of additives of 15% by weight or less, based on 100% by weight of the total weight of the filament. The filament may contain a total amount of additives of 10% by weight or less, based on 100% by weight of the total weight of the filament. Preferably, the filament may contain a total amount of additives of 7% by weight or less, based on 100% by weight of the total weight of the filament. More preferably, the filament may contain a total amount of additives of 5% by weight or less, based on 100% by weight of the total weight of the filament. Even more preferably, the filament may contain a total amount of additives of 4% by weight or less, based on 100% by weight of the total weight of the filament. Even more preferably, the filament may contain a total amount of additives of 3% to 4% by weight, based on 100% by weight of the total weight of the filament. To achieve the stiffness of a filament useful for three-dimensional printing, it is preferable that the filament contains a total amount of additives of 7% by weight or less, and more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the filament.

[0116] The filament can have any diameter suitable for use in a 3D printer. Therefore, the diameter of a filament suitable for three-dimensional printing may be 1.0 mm or more. Preferably, the diameter of the filament may be 1.5 mm or more. More preferably, the diameter of the filament may be 1.6 mm or more. Even more preferably, the diameter of the filament may be 1.7 mm or more. In addition, or alternatively, the diameter of a filament suitable for three-dimensional printing may be 5.0 mm or less. Preferably, the diameter of the filament may be 4.0 mm or less. More preferably, the diameter of the filament may be 3.5 mm or less. Even more preferably, in some embodiments where the diameter of the filament is 3.0 mm or less, the diameter of a filament suitable for three-dimensional printing may be in the range of 1.70 mm to 1.80 mm. In some embodiments, the diameter of a filament suitable for three-dimensional printing may be in the range of 2.80 mm to 3.05 mm.

[0117] Preferably, filaments suitable for three-dimensional printing are biodegradable. More preferably, the filaments are biodegradable in accordance with EN13432. Thus, if a filament has a degree of biodegradation equal to at least 90% of the DIN EN13432 percentage after a predetermined period, it can be considered biodegradable in accordance with EN13432. The general effect of biodegradability is that the filament decomposes within a suitable and verifiable period. Decomposition may occur enzymatically, hydrolytically, oxidatively, and / or by electromagnetic radiation, such as ultraviolet radiation, and may be mainly by the action of microorganisms such as bacteria, yeasts, fungi, and algae. Biodegradability can be quantified, for example, by mixing the filament with compost and storing it for a certain period of time. For example, CO2-free air can be flowed into the mature compost during composting, and the mature compost can be subjected to a predetermined temperature program. Biodegradability can be defined, for example, as the ratio of the net CO2 released by the sample (after subtracting the CO2 released by compost without the sample) to the maximum amount of CO2 that can be released by the sample (calculated from the carbon content of the sample) as the percentage of biodegradation. Biodegradable filaments typically show clear signs of decomposition, such as fungal growth, cracking, and punctures, within just a few days after composting. Other methods for measuring biodegradability are described, for example, in ASTM D 5338 and ASTM D 6400. Preferably, a filament suitable for three-dimensional printing according to the present invention can be obtained by subjecting it to three-dimensional printing, or the resulting three-dimensional printed molded article is biodegradable. More preferably, the three-dimensional printed molded article is biodegradable in accordance with EN13432.

[0118] In some embodiments, the filament suitable for three-dimensional printing is not a hollow fiber or hollow filament. As used herein and as known in the art, the term “hollow fiber” generally refers to any fiber having one or more cavities in cross-section. As used herein, the term “cavity” generally refers to the hollow space present within the cross-section of the fiber. The cavities may be filled with a gas, such as air. Exemplarily, a hollow fiber may have one continuous cavity in cross-section. However, it is also possible for a hollow fiber to contain two or more cavities (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or more cavities). In addition to one or more cavities, a hollow fiber may further contain one or more portions having a dense structure. As used herein, the term “dense structure” may also be called “condensed structure” and generally refers to the fiber material existing in a substantially dense or condensed form, particularly compared to the cavities of a hollow fiber. The terms “dense structure” or “condensed structure” may also encompass the inclusion of pores, which are generally considerably smaller than the cavities in hollow fibers. Hollow fibers containing both cavities and dense (or condensed) structures are sometimes also referred to as segmented fibers or segmented hollow fibers. As an illustrative example, a hollow fiber may consist of alternating cavities and dense structures along the longitudinal direction of the fiber. All of the above definitions of “hollow fiber” also apply to “hollow filament.”

[0119] In particular, in some embodiments, the filament suitable for three-dimensional printing is not a fiber like the one described in international application PCT / EP2022 / 075084. The fiber described in international application PCT / EP2022 / 075084 is also described below. Therefore, in some embodiments, the filament suitable for three-dimensional printing is not the following fiber: Fibers that can be obtained or obtained by a method including the following steps: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fibers are cooled under a temperature gradient to obtain the fibers. The fibers that can be obtained by this method, or obtained, consist of two types of parts, one of which is a thick part and the other of which is a thin part, and have the structure described below herein. Therefore, in some embodiments, the filament suitable for three-dimensional printing is not the following fiber: A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, The fiber comprises two types of portions in the longitudinal direction, one of which is a thick portion and the other is a thin portion, the thick portion and the thin portion extending perpendicular to the longitudinal direction of the fiber, and the extension of the thick portion in the perpendicular direction being greater than the extension of the thin portion in the perpendicular direction; A fiber in which at least a portion of the thicker part has a cavity, and at least a portion of the thinner part has a dense structure. In some embodiments, the filament suitable for three-dimensional printing is not a hollow fiber made from a mixture of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. In some embodiments, the filament suitable for three-dimensional printing is not a split fiber or a split hollow fiber.

[0120] In some embodiments, the filament suitable for three-dimensional printing is a solid filament. In some embodiments, the filament suitable for three-dimensional printing is a non-hollow filament. The terms used herein, and as known in the art, also referred to as “solid filament” or “non-hollow filament,” generally refer to any filament in which the material of the filament exists in a substantially dense or condensed form and does not have cavities as described herein for hollow filaments or hollow fibers. However, the terms “solid filament” or “non-hollow filament” do not preclude the filament from containing a few pores that are generally significantly smaller than the cavities of hollow filaments or hollow fibers.

[0121] It is desirable to stably store filaments suitable for three-dimensional printing and to stably supply filaments to a three-dimensional printer. Therefore, from the viewpoint of long-term storage, stable dispensing, protection from environmental factors including ultraviolet rays, and prevention of twisting, the filament of the present invention is preferably packaged as a roll obtained by winding the filament onto a bobbin, or as a roll housed in a cartridge. Accordingly, the present invention also relates to a roll containing the filament suitable for three-dimensional printing of the present invention. The invention also relates to a cartridge suitable for a three-dimensional printer, containing the filament suitable for three-dimensional printing of the present invention. Specific examples of cartridges include those that not only house a roll obtained by winding the filament onto a bobbin, but also use a moisture-proof or moisture-absorbing material inside, and have a structure in which at least the parts other than the orifice for dispensing the filament are sealed. Typically, a roll obtained by winding three-dimensional printing filament onto a bobbin, or a cartridge containing the roll, is installed inside or around a three-dimensional printer, and the filament is continuously introduced from the cartridge to the three-dimensional printer during three-dimensional printing.

[0122] The present invention relates to three-dimensional printed molded articles, which can or can be obtained by three-dimensional printing using the three-dimensional printing-suitable filament of the present invention. The present invention also relates to three-dimensional printed molded articles comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. Three-dimensional printed molded articles can be obtained by molding them with a three-dimensional printer using a three-dimensional printing-suitable filament. Generally, conventional three-dimensional printers known in the art can be used. Examples of molding methods applied by the three-dimensional printer include material extrusion (ME), powder sintering, inkjet, and stereolithography (SLA). Preferably, the filament of the present invention is used with material extrusion. Three-dimensionally printed molded articles are not particularly limited. Generally, any molded article having a desired shape can be prepared from the filament in a three-dimensional printing process. Examples of three-dimensional printed molded articles that can be obtained or produced from the filament according to the present invention include stationery; toys; covers for mobile phones and smartphones; parts such as grips; school teaching materials; home appliances; parts for automobiles, motorcycles, and bicycles; electrical and electronic equipment; agricultural materials; horticultural materials; fishery materials; civil engineering / construction materials; medical supplies, etc. In some embodiments, the three-dimensional printed molded article may be a plastic card, such as a plastic card in the form of a credit card.

