FI130514B - Textile fiber or web, methods and use related thereto - Google Patents

Textile fiber or web, methods and use related thereto Download PDF

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Publication number
FI130514B
FI130514B FI20195904A FI20195904A FI130514B FI 130514 B FI130514 B FI 130514B FI 20195904 A FI20195904 A FI 20195904A FI 20195904 A FI20195904 A FI 20195904A FI 130514 B FI130514 B FI 130514B
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FI
Finland
Prior art keywords
polymer
weight
textile
polybutylene
binary
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FI20195904A
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Finnish (fi)
Swedish (sv)
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FI20195904A1 (en
Inventor
Martta Asikainen
Tommi Vuorinen
Original Assignee
Woodly Oy
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Priority to FI20195904A priority Critical patent/FI130514B/en
Priority to CN202080073595.7A priority patent/CN114630929A/en
Priority to EP20800231.1A priority patent/EP4048830A1/en
Priority to JP2022522370A priority patent/JP2022553170A/en
Priority to PCT/FI2020/050689 priority patent/WO2021079025A1/en
Priority to US17/771,194 priority patent/US20220372664A1/en
Publication of FI20195904A1 publication Critical patent/FI20195904A1/en
Application granted granted Critical
Publication of FI130514B publication Critical patent/FI130514B/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/013—Regenerated cellulose series
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/082—Melt spinning methods of mixed yarn
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/724—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged forming webs during fibre formation, e.g. flash-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D04H3/011—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention concerns a textile fiber or textile web comprising a binary polymer composition, which binary polymer composition comprises a first polymer being cellulose acetate propionate and a second polymer selected from several polymers. Furthermore, a method and use related thereto are described.

Description

TEXTILE FIBER OR WEB, METHODS AND USE RELATED THERETO
TECHNICAL FIELD
The present disclosure relates to synthetic textile fibers and to their manufacturing. Especially, to a textile fiber or textile web comprising a binary polymer composition.
BACKGROUND
There are various methods for producing textile fibers and textile webs.
Fibers are typically manufactured by various spinning methods. Such methods include wet spinning, dry spinning, melt spinning, extrusion spinning, direct spinning, gel spinning and electrospinning. Of these spinning methods, particularly interesting are the ones where no solvents are needed. Solvents in wet spinning for instance are often highly toxic. Melt spinning is one method where no solvents are needed but the polymer is extruded through the spinneret in molten stage and cooled. The polymer can be in different forms before the spinning process: granulate, fluff, fiber, or raw mate- rials ready to be extruded directly into the spinning process.
These fibers can be further converted into yarn and fabric. Textiles are produced for example by weaving
N and knitting yarn made of fibers.
N Nonwovens are manufactured as sheets or webs 3 of directionally of randomly oriented fibers, that have © 30 not been converted into yarns. These fibers can be
I bonded by for example adhesives, thermal methods, sol- * vent treatments or stitching. The processes for produc-
S ing nonwovens differ from those used for spun fibers. o These methods include melt blowing, where the fibrous
S 35 web or article is produced directly from the polymer of resin using high-velocity air. Spunbond nonwovens are made as continuous process where fibers are spun and then dispersed directly to a web. Nonwovens can also be produced from spun fibers, when the fibers are then cut and opened and laid into a web by a multistep process.
US 5939467A discloses biodegradable polymeric compositions that can be melt processed.
JP 2004204217A discloses polylactic resin com- positions.
CN 107794593A discloses blends of thermo- plastic cellulose and aliphatic aromatic copolyesters and fibers made therefrom.
JP 2000129035A discloses a moldable resin com- position.
US 2004030043A1 discloses a cellulose deriva- tive composition and fiber comprising the same.
JP 2007107142A discloses a spun yarn and a fab- ric comprising the same.
US 2002132960A1 discloses copolyesters and fi- brous materials formed therefrom.
WO 2019160906A1 discloses cellulose ester and polymeric aliphatic polyester compositions and arti- cles.
Publication Liang, N.-Y. et al., J. Polym. Rec. 2018, Vol. 25, 88 discusses the effect of a low-molec- ular-weight compatibilizer on the immiscible blends of cellulose acetate propionate and poly (butylene tereph- thalate).
N
N SUMMARY
© = 30 This Summary is provided to introduce a
T selection of concepts in a simplified form that are
E further described below in the Detailed Description. < This Summary is not intended to identify key features 3 or essential features of the claimed subject matter, nor 2 35 is it intended to be used to limit the scope of the
N claimed subject-matter.