[0123] The present invention also relates to a method for preparing a filament suitable for three-dimensional printing, the preparation method comprising extruding a molten material containing an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate into a filament shape, thereby obtaining a filament. The filament can be further defined as described herein for any filament suitable for three-dimensional printing.

[0124] A molten material for preparing a filament can be prepared using any method for producing molten materials known to those skilled in the art. For example, aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates can be mixed in a non-molten state, for example, by mixing in polymer granules, with the optional addition of one or more further additives. Optionally, the polymer and any additives may be dried before mixing and preparation of the molten material. The mixture can then be heated above the melting point of the polymer to prepare the molten material. For example, mixing and heating may be carried out in an extruder. In some embodiments, the molten material may have a temperature in the range of 200°C to 260°C, preferably 220°C to 250°C, more preferably 230°C to 250°C, and even more preferably 230°C to 240°C, particularly before extrusion. For example, the molten material may be heated to a temperature of 235°C. The molten material is then extruded into the shape of a filament. To obtain a filament, the molten material can be extruded through a nozzle or other orifice having a suitable shape, particularly a circular shape. Optionally, after extrusion, the filament can be cooled, for example, by air cooling or water cooling. Suitable cooling means / apparatus are generally known and can be easily selected by those skilled in the art.

[0125] Preferably, the molten material contains 30 to 70% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 35 to 65% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 40 to 60% by weight or 42 to 62% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 45 to 55% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges may apply when the aliphatic polyester is polybutylene succinate. In a preferred embodiment, the molten material contains 52% by weight of polybutylene succinate, based on a total amount of 100% by weight of polybutylene succinate, aliphatic aromatic polyester, and polyhydroxyalkanoate.

[0126] Preferably, the molten material contains 10 to 60% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 20 to 50% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 25 to 40% by weight or 26 to 46% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 30 to 40% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges are applicable when the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). In a preferred embodiment, the molten material contains 36% by weight of polybutylene adipate terephthalate (PBAT), based on a total amount of aliphatic polyester, polybutylene adipate terephthalate (PBAT), and polyhydroxyalkanoate of 100% by weight.

[0127] Preferably, the molten material contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 3 to 20% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the molten material contains 3 to 18% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the molten material contains 5 to 15% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Preferably, when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), the melt contains 20% by weight or less, more preferably 18% by weight or less of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH).

[0128] The ranges of amounts of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates can also be combined with each other. For example, the molten material may contain 42-62% by weight, preferably 45-55% by weight, of aliphatic polyesters; the molten material may contain 26-46% by weight, preferably 30-40% by weight, of aliphatic-aromatic polyesters; and the molten material may contain 2-22% by weight, preferably 3-20% by weight, more preferably 3-18% by weight, of polyhydroxybutyrate, with each proportion based on 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. A person skilled in the art will readily select appropriate amounts of one or more polymers within the range provided herein, so as not to exceed 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. In particular, these ranges apply when the aliphatic polyester is polybutylene succinate, the aliphatic aromatic polyester is polybutylene adipate terephthalate, and the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In a very preferred embodiment, the molten material comprises 52% by weight of polybutylene succinate, 36% by weight of polybutylene adipate terephthalate, and 12% by weight of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), where each proportion is based on 100% by weight of the total amount of polybutylene succinate, polybutylene adipate terephthalate, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0129] In some embodiments, the polyhydroxyalkanoate may be partially or completely substituted with polylactide (also known as PLA, or polylactic acid or poly(lactic acid)). Therefore, in some embodiments, when the polyhydroxyalkanoate is partially substituted with polylactide, the melt comprises an aliphatic polyester, an aliphatic-aromatic polyester, the polyhydroxyalkanoate, and the polylactide. In some embodiments, when the polyhydroxyalkanoate is completely substituted with polylactide, the melt comprises an aliphatic polyester, an aliphatic-aromatic polyester, and the polylactide. However, in embodiments where the polyhydroxyalkanoate is completely substituted with polylactide, the melt does not contain the polyhydroxyalkanoate.

[0130] Optionally, the molten material may further contain at least one additive. For example, the molten material may contain at least one additive that is commonly known to be used in three-dimensional printing filaments. Optional additives may include, but are not limited to, additives selected from the group consisting of flame retardants, matting agents, markers for certification (e.g., fluorescent markers), antimicrobial agents, plasticizers, colorants, fillers, and any combination thereof.

[0131] Preferably, the molten material contains a flame retardant. More preferably, the flame retardant is a phosphate. In a preferred embodiment, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), and any combination thereof. More preferably, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), and any combination thereof. More preferably, the flame retardant is ammonium dihydrogen phosphate ([NH4][H2PO4]) or diammonium hydrogen phosphate ([NH4]2[HPO4]). Even more preferably, the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]). Alternatively, or in addition, the flame retardant may be a polyphosphate. Preferably, if the flame retardant is a polyphosphate, the flame retardant is ammonium polyphosphate.

[0132] The molten material may contain a flame retardant in an amount of 0.01% to 5% by weight, based on 100% by weight of the total weight of the molten material. Preferably, the molten material contains a flame retardant in an amount of 0.1% to 4% by weight, based on 100% by weight of the total weight of the molten material. More preferably, the molten material contains a flame retardant in an amount of 0.2% to 3% by weight, based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material contains a flame retardant in an amount of 0.3% to 3% by weight, based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material contains a flame retardant in an amount of 0.3% to 2% by weight, based on 100% by weight of the total weight of the molten material. In particular, the above ranges apply when the flame retardant is a phosphate or polyphosphate, preferably when the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]).

[0133] Those skilled in the art will be able to easily select an appropriate amount of additive to be blended into the molten material. For example, the molten material may contain an amount of additive of 15% by weight or less based on 100% by weight of the total weight of the molten material. The molten material may contain an amount of additive of 10% by weight or less based on 100% by weight of the total weight of the molten material. Preferably, the molten material may contain an amount of additive of 7% by weight or less based on 100% by weight of the total weight of the molten material. More preferably, the molten material may contain an amount of additive of 5% by weight or less based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material may contain an amount of additive of 4% by weight or less based on 100% by weight of the total weight of the molten material. Even more preferably, the molten material may contain an amount of additive of 3% to 4% by weight based on 100% by weight of the total weight of the molten material. To achieve the necessary filament rigidity for filaments suitable for three-dimensional printing, it is preferable that the molten material contains 7% by weight or less of additives, and more preferably 3-4% by weight of additives, based on 100% by weight of the total weight of the molten material.

[0134] In some embodiments, the molten material is not extruded through a hollow fiber spinning nozzle to form a filament suitable for three-dimensional printing. As used herein, the term “hollow fiber spinning nozzle” refers to any hollow fiber spinning nozzle commonly known in the art. A merely exemplary example of a hollow fiber spinning nozzle is described, for example, in European Patent Publication No. 2112256, the entire contents of which are incorporated herein by reference.

[0135] In some embodiments, the method for preparing a filament suitable for three-dimensional printing is not the method for preparing fibers as described in international application PCT / EP2022 / 075084, and in particular, in some embodiments, the method for preparing a filament suitable for three-dimensional printing is not the following method. Methods for preparing fibers, including the following: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fibers are cooled under a temperature gradient to obtain the fibers.

[0136] The present invention also relates to a filament suitable for three-dimensional printing that can be obtained or is obtained by a method for preparing a filament suitable for three-dimensional printing according to the present invention.

[0137] The present invention relates to the use of melts comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, wherein the filaments are as defined herein.

[0138] The present invention relates to the use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing.

[0139] [A mixture containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates] The present invention also relates to a mixture comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. Such mixtures can be used, for example, for the manufacture of the fibers of the present invention or filaments suitable for three-dimensional printing.