The invention concerns a textile fiber or textile web comprising a binary polymer composition, which comprises a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight- %, and a second polymer being polybutylene succinate (PBS), in an amount of 25 to 45 weight-%, and in which the total amount of the first and the second polymer is at least 80 weight-% of the binary polymer composition based on the total weight of the binary polymer compostion.
The invention also concerns a textile material comprising the textile fiber or textile web.
Further, the invention concerns a method for manufacturing a textile fiber or a textile web from a binary polymer composition, which method comprises the following steps: - obtaining a homogenous polymer blend of a binary polymer composition comprising at least a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000
Da, in an amount of 55 to 75 weight-%, and a second polymer being polybutylene succinate (PBS), in an amount of 25 to 45 weight-%, wherein the total amount of the
N first and the second polymer is at least 80 weight-%
N based on the total weight of the binary polymer 3 30 composition, and © a) forming said homogenous polymer blend =E into a textile fiber by a spinning method, or = b) forming said homogenous polymer blend
S into a textile web by a method of producing nonwoven o 35 materials.
S The invention also concerns use of a binary polymer composition comprising a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight-%, and a second polymer being polybutylene succinate (PBS), in an amount of 25 to 45 weight-%, and wherein the total amount of the first and the second polymer is at least 80 weight-% based on the total weight of the binary polymer composition, in the manufacture of a textile fiber, a textile web, and/or a textile material.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawing, which are included to provide a further understanding of the embodiments and constitute a part of this specification, illustrate embodiments. In the drawings:
Fig. 1 illustrates Example 1, Scanning electron microscopy of a binary polymer composition suitable for the invention, made of CAP 72.5 % and PBS 27.5 %.
DETAILED DESCRIPTION
Cellulose derivatives are used in textile fibers, but there are challenges regarding the used processes. Wet spinning and dry spinning processes require the use of toxic solvents. A melt spinning process requires the use of a large amounts of & plasticizers and problems arise with the process
S temperatures. It is of high importance that the breaking © elongation is good, and this is hard to obtain with © 30 fibers from cellulose derivatives.
The present invention provides a solution to i these problems. 3 The present invention is based on the finding
D that new environmentally friendly good quality synthetic > 35 textile fibers and webs can be achieved by a binary polymer composition comprising cellulose acetate propionate (CAP) and a second polymer. The second polymer is polybutylene succinate (PBS), and the binary polymer composition may comprise a polymer selected from the group consisting of polypropylene succinate (PPS), 5 polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyethylene furanoate (PEF), polybutylene terephthalate (PBT), polybutylene succinate terephthalate (PBST), and any polyester containing sebacic and/or azelaic acid and/or dodecanedioic acid as dicarboxylic acid alone or in combination with terephthalic acid, and any combination of these).
Especially, in connection with the present invention it was noticed that CAP and the second polymer, PBS, form a homogeneous polymer mixture, i.e. there is no phase separation between the two polymers when the mixture is prepared with the method disclosed herein. This is illustrated by Figure 1 showing a SEM (Scanning Electron
Microscopy) picture of an embodiment of the invention (Example 1). The binary polymer composition may provide a high quality raw-material for textile fiber and web production, with high tensile strength. Long textile fibers can be formed from strong fibers, and length of the fiber is important to provide good spinning results.
The textile fiber according to the invention is expected
N to have a diameter/bredth ratio of more than 100:1.
N Furthermore, it is expected that the strength, 3 30 uniformity, spinnability and durability of the textile © fibers according to the invention are good. =E Mechanical properties of the binary polymer * composition materials are close to commercial plastics
S used for fiber and nonwoven production. Properties can o 35 also be modified with additives. Processing temperatures
S of over 200°C can be used. All fiber and nonwoven applications can be used where thermoplastic properties are required. The melt flow index (MFI) of the binary polymer blend is also applicable to fiber and nonwoven processes.
The material properties of the binary polymer compositions are similar to those of PET. Also, higher break elongation can be achieved. High break elongation is required for fiber applications and weaving processes.
The binary polymer composition used in textile fiber or web applications can also be a recycled feedstock.
The molecular weight and the length of molecular chains can be chosen to best meet the requirements of each fiber or nonwoven application. The mechanical properties and processability can be modified by choosing longer or shorter polymer chains.
To achieve the desired effect, it is essential that the textile fibers and webs comprise at least two polymers, a first polymer and a second polymer (a binary polymer composition). According to one embodiment of the present invention, the binary polymer composition comprises only two polymers, and optionally additives.
The textile fibers and webs according to this invention can be particulary suitable for replacing textile material made of PET (polyethylene terephthalate).
Syntetic PET fiber is widely used as the
N material in various fiber products. The applications
N include industrial and consumer textiles. The fibers and 3 30 webs according to this invention, may have high © mechanical properties that are needed for high strength =E demanding application like ropes, nets and car textiles. = These are typically made of polyester, and the fibers
S and webs according to the invention would be suitable o 35 for these application as an environmentally friendly
S high-quality alternative. Many types of clothing are produced from polyesters as well as household and furnishing textiles including sheets, carpets and rugs, covers and curtains. Nonwovens, filters and sanitary products are also produced from polyesters. The fibers and webs according to the invention could be suitable for all of the above applications.
PET has relatively high carbon footprint and these types of fibers, webs and textiles are not envi- ronmentally friendly. Typically, PET is mostly made from fossil resources. It is very difficult to make PET prod- ucts more sustainable.
Thus, the present invention describes a new kind of textile fiber and web which may replace for example PET and PP in different types of fibers, yarns, textile and non-woven application. PET materials were used as reference examples in tests performed in con- nection with the present invention (described in more detail in the Examples).
The fibers and webs made of binary polymer compositions presented herein have advantageous properties in tests performed in connection with the present invention.
Especially, the binary polymer composition provides good elongation properties. These are measured with tensile strain tests. In the tests they were compared to PET. Similar PET grades are used in the fiber production as plastic grade PET, this is one of the major recycled PET applications for plastic bottles
N and the like. It hase been shown in tests performed in
N connection with the present invention that the binary 3 30 polymer compositions for textile fiber or textile web © applications may withstand recycling well. =E Also, the materials according to the invention = based on binary polymer compositions presented herein
S can be processed with the same fiber and web production o 35 equipments as used with known material, such as PET
S fibers. This is beneficial, since no large investments in new eguipment is needed.
Furthermore, the fibers and webs made from binary polymer compositions presented herein may have a low environmental impact. This has been shown in tests.
Their global warming potential is much lower, and the renewable content is much higher than those of e.g. PET.
One aim of the invention is to achieve an environmentally friendly textile solution, which could replace traditional synthetic textile materilas based on fossil raw-materials. Thus, biopolymers are preferred in the binary polymer composition.
Biopolymers are polymers which are made, either partially or completely, from renewable resources.
Another definition of biopolymers are polymers which are biodegradable. It is enough for a biopolymer to fulfil one of these definitions.
The invention concerns a textile fiber or textile web comprising a binary polymer composition, which comprises a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-3, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight- %,and a second polymer being polybutylene succinate (PBS) in an amount of 25 to 45 weight-%, and the total amount of said first and said second polymer is at least 80 weight-% based on the total weight of said binary polymer composition. The binary polymer compsition may further comprise a polymer selected from the group
N consisting of polybutylene succinate (PBS),
N polypropylene succinate (PPS), polybutylene succinate 3 30 adipate (PBSA), polybutylene adipate terephthalate © (PBAT), polylactic acid (PLA), polycaprolactone (PCL),
I polybutylene adipate (PBA), polyhydroxyalkanoate (PHA), * polyhydroxybutyrate (PHB), polyethylene furanoate
S (PEF), polybutylene terephthalate (PBT), polybutylene o 35 succinate terephthalate (PBST), and any polyester
S containing sebacic and/or azelaic acid and/or dodecanedioic acid as dicarboxylic acid alone or in combination with terephthalic acid, and any combination of these. The total amount of the first and the second polymer is at least 80 weight-% of the binary polymer composition based on the total weight of the binary polymer compostion.
According to an embodiment of the invention, the total amount of the first polymer and said second polymer it at least 80 wt.%. Typically, the amount is at least 90 wt.%, or at least 95 wt.%, based on the total weight of the binary polymer composition the rest being other polymers and/or additives such as softeners, pigments, stabilizers or other additives for use in plastic compositions.
According to an embodiment of the invention, the binary polymer composition comprises the first polymer in an amount of 60 to 75 weight-%, or 65 to 75 weight-%, and the second polymer in an amount of 25 to 40 weight-%, or 25 to 35 weight-%.
According to an embodiment of the invention, the binary polymer composition comprises recycled binary polymer composition comprising cellulose acetate propionate (CAP) and polybutylene succinate (PBS).
The invention also concerns a textile material comprising the textile fiber or textile web according to any embodiment described herein.