[0140] The aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate contained in the mixture can be further defined as described herein, and in particular can be defined as described herein for any fiber or any filament suitable for three-dimensional printing. In a very preferred embodiment, the aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyalkoxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Thus, the present invention also relates to mixtures containing polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0141] In some embodiments, the mixture essentially consists of an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate. In some embodiments, the mixture essentially consists of polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In some embodiments, the mixture consists of an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate. In some embodiments, the mixture consists of polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0142] In the mixture, aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates may be present in the form of particles. Exemplary examples of particles that can be used in the mixture can be selected from the group consisting of granules, pellets, extrudes, beads, spheres, and any combination thereof. Preferably, the aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates are in granular form. In a very preferred embodiment, the mixture comprises granular polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). The present invention also relates to granules comprising polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). To prepare fibers or filaments suitable for three-dimensional printing, the mixture containing polymer particles can be heated above the melting point of the polymer. Therefore, in some embodiments, the mixture may exist in the form of a molten material. This molten material can be subjected to spinning of fibers or extrusion into a filament suitable for three-dimensional printing, as described herein.

[0143] Preferably, the mixture contains 30 to 70% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the mixture contains 35 to 65% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 40 to 60% by weight or 42 to 62% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 45 to 55% by weight of aliphatic polyester, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges may apply when the aliphatic polyester is polybutylene succinate. In a preferred embodiment, the mixture contains 52% by weight of polybutylene succinate, based on a total amount of 100% by weight of polybutylene succinate, aliphatic aromatic polyester, and polyhydroxyalkanoate.

[0144] Preferably, the mixture contains 10 to 60% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the mixture contains 20 to 50% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 25 to 40% by weight or 26 to 46% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 30 to 40% by weight of aliphatic-aromatic polyester based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges are applicable when the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT). In a preferred embodiment, the mixture contains 36% by weight of polybutylene adipate terephthalate (PBAT) based on a total amount of aliphatic polyester, polybutylene adipate terephthalate (PBAT), and polyhydroxyalkanoate of 100% by weight.

[0145] Preferably, the mixture contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the mixture contains 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 3 to 20% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. Even more preferably, the mixture contains 3 to 18% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. More preferably, the mixture contains 5 to 15% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. In particular, these ranges can be applied when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). Preferably, when the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), the mixture contains 20% by weight or less, more preferably 18% by weight or less of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH), based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH).

[0146] The range of amounts of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates can also be combined with each other. For example, a mixture may contain 42-62% by weight, preferably 45-55% by weight, of aliphatic polyesters; a mixture may contain 26-46% by weight, preferably 30-40% by weight, of aliphatic-aromatic polyesters; a mixture may contain 2-22% by weight, preferably 3-20% by weight, more preferably 3-18% by weight, of polyhydroxybutyrate, where the proportion of each is based on 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. A person skilled in the art will readily select appropriate amounts of one or more polymers within the range provided herein, so as not to exceed 100% by weight of the total amount of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. In particular, these ranges apply when the aliphatic polyester is polybutylene succinate, the aliphatic aromatic polyester is polybutylene adipate terephthalate, and the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). In a very preferred embodiment, the mixture comprises 52% by weight of polybutylene succinate, 36% by weight of polybutylene adipate terephthalate, and 12% by weight of polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), where each proportion is based on 100% by weight of the total amount of polybutylene succinate, polybutylene adipate terephthalate, and polyhydroxybutyrate-co-hydroxyhexanoate, preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).

[0147] Optionally, the mixture may further contain at least one additive. For example, the mixture may contain at least one additive that is commonly known to be used in textile fibers or three-dimensional printing filaments. Optional additives may include, but are not limited to, additives selected from the group consisting of flame retardants, matting agents, markers for certification (e.g., fluorescent markers), antimicrobial agents, plasticizers, colorants, fillers, and any combination thereof.

[0148] Preferably, the mixture contains a flame retardant. More preferably, the flame retardant is a phosphate. In a preferred embodiment, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), and any combination thereof. More preferably, the flame retardant is selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), and any combination thereof. More preferably, the flame retardant is ammonium dihydrogen phosphate ([NH4][H2PO4]) or diammonium hydrogen phosphate ([NH4]2[HPO4]). Even more preferably, the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]). Alternatively, or in addition, the flame retardant may be a polyphosphate. Preferably, if the flame retardant is a polyphosphate, the flame retardant is ammonium polyphosphate.

[0149] The mixture may contain a flame retardant in an amount of 0.01% to 5% by weight, based on 100% by weight of the total weight of the mixture. Preferably, the mixture contains a flame retardant in an amount of 0.1% to 4% by weight, based on 100% by weight of the total weight of the mixture. More preferably, the mixture contains a flame retardant in an amount of 0.2% to 3% by weight, based on 100% by weight of the total weight of the mixture. Even more preferably, the mixture contains a flame retardant in an amount of 0.3% to 3% by weight, based on 100% by weight of the total weight of the mixture. Even more preferably, the mixture contains a flame retardant in an amount of 0.3% to 2% by weight, based on 100% by weight of the total weight of the mixture. In particular, the above ranges apply when the flame retardant is a phosphate or polyphosphate, preferably when the flame retardant is diammonium hydrogen phosphate ([NH4]2[HPO4]).

[0150] Those skilled in the art will be able to easily select an appropriate amount of additive to be added to the mixture. For example, the mixture may contain an amount of additive of 15% by weight or less based on 100% by weight of the total weight of the mixture. The mixture may contain an amount of additive of 10% by weight or less based on 100% by weight of the total weight of the mixture. Preferably, the mixture may contain an amount of additive of 7% by weight or less based on 100% by weight of the total weight of the mixture. More preferably, the mixture may contain an amount of additive of 5% by weight or less based on 100% by weight of the total weight of the mixture. Even more preferably, the mixture may contain an amount of additive of 4% by weight or less based on 100% by weight of the total weight of the mixture. Even more preferably, the mixture may contain an amount of additive of 3% to 4% by weight based on 100% by weight of the total weight of the mixture. To achieve a stiffness useful for textile fibers or filaments suitable for three-dimensional printing, it is preferable that the mixture contains an amount of additive of 7% by weight or less, and more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the mixture.

[0151] The present invention relates to the use of a mixture comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the production of fibers, the fibers being as defined herein.

[0152] The present invention also relates to the use of aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures comprising polyhydroxyalkanoates for the production of fibers.

[0153] The present invention also relates to the use of aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures comprising polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, wherein the filaments are as defined herein.

[0154] The present invention also relates to the use of aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures containing polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing.

[0155] It should be noted that, as used herein, the singular forms “a,” “an,” and “the” include multiple references unless the context explicitly indicates otherwise. For example, a reference to “a reagent” includes one or more such different reagents, and a reference to “the method” includes equivalent steps and methods known to those skilled in the art, which may be modified or substituted for the method described herein.

[0156] Unless otherwise specified, the term "at least" preceding a series of elements is understood to refer to each element in the series. Those skilled in the art will recognize, or can verify without performing any more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed within the invention.

[0157] As used herein, the terms "and / or" include the meanings of "and," "or," and "all or any combination of the elements connected by the term."

[0158] The terms "less than" or "greater than" do not include specific numbers. For example, "less than 20" means less than the given number. Similarly, "greater than" means greater than the given number; for example, "greater than 80%" means greater than 80% of the given number.

[0159] Throughout this specification and the subsequent claims, unless otherwise specified in the context, the word “comprise,” and variations such as “comprises,” and “comprising,” are understood to mean including the integer or process, or group of integers or processes, described herein, but not to mean excluding other integers or processes, or groups of integers or processes. As used herein, the term “comprising” may be replaced by the terms “containing” or “including,” and as used herein, it may also be replaced by the term “having.”

[0160] As used herein, “consisting of” excludes any element, step, or component not specified in the claim elements. As used herein, “consisting essentially of” does not exclude any material or step that does not materially affect the basic and novel characteristics of the claim. In each example herein, any of the terms “comprising,” “consisting essentially of,” and “consisting of” may be replaced with any of the other two terms.

[0161] "Including" means "including but not limited to." "Including" and "including but not limited to" are used interchangeably.