According to an embodiment of the invention, the textile material is selected from the group & consisting of a fiber, a varn, textiles, fabrics,
N nonwovens, textile products for one of the following 3 30 applications; apparel, household, industrial, © technical, ropes, nets and car textiles, household and =E furnishing textiles including sheets, carpets and rugs, > covers and curtains, and nonwovens, such as filters and
S sanitary products. o 35 According to an embodiment of the invention,
S the textile material is recyclable.
Further, the invention relates to a method for manufacturing a textile fiber or a textile web from a binary polymer composition. The method of the invention comprises the following steps: - obtaining a homogenous polymer blend of a binary polymer composition comprising at least a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight-%, and a second polymer being polybutylene succinate (PBS) in an amount of 25 to 45 weight-%, and wherein the total amount of said first and said second polymer is at least 80 weight-% based on the total weight of said binary polymer compostion, and a) forming said homogenous polymer blend into a textile fiber by a spinning method, or b) forming said homogenous polymer blend into a textile web by a method of producing nonwoven materials.
According to one embodiment the binary polymer composition comprises a polymer selected from the group consisting of polybutylene succinate (PBS), polypropylene succinate (PPS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), polyhydroxyalkanoate (PHA),
N polyhydroxybutyrate (PHB), polyethylene furanoate
N (PEF), polybutylene terephthalate (PBT), polybutylene 3 30 succinate terephthalate (PBST), and any polyester © containing sebacic and/or azelaic acid and/or
Ek dodecanedioic acid as dicarboxylic acid alone or in = combination with terephthalic acid, and any combination 5 of these). | | NU
O 35 According to one embodiment, obtaining a
S homogenous polymer blend is not performed in a separate step, but rather in the same step as forming the blend into a textile fiber or textile web.
According to an embodiment of the invention, the method of forming the homogenous polymer blend into a textile fiber is done by a spinning method selected from the group consisting of wet spinning, dry spinning, melt spinning, extrusion spinning, direct spinning, gel spinning and electrospinning. Preferably, melt spinning and/or direct spinning are used.
According to an embodiment of the invention, forming said homogenous polymer blend into a textile web is done by melt blow and/or spunbond.
According to an embodiment of the invention, obtaining the homogenous polymer blend is performed by melt-mixing. The melt-mixing is performed at a temperature between 200°C and 300°C. Preferably the temperature is between 200°C and 270°C, or between 210°C and 250°C, or between 210°C and 230°C.
According to an embodiment of the invention, obtaining a homogenous polymer blend is done by a recycling process.
The method may be used to obtain a textile fiber or a textile web based on a binary polymer composition according to any one of the embodiments described herein.
The invention also concerns use of a binary polymer composition comprising a first polymer being & cellulose acetate propionate (CAP), with a propionyl
N content of 30 to 51 weight-%, and a number average molar 3 30 mass of between 85,000 and 95,000 Da, in an amount of © 55 to 75 weight-%, and a second polymer being
Ek polybutylene succinate (PBS) in an amount of 25 to 45 * weight-%, and wherein the total amount of said first and
S said second polymer is at least 80 weight-% based on the o 35 total weight of said binary polymer compostion, in the
S manufacture of a textile fiber, a textile web, and/or a textile material.
According to one embodiment, the binary polymer composition comprises a polymer selected from the group consisting of polybutylene succinate (PBS), polypropylene succinate (PPS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyethylene furanoate (PEF), polybutylene terephthalate (PBT), polybutylene succinate terephthalate (PBST), and any polyester containing sebacic and/or azelaic acid and/or dodecanedioic acid as dicarboxylic acid alone or in combination with terephthalic acid, and any combination of these).
According to one embodiment, PBS is used, and the PBS has a number average molar mass in the range of 30,000 to 100,000 Da. Typically, 50,000 to 80,000 Da, or for example 60,000 to 70,000 Da.
According to one very specific embodiment, the binary polymer composition comprises CAP in an amount of 60 to 75 weight-%, or 65 to 75 weight-%. The compo- sition then comprises the second polymer in an amount of 25 to 40 weight-%, or 25 to 35 weight-%. Weight-%:s are based on the total weight of the composition. Op- tionally, the mixture comprises at least one additive such as softeners, pigments, stabilizers and/or other
N additives for use in plastic compositions.