[0162] Where used herein, the term “approximately” is understood to mean that each value or range (such as pH, concentration, percentage, molar concentration, or time) may vary by up to 5% or 10% from the given value. For example, if a compound has a composition of approximately 5 mg / ml, it is understood to mean that the composition may range from 4.5 to 5.5 mg / ml.

[0163] The present invention is not limited to, and should be understood to be, any specific methodologies, protocols, materials, reagents, and substances described herein, but may be modified. The terms used herein are for the sole purpose of describing specific embodiments and are not intended to limit the scope of the invention as defined solely by the claims.

[0164] All publications cited throughout this specification (including all patents, patent applications, scientific publications, and manuals) are incorporated herein by reference, whether as stated above or below. Nothing in this specification shall be construed as acknowledging that there are no prior rights prior to disclosures by prior art. To the extent that any material incorporated by reference conflicts with or conflicts with this specification, this specification shall prevail.

[0165] The contents of all documents and patent documents cited herein are incorporated in their entirety by reference.

[0166] The present invention is further characterized by the following: 1. Fibers made from a mixture containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. 2. Aliphatic polyesters are aliphatic C2-C 20 Dicarboxylic acids and aliphatic C2-C 12 The fibers described in item 1, including diols. 3. Aliphatic polyesters are fibers as described in paragraph 1 or 2, selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-bristlate (PBSBr), and combinations thereof. 4. The aliphatic polyester is a fiber as described in any one of the following three paragraphs, selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-bristlate (PBSBr), and combinations thereof. 5. The aliphatic polyester is polybutylene succinate (PBS), as described in any one of the sections 1 to 4. 6. A fiber according to any one of paragraphs 1 to 5, comprising 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 7. Aliphatic-aromatic polyesters are C2-C 12 A fiber according to any one of the following paragraphs, comprising an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an aliphatic C2-C12 diol. 8. The aliphatic-aromatic polyester is selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof, as described in any one of the paragraphs 1 to 7. 9. The aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), the fiber as described in any one of subsections 1 to 8. 10. A fiber according to any one of the items 1 to 10, comprising 10 to 60% by weight of aliphatic-aromatic compounds, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 11. Polyhydroxyalkanoates are C3-C 18 A fiber that is a hydroxyalkyl carboxylic acid, as described in any one of items 1 to 10. 12. The polyhydroxyalkanoate is selected from the group consisting of polyhydroxybutyrate-co-hydroxyhexanoate, polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, and combinations thereof, as described in any one of the items 1 to 11. 13. The polyhydroxyalkanoate is selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and any combination thereof, as described in any one of the items 1 to 12. 14. The fiber according to any one of items 1 to 13, wherein the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate. 15. The fiber described in any one of the paragraphs 1 to 14, wherein the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). 16. A fiber according to any one of sub-sub 17. A fiber according to any one of sub-sub 18. A fiber according to any one of sub-sub 19. A fiber according to any one of the paragraphs 1 to 18, wherein some or all of the polyhydroxyalkanoate is substituted with polylactide. 20. A woven fiber, as described in any one of paragraphs 1 through 19. 21. A fiber according to any one of the paragraphs 1 to 20, further comprising at least one additive. 22. The fiber according to paragraph 21, wherein at least one additive is selected from the group consisting of flame retardants, matting agents, fluorescent markers, antimicrobial agents, plasticizers, fillers, and any combination thereof. 23. The additive is a flame retardant, as described in paragraph 22. 24. The fiber according to paragraph 23, wherein the flame retardant is a phosphate selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), ammonium phosphate, and any combination thereof. 25. The fiber described in subheading 24, wherein the phosphate is diammonium hydrogen phosphate ([NH4]2[HPO4]). 26. A fiber according to any one of items 22 to 25, comprising 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight, of a weight of 100% of the total weight of the fiber, containing a flame retardant. 27. The additive is a matting agent, as described in paragraph 22. 28. The matting agent is zinc sulfide, as described in paragraph 27. 29. The additive is a fluorescent marker, as described in section 22. 30. The additive is an antimicrobial agent, as described in Section 22. 31. The fiber according to item 30, wherein the antimicrobial agent is preferably zinc encapsulated in polyethylene terephthalate. 32. The additive is a filler, the fiber as described in heading 31. 33. A fiber as described in heading 32, which is lignin or contains lignin as a filler. 34. The fiber according to any one of items 21 to 33, comprising an additive in a total amount of 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3-4% by weight, based on 100% by weight of the total weight of the fiber. 35. The fiber titer is 0.5 to 8 den, preferably 0.8 to 6 den, more preferably 0.9 to 3 den, even more preferably 1.0 to 2 den, even more preferably 1.0 to 1.5 den, and even more preferably 1.1 to 1.2 den. The fibers described in any one of paragraphs 1 through 34. 36. A staple fiber, as described in any one of the three paragraphs 1 through 35. The fiber according to item 36, having a staple length of 37.2 to 80 mm, preferably 5 to 70 mm, more preferably 10 to 60 mm, even more preferably 15 to 50 mm, even more preferably 20 to 40 mm, even more preferably 22 to 35 mm, and even more preferably 25 to 32 mm. 38. A filament, as described in any one of paragraphs 1 through 35. 39. A fiber described in any one of headings 1 to 38, which is biodegradable in accordance with EN13432. 40. Fibers described in any one of paragraphs 1 to 39 that are not obtainable by a method including the following steps: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and - The precursor fibers are cooled under a temperature gradient to obtain the fibers. 41. Fibers described in any one of paragraphs 1 through 40, other than the following fibers: Made from a mixture containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, In the longitudinal direction, it comprises two types of parts, one of which is a thick part and the other is a thin part, and the thick and thin parts extend perpendicular to the longitudinal direction of the fiber, with the extension of the thick part in the perpendicular direction being greater than the extension of the thin part in the perpendicular direction. A fiber in which at least a portion of the thicker part has a hollow structure, and in which at least a portion of the thinner part has a dense structure. 42. Fibers according to any one of the following sections, 1 to 41, that are not hollow fibers made from a mixture of aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates. 43. A fiber described in any one of the paragraphs 1 to 42, which is not a split fiber or a split hollow fiber. 44. Yarn containing the fibers described in any one of paragraphs 1 through 43. 45. A textile comprising a fiber as described in any one of headings 1 to 43 or a yarn as described in heading 44. 46. ​​Textiles described in heading 45, which are for clothing or household use. 47. The garment is preferably selected from the group consisting of shirts, polo shirts, trousers, jackets, underwear, socks, coats, shoes, and shoelaces, as described in paragraph 46. 48. Household textiles are textiles described in paragraph 47, selected from the group consisting of curtains, rugs, blankets, bed sheets, quilts, duvet covers, cushion covers and towels. 49. A method for producing the fibers described in any one of paragraphs 1 to 43, - A molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate is spun through a spinning nozzle to obtain precursor fibers; and - Cooling the precursor fibers to obtain the fibers, Methods that include... 49a. The method according to item 49, wherein the temperature of the molten material is in the range of 200°C to 260°C, preferably in the range of 220°C to 250°C, more preferably in the range of 230°C to 250°C, and even more preferably in the range of 230°C to 240°C. 50. Cooling is performed by air cooling, as described in paragraph 49. 51. The method according to paragraph 49 or 50, wherein the molten material contains 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 52. The method according to paragraphs 49 to 51, wherein the molten material contains 10 to 60% by weight of aliphatic-aromatic compounds, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 53. The method according to any one of headings 49 to 52, wherein the molten material contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 54. The method according to any one of headings 49 to 53, wherein the material contains 42 to 62% by weight of aliphatic polyester, 26 to 46% by weight of aromatic-aliphatic polyester, and 2 to 22% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aromatic-aliphatic polyester, and polyhydroxyalkanoate. 55. The method according to any one of the paragraphs 49 to 54, wherein some or all of the polyhydroxyalkanoate is substituted with polylactide. 56. The method according to any one of headings 49 to 55, wherein the molten material further comprises at least one additive. 57. The method according to claim 56, wherein at least one additive is selected from the group consisting of flame retardants, matting agents, fluorescent markers, antimicrobial agents, plasticizers, fillers, and any combination thereof. 58. The additive is a flame retardant, as described in paragraph 57. 59. The method according to item 58, wherein the molten material contains 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the molten material. 60. The total amount of additives is 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3-4% by weight, based on 100% by weight of the total weight of the molten material, and the method according to any one of items 56 to 59. 61. The method described in any one of the headings 49 to 60, wherein the fibers are prepared as staple fibers. 62. The method according to any one of the items 49 to 60, wherein the fibers are prepared as filaments. 63. The method described in any one of headings 49 to 62, wherein the spinning nozzle is not a hollow fiber spinning nozzle. 64. The method described in any one of paragraphs 49 to 63, -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and -Precursor fibers are cooled under a temperature gradient to obtain the fibers. A method, not a method, for preparing fibers that include [the specified element]. 65. Fibers that can be obtained or obtained by the method described in any one of the paragraphs 49 to 64. 66. Use for the preparation of fibers of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, as specified in any one of headings 1 to 43. 67. Use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of fibers. 68. Use for the manufacture of fibers comprising aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures of polyhydroxyalkanoates, wherein the fibers are as defined in any one of subheadings 1 to 43. 69. Use of aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures containing polyhydroxyalkanoates for the manufacture of fibers. 70. A filament suitable for three-dimensional printing, made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 71. Aliphatic polyesters are aliphatic C2-C 20 Dicarboxylic acids and aliphatic C2-C 12 A filament containing a diol, as described in Section 70. 72. The aliphatic polyester is a filament as described in Section 70 or 71, selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-bristlate (PBSBr), and any combination thereof. 73. The aliphatic polyester is selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brushate (PBSBr), and any combination thereof, as described in any one of the items 70 to 72. 74. The aliphatic polyester is polybutylene succinate (PBS), as described in any one of the sections 70 to 73. 75. A filament according to any one of the following headings, 70 to 74, comprising 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 76. Aliphatic-aromatic polyesters are filaments according to any one of the following paragraphs, 70 to 75, comprising C2-C12 aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic C2-C12 diols. 77. The aliphatic-aromatic polyester is a filament according to any one of the following paragraphs, 70 to 76, selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof. 78. The aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), as described in any one of the three headings 70 to 77. 79. A filament according to any one of the following headings, 70 to 78, comprising 10 to 60% by weight of aliphatic-aromatic compounds, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 80. Polyhydroxyalkanoates are C3-C 18 A filament according to any one of paragraphs 70 to 79, wherein the filament is a hydroxyalkyl carboxylic acid. 81. The polyhydroxyalkanoate is selected from the group consisting of polyhydroxybutyrate-co-hydroxyhexanoate, polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, and any combination thereof, as described in any one of paragraphs 70 to 80. 82. The polyhydroxyalkanoate is a filament according to any one of the following paragraphs, 70 to 81, selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and any combination thereof. 83. The filament according to any one of the following paragraphs, 70 to 82, wherein the polyhydroxyalkanoate is polyhydroxybutyrate-co-hydroxyhexanoate. 84. The filament according to any one of the following paragraphs, 70 to 83, wherein the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). 85. A filament according to any one of the following headings, 70 to 84, comprising 1 to 25% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 86. A filament according to any one of the following headings, 70 to 85, comprising 42 to 62% by weight of aliphatic polyester, 26 to 46% by weight of aromatic-aliphatic polyester, and 2 to 22% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aromatic-aliphatic polyester, and polyhydroxyalkanoate of 100% by weight. 87. A filament according to any one of the following sections, 70 to 86, wherein the aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). 88. A filament according to any one of the paragraphs 70 to 87, wherein part or all of the polyhydroxyalkanoate is substituted with polylactide. 89. A filament according to any one of the headings 70 to 88, wherein the fiber further comprises at least one additive. 90. The filament according to paragraph 89, wherein at least one additive is selected from the group consisting of flame retardants, matting agents, fluorescent markers, antimicrobial agents, plasticizers, fillers, and any combination thereof. 91. The additive is a flame retardant, as described in Section 90. 92. The filament according to paragraph 91, wherein the flame retardant is a phosphate selected from the group consisting of ammonium dihydrogen phosphate ([NH4][H2PO4]), diammonium hydrogen phosphate ([NH4]2[HPO4]), triammonium phosphate ([NH4]3[PO4]), ammonium phosphate, and any combination thereof. 93. The phosphate is diammonium hydrogen phosphate ([NH4]2[HPO4]), as described in section 92. 94. A filament according to any one of paragraphs 90 to 93, comprising 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the filament. 95. The additive is a matting agent, as described in Section 90. 96. The matting agent is zinc sulfide, as described in item 95. 97. The additive is a fluorescent marker, as described in Section 90. 98. The additive is an antimicrobial agent, as described in Section 90. 99. The filament according to paragraph 98, wherein the antimicrobial agent is preferably zinc encapsulated in polyethylene terephthalate. 100. The additive is a filler, as described in Section 90 of the filament. 101. The filament described in Section 100, wherein the filler is lignin or contains lignin. 102. The filament according to any one of paragraphs 89 to 101, wherein the amount is 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3-4% by weight, based on 100% by weight of the total weight of the filament. 103. The diameter of the filament is 1.0 mm or more, preferably 1.5 mm or more, more preferably 1.6 mm or more, and even more preferably 1.7 mm or more; and The filament according to any one of items 70 to 102, wherein the diameter of the filament is 5.0 mm or less, preferably 4.0 mm or less, more preferably 3.5 mm or less, and even more preferably 3.0 mm or less. 104. The filament according to item 103, wherein the diameter of the filament is preferably in the range of 1.70 mm to 1.80 mm. 105. The filament according to item 103, wherein the diameter of the filament is preferably in the range of 2.80 mm to 3.05 mm. 106. A filament described in any one of subheadings 70 to 105, which is biodegradable in accordance with EN13432. 107. Filaments described in any one of the following sections, 70 to 106, that can be obtained by a method including the following steps, or are not fibers obtained by such a method: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and - The precursor fibers are cooled under a temperature gradient to obtain the fibers. 108. Filaments described in any one of the following sections, 70 to 107, that are not fibers: A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, In the longitudinal direction, the fiber comprises two types of parts, one of which is a thick part and the other of which is a thin part, with the thick and thin parts extending perpendicular to the longitudinal direction of the fiber, and the vertical extension of the thick part being greater than the vertical extension of the thin part; A fiber in which at least a portion of the thicker part has a hollow structure, and in which at least a portion of the thinner part has a dense structure. 109. A filament according to any one of the headings 70 to 108, which is not a hollow fiber, made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 110. A filament as described in any one of the sections 70 to 109, which is not a split fiber or a split hollow fiber. 111. A roll containing a filament suitable for three-dimensional printing as described in any one of sections 70 to 110. 112. A cartridge suitable for three-dimensional printing, containing a filament suitable for three-dimensional printing as described in any one of sections 70 to 110. 113. A three-dimensional printed article that can be obtained, or is obtained, by subjecting a filament suitable for three-dimensional printing as described in any one of paragraphs 70 to 110 to three-dimensional printing. 114. A method for preparing a filament suitable for three-dimensional printing as described in any one of paragraphs 70 to 110, comprising extruding a molten material comprising an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate into a filament shape. 114a. The method according to item 114, wherein the temperature of the molten material is in the range of 200°C to 260°C, preferably in the range of 220°C to 250°C, more preferably in the range of 230°C to 250°C, and even more preferably in the range of 230°C to 240°C. 115. The method according to claim 114, wherein the molten material contains 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 116. The method according to paragraph 114 or 115, wherein the molten material contains 10 to 60% by weight of aliphatic-aromatic compounds, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. 117. The method according to any one of headings 114 to 116, wherein the molten material contains 1 to 25% by weight of polyhydroxyalkanoate based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. 118. The method according to any one of headings 114 to 117, wherein the molten material contains 42 to 62% by weight of aliphatic polyester, 26 to 46% by weight of aromatic-aliphatic polyester, and 2 to 22% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aromatic-aliphatic polyester, and polyhydroxyalkanoate of 100% by weight. 119. A method according to any one of paragraphs 114 to 118, wherein part or all of the polyhydroxyalkanoate is substituted with polylactide. 120. A method according to any one of headings 114 to 119, wherein the molten material further comprises at least one additive. 121. The method according to claim 120, wherein at least one additive is selected from the group consisting of flame retardants, matting agents, fluorescent markers, antimicrobial agents, plasticizers, fillers, and any combination thereof. 122. The method described in heading 121, wherein the additive is a flame retardant. 123. The method of item 122, wherein the molten material contains 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the molten material. 124. The method according to any one of items 120 to 123, wherein the total amount of additives is 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the molten material. 125. The method described in any one of paragraphs 114 to 124, other than the following: A method for preparing fibers, comprising the following steps: -Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fibers are cooled under a temperature gradient to obtain the fibers. 126. Filaments that can be obtained or obtained by any one of the methods described in paragraphs 114 to 125. 127. Use of melts comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, wherein the filaments are as defined in any one of the items 70 to 110. 128. Use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing. 129. A method for preparing filaments suitable for three-dimensional printing of mixtures comprising aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates, wherein the filaments are as defined in any one of the items 70 to 110. 130. Use of a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate for the preparation of filaments suitable for three-dimensional printing.