N According to one very specific embodiment, the 3 30 binary polymer composition consists of CAP in an amount © of 60 to 75 weight-%, or 65 to 75 weight-%, and PBS in
Ek an amount of 25 to 40 weight-% or 25 to 35 weight-%, = based on the total weight of the composition, and op-
S tionally at least one additive, such as softeners, pig- o 35 ments, dyes, stabilizers and/or other additives for use
S in plastic compositions, and/or other thermoplastic pol- ymers compatible with CAP and PBS.
According to one embodiment, the binary polymer composition comprises at least one softener. For exam- ple, triethyl citrate (TEC).
According to one specific embodiment, CAP has an acetyl content of 0.8 to 2.0 wt.%, or 1.0 to 1.5 wt.%, and/or a propionyl content of 30 to 51 wt.%, or 40 to 50 wt.%, and/or a hydroxyl content of 1.0 to 2.5 wt.%, or 1.5 to 2.0 wt.%.
Suitably, if CAP is used, the number average molar mass of the CAP polymer is above 20,000 Da. Ac- cording to one embodiment, the number average molar mass is between 85,000 and 95,000 Da, or between 85,000 and 91,000 Da, for example 90,000 Da, 91,000 Da or 92,000
Da. A number average molar mass within the above defined ranges may provide a resilient material with mechanical properties that withstand processing and form durable textile fibers.
All number average molar mass measurements per- formed in connection with the invention were measured with size exclusion chromatography (SEC) using chloro- form eluent for the number average molar mass measure- ments. The SFC measurements were performed in chloro- form eluent (0.6 ml/min, T=30 °C) using Styragel HR 4 and 3 columns with a pre-column. The elution curves were detected using Waters 2414 Refractive index detector.
The molar mass distributions (MMD) were calculated against 10 x PS (580 —- 3040000 g/mol) standards, using & Waters Empower 3 software.
N Different grades of cellulose esters, such as 3 30 cellulose acetate propionate, are commercially availa- © ble from several suppliers. In the disclosed binary pol- =E ymer composition, the polymer raw materials affect the * properties of the formed mixture. In other words, the
S combined properties of the polymers need to be evaluated o 35 when forming the composition according to the invention.
S For example, if one of the polymers has a high number average molar mass, such as 90,000 Da or 70,000 Da, it could be suitable to combine this polymer with another polymer having a lower number average molar mass. Al- ternatively, or additionally, a higher amount of sof- tener may be used together with polymers with a high molar mass. The suitable number average molar mass de- pends on the end use of the composition, i.e. the most suitable cellulose ester grade may be different depend- ing on the intended end use. Cellulose esters may have different grades of substitution. The CAP suitable for the composition of the present invention suitably has an acetyl content of 0.8 to 2.0 wt.%. Typically, 1.0 to 1.5 wt.%, for example 1.3 wt.%. The CAP suitable for the composition of the present invention suitably has a pro- pionyl content of 30 to 51 wt.%. Typically, it may be 40 to 50 wt.%. A very specific example is 48 wt.%. The
CAP suitable for the composition of the present inven- tion suitably has hydroxyl content of 1.0 to 2.5 wt.%.
Typically, 1.5 to 2.0 wt.%, for example 1.7 wt.%. In addition, the glass transition temperature is suitably 140 to 155 °C. Typically, 142 to 152 °C, for example 147 °C.
According to one embodiment, if PBS is used, the PBS suitable for the composition of the present invention has a number average molar mass in the range of 30,000 to 100,000 Da. Typically, 50,000 to 80,000 Da; or 60,000 to 70,000 Da. The number average molar mass of the PBS may be for example 65,000 to 70,000 Da, such
AN as for example 68,000 Da, 69,000 Da or 70,000 Da.
N Melt flow index (or melt flow rate) is a meas- 3 30 ure to describe ease of flow of the melt of a thermo- © plastic polymer or plastic. The melt flow index can be
I used to characterize a polymer or a polymer mixture. For = polyolefins, i.e. polyethylene (PE, at 190 °C) and pol-
S ypropylene (PP, at 230 *C) the MFI is commonly used to o 35 indicate order of magnitude for its melt viscosity. In
S standardized MFI measuring instrument a constant pres- sure generates shear stress which pushes melt plastic through a die. Typically, MFI is inversely proportional to molecular weight. For an embodiment of the binary polymer composition tested in connection with the in- vention the MFI was measured at two temperatures 215 and 240 °C. According to one very specific embodiment, the binary polymer composition has a melt flow index of 6 to 8 g/10 min. Suitably, about 7 g/10 min, or 6.9 g/10 min. Measured at: load 2.16 kg, at 215 °C, and/ or about 26 to 28 g/10 min, 27 g/10 min, or 27.1 g/10 min, load 2.16 kg, at 240 °C.