[0167] A better understanding of the present invention and its advantages will be provided by the following examples, which are provided for illustrative purposes only. The examples are not intended to limit the scope of the invention in any way. [Examples]

[0168] [Example 1] Preparation of fibers according to an embodiment of the present invention The following components (masterbatch of polymer I, polymer II, polymer III, and additives) were used in the preparation of fibers according to embodiments of the present invention: Polymer I: Polybutylene succinate (PBS, Mitsubishi Chemical Bio-Corporation PBS FZ71, bio-based) Polymer II: Polybutylene adipate terephthalate (PBAT, BASF ECOFLEX PBAT) Polymer III: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PBHB, Kaneka Corporation AONILEX X151A, bio-based) Masterbatch: The masterbatch contains the amounts of additives shown in Table 1 below.

[0169] [Table 1]

[0170] Fibers according to embodiments of the present invention were prepared using a Fourne pilot melt spinning machine (built in 2013, Fourne Maschinenbau GmbH, Alfter-Impekoven, Germany), along with an add-on module for allowing side flow of masterbatch additives, a spinning nozzle (any spinning nozzle suitable for melt spinning of fibers can be used; in this embodiment, the nozzle has a circular orifice and is not a hollow fiber spinning nozzle), and a fiber post-processing line. The fiber post-processing line performed further external processing using the steps of lead, suction structure, immersion bath, draft system I, stretching bath, draft system II, steam, draft system III, revive roller, crimp, drying, and staple cutting machine.

[0171] Polymer I (15,600 g, polybutylene succinate (PBS)), Polymer II (10,800 g, polybutylene adipate terephthalate (PBAT)), and Polymer III (3,600 g, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)) were added to the melt spinning machine as granules. Furthermore, 1.650 kg of powdered masterbatch (additive) was added to the module via a simple screw feeder to allow lateral flow; the moisture content was approximately 0.1% by weight. Polymers I, II, and III, as well as the masterbatch (additive), were dried in a vacuum drying cabinet at 60°C for 24 hours prior to addition.

[0172] The following process parameters were used: Flow velocity: 2.5 kg / h, flow rate 5.12 m / min or less; Processing temperature: 230~250℃ (e.g., 235℃); Distance between spinning nozzle and godet: 200 cm; Takeoff Godet: 85℃ 800m / min; Godet Roller 1: 80℃ 980m / min; Godet Roller 2: 80℃ 1350m / min; Cooling was achieved using air cooling, which supplied airflow to the precursor fibers from both sides.

[0173] Figure 1 schematically shows a melt spinning apparatus and fiber preparation process that can be used to prepare fibers. The melt spinning apparatus in Figure 1 is equipped with a spinning nozzle 1 having a circular orifice. In this example, a molten material consisting of three polymers with a processing temperature of 250°C is spun using an extruder through the spinning nozzle 1 (not a hollow fiber spinning nozzle in this example) to obtain high-temperature precursor fibers 3. To cool the precursor fibers 3, an airflow 7 is supplied from both sides of the precursor fibers 3. The airflow 7 may be supplied by an air cooling device schematically implied by snowflakes. In this example, the air used for the airflow 7 has ambient temperature (approximately 20°C). As a result of air cooling, fibers 11 are obtained. The fibers 11 are then wound up by a godet roll 13.

[0174] Figure 2 shows an extended scheme for further processing of fibers by preparation and post-treatment according to embodiments of the present invention. As shown in Figure 2, the fibers may be, for example, finished, cut and compressed and packaged.

[0175] [Example 2] Antimony content test For example, the antimony content of the fibers obtained as in Example 1 was measured at the Dr. Matt Institute in Shahn, Liechtenstein. In principle, antimony, being a harmful element, may be present as a residue of catalysts used in the polymer manufacturing process. The antimony content was tested as follows: The fibers from Example 1 were placed in water and (a) heated to the boiling point of the water; (b) stored in water for 8 weeks; and (c) further stored for 4 weeks in a cup filled with water and air (sealed, 1 / 3 air, 2 / 3 water). Antimony was not detected in the fibers or in the water (antimony S6 < 0.1 mg / kg ICP-MS). Therefore, this test demonstrates that the fibers can be prepared without using toxic antimony.

[0176] [Example 3] Further properties of fibers according to an embodiment of the present invention Table 2 below shows further properties of fibers according to embodiments of the present invention (for example, those obtained as described in Example 1) compared with known commercially available fibers used in the manufacture of textiles.

[0177] [Table 2]

[0178] As can be seen from Table 2, the fibers according to the embodiments of the present invention can be prepared using flame retardants, are aqueous, can be prepared without antimony, are biodegradable according to EN13432, are stain-resistant, wrinkle-resistant, and can be prepared with a proportion of renewable raw materials. The preparation of the fibers according to the embodiments of the present invention requires far less water consumption than that of cotton. Furthermore, the area required per ton (1000 kg) for the preparation of the fibers according to the embodiments of the present invention is also far smaller than that of cotton. Therefore, the fibers according to the embodiments of the present invention are more beneficial from an ecological standpoint compared to cotton.

[0179] [Example 4] Clothing containing fibers according to an embodiment of the present invention A shirt was manufactured using fibers according to embodiments of the present invention (for example, those obtained as described in Example 1), particularly yarn made from those fibers.

[0180] Figure 3 is a photograph showing, in particular, granules 15 of a mixture that can be used to prepare fibers or filaments suitable for injection molding according to the present invention. Figure 3 also shows fibers 17 according to embodiments of the present invention (for example, those obtained as described in Example 1), and yarn 19 made from the fibers wound on a bobbin. Figure 3 also shows a shirt 21 made from the fibers, in particular from yarn made from fibers containing about 40% fibers and about 60% cotton according to embodiments of the present invention. Figure 4 is a photograph showing a further appearance of the shirt 21.

[0181] [Example 5] Preparation of a filament for three-dimensional printing according to an embodiment of the present invention The same components as those described in Example 1 (a masterbatch of polymer I, polymer II, polymer III, and the additives shown in Table 1) were also used to prepare the filament for three-dimensional printing according to the embodiment of the present invention.

[0182] Polymer I (15,600 g, polybutylene succinate (PBS)), Polymer II (10,800 g, polybutylene adipate terephthalate (PBAT)), and Polymer III (3,600 g, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)) were mixed with 1.650 kg of masterbatch (additive). The moisture content was approximately 0.1% by weight. Polymers I, II, III and the masterbatch (additive) were dried in a vacuum drying cabinet at 60°C for 24 hours before addition.

[0183] A molten material with a diameter of 1.75 mm was prepared and extruded from a nozzle with a diameter of 2.5 mm at a melting temperature of 30 to 250°C (e.g., 235°C) using a single-screw molten compounding extruder, and then cooled in water at 40°C to obtain a filament with a diameter of 1.75 mm.

[0184] A filament 23 suitable for three-dimensional printing according to an embodiment of the present invention can be prepared, for example, as described in Embodiment 5, and is shown in Figure 3.

[0185] Using this filament, we manufactured credit card-shaped plastic cards with a conventional 3D printer.

Claims

1. A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, Aliphatic polyesters are aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C ２０ Contains diols, fiber.

2. The aforementioned fibers are not hollow fibers. The fiber according to claim 1.

3. The aliphatic polyester is selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasilate (PBSBr), and any combination thereof. The aliphatic polyester is preferably selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasilate (PBSBr), and any combination thereof. The aliphatic polyester is more preferably polybutylene succinate (PBS), The aforementioned fiber preferably contains 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The fiber according to claim 1 or 2.

4. The aliphatic-aromatic polyester is C ２ -C １２ Aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic C ２ -C １２ Contains diol, The aliphatic-aromatic polyester is preferably selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof. The aliphatic-aromatic polyester is more preferably polybutylene adipate terephthalate (PBAT), The fiber preferably contains 10 to 60% by weight of aliphatic-aromatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The fiber according to any one of claims 1 to 3.

5. The polyhydroxyalkanoate is C ３ -C １８ hydroxyalkyl carboxylic acid, The polyhydroxyalkanoate is preferably selected from the group consisting of polyhydroxybutyrate-co-hydroxyhexanoate, polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, and any combination thereof. The polyhydroxyalkanoate is more preferably selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and any combination thereof. The polyhydroxyalkanoate is most preferably polyhydroxybutyrate-co-hydroxyhexanoate. The polyhydroxyalkanoate is more preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), The fiber preferably contains 1 to 25% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The fiber according to any one of claims 1 to 4.

6. Based on a total amount of aliphatic polyesters, aromatic-aliphatic polyesters, and polyhydroxyalkanoates of 100% by weight, the product contains 42-62% by weight of aliphatic polyesters, 26-46% by weight of aromatic-aliphatic polyesters, and 2-22% by weight of polyhydroxyalkanoates. The fiber according to any one of claims 1 to 5.

7. The aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). The fiber according to any one of claims 1 to 6.

8. The polyhydroxyalkanoate is partially or entirely substituted with polylactide. The fiber according to any one of claims 1 to 7.

9. The aforementioned fiber is a woven fiber. The fiber according to any one of claims 1 to 8.

10. The fiber further comprises at least one additive, and the fiber preferably contains a total amount of the additive of 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the fiber. The fiber according to any one of claims 1 to 9.

11. The at least one additive is preferably selected from the group consisting of flame retardants, matting agents, fluorescent markers, antibacterial agents, plasticizers, colorants, fillers, and any combination thereof. The aforementioned additive is a flame retardant, The aforementioned flame retardant is ammonium dihydrogen phosphate ([NH ４ ] [H ２ PO ４ ]), diammonium hydrogen phosphate ([NH ４ ] ２ [HPO] ４ ]), triammonium phosphate ([NH ４ ] ３ [PO ４ A phosphate selected from the group consisting of ammonium phosphate and any combination thereof, The phosphate is more preferably diammonium hydrogen phosphate ([NH ４ ] ２ [HPO] ４ ]) or, The fibers more preferably contain 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and / or 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the fibers, and / or The additive is optionally a matting agent, preferably zinc sulfide, and / or the additive is optionally a fluorescent marker, and / or the additive is optionally an antimicrobial agent, preferably zinc encapsulated in polyethylene terephthalate, and / or the additive is optionally a filler, preferably lignin or containing lignin. The fiber according to claim 10.

12. The fiber titer is 0.5 to 8 den, preferably 0.8 to 6 den, more preferably 0.9 to 3 den, even more preferably 1.0 to 2 den, even more preferably 1.0 to 1.5 den, and even more preferably 1.1 to 1.2 den. The fiber according to any one of claims 1 to 11.

13. The aforementioned fibers are staple fibers. The aforementioned fibers have a staple length of 2 to 80 mm, preferably 5 to 70 mm, more preferably 10 to 60 mm, even more preferably 15 to 50 mm, even more preferably 20 to 40 mm, even more preferably 22 to 35 mm, and even more preferably 25 to 32 mm. The fiber according to any one of claims 1 to 12.

14. The aforementioned fiber is a filament. The fiber according to any one of claims 1 to 12.

15. The aforementioned fibers are biodegradable in accordance with EN13432. The fiber according to any one of claims 1 to 14.

16. The aforementioned fiber is - Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and - Cooling the precursor fibers under a temperature gradient to obtain the fibers, It is possible to obtain, or not obtain, the fibers, and / or, The aforementioned fiber is A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, The fiber comprises two types of parts in the longitudinal direction, one of which is a thick part and the other of which is a thin part, and the thick and thin parts extend perpendicular to the longitudinal direction of the fiber, with the extension of the thick part in the perpendicular direction being greater than the extension of the thin part in the perpendicular direction; At least a portion of the thicker portion is hollow, and at least a portion of the thinner portion is not a dense fiber, and / or The aforementioned fibers are not hollow fibers made from a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, and / or The aforementioned fibers are not split fibers or split hollow fibers. The fiber according to any one of claims 1 to 15.

17. A yarn containing the fibers described in any one of claims 1 to 16.

18. A fabric comprising the fibers described in any one of claims 1 to 16 or the yarn described in claim 17, The aforementioned fabric is preferably a fabric for clothing or household use. The aforementioned clothing is preferably selected from the group consisting of shirts, polo shirts, trousers, jackets, underwear, socks, coats, shoes, and shoelaces. The aforementioned household textiles are preferably selected from the group consisting of curtains, rugs, blankets, bed sheets, futons, futon covers, cushion covers, and towels. fabric.

19. A method for preparing the fibers according to any one of claims 1 to 16, - Spinning a molten material containing an aliphatic polyester, an aliphatic-aromatic polyester, and a polyhydroxyalkanoate through a spinning nozzle to obtain precursor fibers; and, - Cool the precursor fiber to obtain the fiber, Includes, Preferably, the temperature of the molten material is in the range of 200°C to 260°C, preferably 220°C to 250°C, more preferably 230°C to 250°C, even more preferably 230°C to 240°C, and / or The cooling is preferably carried out by air cooling. The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diols, method.

20. The molten material contains 30 to 70% by weight of aliphatic polyester, and / or, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The molten material contains 10 to 60% by weight of aliphatic-aromatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight, and / or The molten material contains 1 to 25% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. The method according to claim 19.

21. The molten material contains 42 to 62% by weight of aliphatic polyester, 26 to 46% by weight of aromatic-aliphatic polyester, and 2 to 22% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aromatic-aliphatic polyester, and polyhydroxyalkanoate of 100% by weight. The method according to claim 19 or 20.

22. The polyhydroxyalkanoate is partially or entirely substituted with polylactide. The method according to any one of claims 19 to 21.

23. The molten material further comprises at least one additive, The total amount of the additive is preferably 15% by weight or less, more preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the molten material. The at least one additive is preferably selected from the group consisting of flame retardants, matting agents, fluorescent markers, antibacterial agents, plasticizers, fillers, and any combination thereof. The additive is optionally a flame retardant, and the molten material contains 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight of the flame retardant, based on 100% by weight of the total weight of the molten material. The method according to any one of claims 19 to 22.

24. The aforementioned fibers are prepared as staple fibers, or the aforementioned fibers are prepared as filaments. The method according to any one of claims 19 to 23.

25. The aforementioned spinning nozzle is not a hollow fiber spinning nozzle, and / or, The aforementioned method, - Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - The precursor fiber is cooled under a temperature gradient to obtain the fiber. This is not a method for preparing fibers that include The method according to any one of claims 19 to 24.

26. A fiber that can be obtained by the method described in any one of claims 19 to 25, wherein the fiber is preferably not a hollow fiber. fiber.

27. A melt containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates is used for the preparation of fibers, The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ The fiber contains a diol, and preferably the fiber is as defined in any one of claims 1 to 16. use.

28. Use for the production of fibers comprising aliphatic polyesters, aliphatic-aromatic polyesters, and mixtures of polyhydroxyalkanoates, The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diol, Preferably, the fiber is as defined in any one of claims 1 to 16. use.

29. A filament suitable for three-dimensional printing, made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diols, filament.