According to one embodiment, the binary polymer composition suitable for the solution according to the invention comprises CAP and the second polymer, PBS, in combination with another component, which is selected from the list consisting of a cellulose ester, such as cellulose acetate or cellulose acetate butyrate (CAB), and polybutylene succinate (PBS), polypropylene succin- ate (PPS), polybutylene succinate adipate (PBSA), poly- butylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyethylene furanoate (PEF), polybutylene ter- ephthalate (PBT), polybutylene succinate terephthalate (PBST), and any polyester containing sebacic and/or azelaic acid and/or dodecanedioic acid as dicarboxylic acid alone or in combination with terephthalic acid, and any combination of these. According to one embodiment, & the binary polymer composition comprises also other sim-
N ilar polymers, which are compatible with CAP and the 3 30 second polymer, such as PBS. © The elongation and other mechanical properties =E of the binary polymer compositions can also be modified = with small amounts of additives to reach the elongation
S and other properties required. Thus, thee binary polymer o 35 composition may also comprise other components, such as
S additives typically used in textile fibers or textile webs. These additives are for example softeners or plas- ticizers, fillers, aids, pigments, stabilizers or other agents. Typically, the amounts of these additives vary between 0.01 to 10 weight-% based on the weight of the binary polymer composition used in the invention. The amount of one additive may for example be 0.1 to 5 weight-% based on the total weight of the composition.
The solution according to the present invention has several advantages. The most important are: - Providing an environmentally friendly synthetic textile material, manufactured from biopolymers, and which is a high- quality material suitable for replacing conventional textile materials. - Providing a solution where the manufacturing processes of cellulose based textile fibers or textile webs do not require the use of large amounts of toxic solvents, or a large amount of plasticizers. - In addition, the material can be made out of food-grade materials, which means that they can be used for food/medical products.
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EXAMPLES
Reference will now be made in detail to various embodiments, an example of which is illustrated in the accompanying drawing.
The description below discloses some embodiments in such a detail that a person skilled in the art is able to utilize the embodiments based on the disclosure. Not all steps or features of the embodiments are discussed in detail, as many of the steps or features will be obvious for the person skilled in the art based on this specification.
For reasons of simplicity, item numbers will be maintained in the following exemplary embodiments in the case of repeating components.
Fig. 1 illustrates Example 1, Scanning electron microscopy of a binary polymer composition suitable for the invention, made of CAP 72.5 % and PBS 27.5 %.
The following raw materials have been used in the
Examples; properites are indentified in Table 1 to Table 3.
Table 1: Cellulose acetate propionate (CAP)
Entry Compound |Mn g/mol |Mw g/mol Eluent/
HPSEC system 1 CAP 90,000 221,000 2.5 Chloro- form
S 25 Cellulose acetate propionate had degree of substitu-
S tion of: © - acetyl content 1.2 wt % © - propionyl content 48 wt %
T - hydroxyl content 1.7 wt %
E 30 jami a + Table 2: Polybutylene succinate (PBS)
S Entry Compound |Mn g/mol |Mw g/mol Eluent/ 8 HPSEC
O system
N 1 PBS 76,000 215,000 2.8 Chloro- form
The number average molar mass measurements (Mn) were performed with size exclusion chromatography (SEC) us- ing chloroform eluent for the number average molar mass measurements, the samples (Entries 1 to 4), were dissolved overnight using chloroform (concentration of 1 mg/ml). Samples were filtered (0.45 um) before the measurement.
The SEC measurements were performed in chloroform elu- ent (0.6 ml/min, T=30 °C) using Styragel HR 4 and 3 columns with a pre-column. The elution curves were de- tected using Waters 2414 Refractive index detector.
The molar mass distributions (MMD) were calculated against 10 x PS (580 — 3,040,000 g/mol) standards, us- ing Waters Empower 3 software.
Table 3: Tg values of used raw materials.
Example 1: Production and properties of binary polymer mixtures
Homogeneous mixtures of a binary polymer composition were formed into granulate and films. n Homogeneous polymer mixtures were obtained by melt
N mixing. The mixing was conducted at temperatures between > 210-230°C for a time period of 30 sec to 4 min.
TF The binary polymer blend consisting of 72.5 % e 30 CAP and 27.5 % of PBS was made into a film. The film was
E treated with liquid nitrogen. The samples were broken < under liquid nitrogen to give perfect cross-section view 3 into the film. The SEM cross-section views did not show
D any fine structure and is homogeneous showing excellent
N 35 miscibility of the polymer blend (Figure 1).
Particularly important is the breaking elongation of the material. The elongation is also called tensile strain.
This can be measured for yield and for break. The elongation at break for the binary polymer blend is measured to be upto 97%.
Table 4: mechanical properties of binary polymer mixture film of 40 pm (SFS-FN ISO 527-3/2/100)
Entry CAP PBS Tensile | Tensile | Tensile | Tensile stress strain stress strain at at at at yield yield break break (MPa) (5) (MPa) (5)
Table 5: mechanical properties of PET film of thickness 300 um (EN ISO 527-3)
Entry Polymer Tensile Tensile Tensile stress strain strain maximum at maxi- | at break load mum load (%) (MPa) (5)
Table 6: mechanical properties of binary polymer mixture film of thickness 300 pm (EN ISO 527-3)
Entry CAP PBS Addi- Tensile | Tensile | Tensile tive stress strain strain at at at yield yield break (MPa) (5) (5) [essere 8 |] [35.8 ja [44.0
N
S
N
2 In film applications, the elongation
O properties are much higher with the binary polymer r 20 mixtures than with the PET films. Similar PET grades are
T a used in the fiber production than plastic grade PET,
S this is one of the major recycled PET applications for 8 plastic bottles and the like.
O
N
The MFI (melt flow index) of the binary polymer blends is suitable for fiber production at different temperatures.
Table 7: MFI of binary polymer mixtures
Kg
Example 2: Production of fibers from binary polymer mixtures
Based on test done to evaluate the properties of the raw material (Example 1), it is expected that a binary polymer composition comprising CAP and PRS can be processed into fibers with various methods.
According to one alternative, a melt-spund fiber could be manufactures.
For the production of melt-spun filaments of fibers with binary polymer compositions comprising CAP and PBS, a ready compounded binary polymer could be used and fed to the spinning process. Alternatively, feeding the CAP and PBS polymers separately directly into the spinning process could be done.
The products based on a melt-spun process are fibres, from which different fiber and yarn products can & 25 be made. The yarn can also be woven or knitted into
N textiles and fabrics for various applications. = 2 Fxample 3: Production of nonwoves from binary = polymer mixtures - 30
S Based on test done to evaluate the properties o of the raw material (Example 1), it is expected that a a binary polymer composition comprising CAP and PBS can be processed into nonwovens with the at least the following methods; melt blown process and a spunbond process.
A ready compounded binary polymer could be used and fed to the web forming process. Alternatively, feeding the CAP and PBS polymers separately directly into the process.
The products and finished articles from a melt blown process and a spunbond process are nonwoven textiles.
KK KKK
It is obvious to a person skilled in the art that with the advancement of technology, the basic idea may be implemented in various ways. The embodiments are thus not limited to the examples described above; instead they may vary within the scope of the claims.
The embodiments described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined together to form a further embodiment. A product, a system, a method, or a use, disclosed herein, may comprise at least one of the embodiments described hereinbefore. It will be understood that the benefits and advantages described above may relate to one embodiment or may relate to several embodiments. The embodiments are not limited to those that solve any or all of the stated problems
N or those that have any or all of the stated benefits and
N advantages. It will further be understood that 3 30 reference to 'an' item refers to one or more of those © items. The term “comprising” is used in this =E specification to mean including the feature(s) or act (s) = followed thereafter, without excluding the presence of
S one or more additional features or acts. o 35 &

Claims (17)

1. A textile fiber or textile web comprising a binary polymer composition, characterized in that the binary polymer composition comprises a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight-%, and a second polymer being polybutylene succinate (PBS) in an amount of 25 to 45 weight-%, and the total amount of said first and said second polymer is at least 80 weight-% based on the total weight of said binary polymer composition.
2. The textile fiber or textile web according to claim 1, characterized in that the binary polymer composition comprises a polymer selected from the group consisting of polypropylene succinate (PPS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyethylene furanoate (PEF), polybutylene terephthalate (PBT), polybutylene succinate terephthalate (PBST), and any polyester containing sebacic and/or azelaic acid and/or dodecanedioic acid as dicarboxylic acid alone or in combination with terephthalic acid, and any combination of these.
n 3. The textile fiber or textile web according S to any one of the preceding claims, characterized in b that the total amount of said first polymer and said 7 30 second polymer is at least 80 wt.%, or at least 90 wt.%, A or at least 95 wt.%, based on the total weight of the E binary polymer composition, the rest being other < polymers and/or additives such as softeners, pigments, 3 stabilizers or other additives for use in plastic 2 35 compositions.