30. The aliphatic polyester is selected from the group consisting of polybutylene succinate (PBS), polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasilate (PBSBr), and any combination thereof. The aliphatic polyester is preferably selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polybutylene succinate-co-azelate (PBSAz), polybutylene succinate-co-brasilate (PBSBr), and any combination thereof. The aliphatic polyester is more preferably polybutylene succinate (PBS), The filament preferably contains 30 to 70% by weight of aliphatic polyester, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The filament according to claim 29.

31. The aliphatic-aromatic polyester is C ２ -C １２ Aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and aliphatic C ２ -C １２ Contains diol, The aliphatic-aromatic polyester is preferably selected from the group consisting of polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate (PBSeT), and any combination thereof. The aliphatic-aromatic polyester is more preferably polybutylene adipate terephthalate (PBAT), The filament preferably contains 10 to 60% by weight of aliphatic-aromatic compounds, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The filament according to claim 29 or 30.

32. The aforementioned polyhydroxyalkanoate is C ３ -C １８ It is a hydroxyalkyl carboxylic acid, The polyhydroxyalkanoate is preferably selected from the group consisting of polyhydroxybutyrate-co-hydroxyhexanoate, polyhydroxybutyrate, polyhydroxyvalerate, polyhydroxybutyrate-co-hydroxyvalerate, and any combination thereof. The polyhydroxyalkanoate is more preferably selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), poly-3-hydroxyvalerate (PHV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and any combination thereof. The polyhydroxyalkanoate is more preferably polyhydroxybutyrate-co-hydroxyhexanoate. The polyhydroxyalkanoate is most preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), The filament contains 1 to 25% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The filament according to any one of claims 29 to 31.

33. Based on a total amount of aliphatic polyesters, aromatic-aliphatic polyesters, and polyhydroxyalkanoates of 100% by weight, the product contains 42-62% by weight of aliphatic polyesters, 26-46% by weight of aromatic-aliphatic polyesters, and 2-22% by weight of polyhydroxyalkanoates. The filament according to any one of claims 29 to 32.

34. The aliphatic polyester is polybutylene succinate (PBS), the aliphatic-aromatic polyester is polybutylene adipate terephthalate (PBAT), and the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH). The filament according to any one of claims 29 to 33.

35. The polyhydroxyalkanoate is partially or entirely substituted with polylactide. The filament according to any one of claims 29 to 34.

36. The filament further comprises at least one additive, preferably comprising a total amount of the additive of 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3-4% by weight, based on 100% by weight of the total weight of the filament. The filament according to any one of claims 29 to 35.

37. The at least one additive is preferably selected from the group consisting of flame retardants, matting agents, fluorescent markers, antibacterial agents, plasticizers, fillers, and any combination thereof. The aforementioned additive is optionally a flame retardant. The flame retardant is preferably ammonium dihydrogen phosphate ([NH ４ ] [H ２ PO ４ ]), diammonium hydrogen phosphate ([NH ４ ] ２ [HPO] ４ ]), triammonium phosphate ([NH ４ ] ３ [PO ４ A phosphate selected from the group consisting of ammonium hydrogen phosphate and any combination thereof, wherein the phosphate is more preferably diammonium hydrogen phosphate ([NH4H4). ４ ] ２ [HPO] ４ ]) and The fiber more preferably contains 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and / or 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the filament, The additive is optionally a matting agent, preferably zinc sulfide, and / or the additive is optionally a fluorescent marker, and / or the additive is optionally an antimicrobial agent, preferably zinc encapsulated in polyethylene terephthalate, and / or the additive is optionally a filler, preferably lignin or containing lignin. The filament according to claim 36.

38. The diameter of the filament is 1.0 mm or more, preferably 1.5 mm or more, more preferably 1.6 mm or more, and even more preferably 1.7 mm or more; and / or, The diameter of the filament is 5.0 mm or less, preferably 4.0 mm or less, more preferably 3.5 mm or less, even more preferably 3.0 mm or less, and / or The diameter of the filament is preferably in the range of 1.70 mm to 1.80 mm, and / or The diameter of the filament is preferably in the range of 2.80 mm to 3.05 mm. The filament according to any one of claims 29 to 37.

39. The filament is biodegradable in accordance with EN13432. The filament according to any one of claims 29 to 38.

40. The aforementioned filament is A method that includes the following steps: - Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and, - Cooling the precursor fibers under a temperature gradient to obtain the fibers; It is possible to obtain by, or not obtain the fibers, and / or The aforementioned filament is A fiber made from a mixture containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, The fiber comprises two types of parts in the longitudinal direction, one of which is a thick part and the other of which is a thin part, and the thick and thin parts extend perpendicular to the longitudinal direction of the fiber, with the extension of the thick part in the perpendicular direction being greater than the extension of the thin part in the perpendicular direction; At least a portion of the thicker portion is hollow, and at least a portion of the thinner portion is not a dense fiber, and / or The filament is not a hollow fiber made from a mixture of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, and / or The aforementioned filament is not a segmented fiber or a segmented hollow fiber. The filament according to any one of claims 29 to 39.

41. A roll comprising the filament according to any one of claims 29 to 40, suitable for three-dimensional printing.

42. A cartridge suitable for a three-dimensional printing printer, comprising a filament according to any one of claims 29 to 40, which is suitable for three-dimensional printing.

43. A three-dimensional printed molded article that can be obtained, or is obtained, by subjecting a filament suitable for three-dimensional printing as described in any one of claims 29 to 40 to three-dimensional printing.

44. Extruding a molten material containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates into a filament shape. Preferably, the temperature of the molten material is in the range of 200°C to 260°C, more preferably in the range of 220°C to 250°C, more preferably in the range of 230°C to 250°C, and even more preferably in the range of 230°C to 240°C. The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diols, A method for preparing a filament suitable for three-dimensional printing according to any one of claims 29 to 40.

45. The molten material contains 30 to 70% by weight of aliphatic polyester, and / or based on a total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate of 100% by weight. The molten material contains 10 to 60% by weight of aliphatic-aromatic compounds, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate, and / or The molten material contains 1 to 25% by weight of polyhydroxyalkanoate, based on 100% by weight of the total amount of aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate. The method according to claim 44.

46. The molten material contains 42 to 62% by weight of aliphatic polyester, 26 to 46% by weight of aromatic-aliphatic polyester, and 2 to 22% by weight of polyhydroxyalkanoate, based on a total amount of aliphatic polyester, aromatic-aliphatic polyester, and polyhydroxyalkanoate of 100% by weight. The method according to claim 44 or 45.

47. The polyhydroxyalkanoate is partially or entirely substituted with polylactide. The method according to any one of claims 44 to 46.

48. The molten material further comprises at least one additive, The total amount of the additive is preferably 15% by weight or less, more preferably 10% by weight or less, more preferably 7% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, and even more preferably 3 to 4% by weight, based on 100% by weight of the total weight of the molten material. The at least one additive is preferably selected from the group consisting of flame retardants, matting agents, fluorescent markers, antibacterial agents, plasticizers, fillers, and any combination thereof. The aforementioned additive is preferably a flame retardant. The molten material more preferably contains 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 2% by weight of a flame retardant, based on 100% by weight of the total weight of the molten material. The method according to any one of claims 44 to 47.

49. - Spinning a molten material containing aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate through a hollow fiber spinning nozzle to obtain precursor fibers; and - Cooling the precursor fibers under a temperature gradient to obtain the fibers, This is not a method for preparing fibers that include The method according to any one of claims 44 to 48.

50. A filament that can be obtained or obtained by the method described in any one of claims 44 to 49.

51. The use of melts containing aliphatic polyesters, aliphatic-aromatic polyesters, and polyhydroxyalkanoates for the preparation of filaments suitable for three-dimensional printing, The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diol, The filament is preferably as defined in any one of claims 29 to 40. use.

52. The use of a mixture comprising aliphatic polyester, aliphatic-aromatic polyester, and polyhydroxyalkanoate for the preparation of filaments suitable for three-dimensional printing, The aliphatic polyester is aliphatic C ２ -C ２０ Dicarboxylic acids and aliphatic C ２ -C １２ Contains diol, The filament is preferably as defined in any one of claims 29 to 40. use.

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