N 4. The textile fiber or textile web according to any one of the preceding claims, characterized in that said binary polymer composition comprises the first polymer in an amount of 60 to 75 weight-%, or 65 to 75 weight-%, and said second polymer in an amount of 25 to 40 weight-%, or 25 to 35 weight-%.
5. The textile fiber or textile web according to any one of the preceding claims, characterized in that the second polymer is PBS.
6. The textile fiber or textile web according to any one of the preceding claims, characterized in that it comprises recycled binary polymer composition comprising cellulose acetate propionate (CAP) and polybutylene succinate (PBS).
7. A textile material comprising the textile fiber or textile web according to any one of the claims 1 to 6.
8. The textile material according to claim 7, characterized in that it is selected from the group consisting of a fiber, a varn, textiles, fabrics, nonwovens, textile products for one of the following applications; apparel, household, industrial, technical, ropes, nets and car textiles, household and furnishing textiles including sheets, carpets and rugs, covers and curtains, and nonwovens, such as filters and sanitary products.
9. The textile material according to claim 7 or 8, characterized in that it is recyclable.
10. A method for manufacturing a textile fiber & or a textile web from a binary polymer composition, N characterized in that the method comprises the following 3 30 steps: © - obtaining a homogenous polymer blend of a =E binary polymer composition comprising at * least a first polymer being cellulose S acetate propionate (CAP), with a propionyl o 35 content of 30 to 51 weight-%, and a number S average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight-
%, and a second polymer being polybutylene succinate (PBS) in an amount of 25 to 45 weight-%, and the total amount of said first and said second polymer is at least 80 weight-% based on the total weight of said binary polymer composition, and a) forming said homogenous polymer blend into a textile fiber by a spinning method, or b) forming said homogenous polymer blend into a textile web by a method of producing nonwoven materials.
11. The method according to claim 10, characterized in that forming said homogenous polymer blend into a textile fiber is done by a spinning method selected from the group consisting of wet spinning, dry spinning, melt spinning, extrusion spinning, direct spinning, gel spinning and electrospinning, preferably melt spinning and/or direct spinning.
12. The method according to claim 10 or 11, characterized in that the binary polymer composition comprises a polymer selected from the group consisting of polypropylene succinate (PPS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene adipate (PBA), N polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), N polyethylene furanoate (PEF), polybutylene 3 30 terephthalate (PBT), polybutylene succinate © terephthalate (PBST), and any polyester containing Ek sebacic and/or azelaic acid and/or dodecanedioic acid * as dicarboxylic acid alone or in combination with S terephthalic acid, and any combination of these. o 35
13. The method according to claim 10, 11 or 12, S characterized in that forming said homogenous polymer blend into a textile web is done by melt blow and/or spunbond.
14. The method according to any of the claims 10 to 13, characterized in that obtaining the homogenous polymer blend is performed by melt-mixing and the melt- mixing is performed at a temperature between 200°C and 300°C, or between 200°C and 270°C, or between 210°C and 250°C, or between 210°C and 230°C.
15. The method according to claim any one of the claims 10 to 14, characterized in that obtaining a homogenous polymer blend is done by a recycling process.
16. Use of a binary polymer composition comprising a first polymer being cellulose acetate propionate (CAP), with a propionyl content of 30 to 51 weight-%, and a number average molar mass of between 85,000 and 95,000 Da, in an amount of 55 to 75 weight- %, and a second polymer being polybutylene succinate (PBS) in an amount of 25 to 45 weight-%, and wherein the total amount of said first and said second polymer is at least 80 weight-% based on the total weight of said binary polymer compostion, in the manufacture of a textile fiber, a textile web, and/or a textile material, or any combination of these.
17. The use according to claim 16, wherein the binary polymer composition comprises a polymer selected from the group consisting of polypropylene succinate (PPS), polybutylene succinate adipate (PBSA), N polybutylene adipate terephthalate (PBAT), polylactic N acid (PLA), polycaprolactone (PCL), polybutylene 3 30 adipate (PBA), polyhydroxyalkanoate (PHA), © polyhydroxybutyrate (PHB), polyethylene furanoate Ek (PEF), polybutylene terephthalate (PBT), polybutylene * succinate terephthalate (PBST), and any polyester S containing sebacic and/or azelaic acid and/or o 35 dodecanedioic acid as dicarboxylic acid alone or in S combination with terephthalic acid, and any combination of these.
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