EP4673594A1 - Yarns useful in arc, cut, heat & flame-resistant fabrics and articles comprising the same - Google Patents
Yarns useful in arc, cut, heat & flame-resistant fabrics and articles comprising the sameInfo
- Publication number
- EP4673594A1 EP4673594A1 EP23924525.1A EP23924525A EP4673594A1 EP 4673594 A1 EP4673594 A1 EP 4673594A1 EP 23924525 A EP23924525 A EP 23924525A EP 4673594 A1 EP4673594 A1 EP 4673594A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- yarn
- ply
- cut
- aramid
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
- D02G3/28—Doubled, plied, or cabled threads
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/16—Yarns or threads made from mineral substances
- D02G3/18—Yarns or threads made from mineral substances from glass or the like
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
- D02G3/328—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic containing elastane
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/36—Cored or coated yarns or threads
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/442—Cut or abrasion resistant yarns or threads
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
Definitions
- This invention relates to yarns and fabrics suitable for use in articles of protective apparels that have arc-resistant, cut-resistant, heat-resistant and flame-resistant properties. Particularly, this invention relates to ply-twisted yarn for use in arc, cut, heat and flame protection articles.
- Gloves/sleeves made with DuPont fiber only can provide medium cut &heat /flame protection but very marginal arc protection.
- Glove/sleeves made with generic aramid /glass/modacrylic blends CANNOT provide either consistent high cut &arc rating performance or good dexterity /comfort.
- Yarns comprising modacrylic fiber, p-aramid fiber, and m-aramid fiber that are useful for the production of fabrics which possess arc and flame protective properties are disclosed, for example, in U.S. Pat. Nos. 7,065,950 and 7,348,059. These yarns may further comprise, as an optional component, 2 to 15 weight percent of an abrasion –resistant fiber such as nylon and/or 1 to 5 weight percent of an antistatic component.
- an abrasion –resistant fiber such as nylon and/or 1 to 5 weight percent of an antistatic component.
- a ply-twisted yarn suitable for used in a flame-retardant, cut-resistant fabric is disclosed, for example in US 2022/0325443 A1.
- the ply -twisted yarn comprises (a) at least one first yarn comprising at least 50 weight percent heat -resistant polymeric fiber, wherein at least 30 weight percent of the polymeric fiber present in the at least one first yarn is cut -resistant heat –resistant polymeric fiber having a cut resistance of 500 grams force or higher per ASTM F2992-15 ; and (b) at least one second yarn having a sheath/core construction with a sheath of halogenated self-extinguishing staple fibers and a core comprising at least one continuous elastic filament.
- Glove or sleeve or clothing made with innovated yarn could effectively protect workers from being harmed from the mentioned multiple hazards with an integrated technical solution.
- This invention relates to yarns and fabrics suitable for use in articles of protective apparels that have arc-resistant, cut-resistant, heat-resistant and flame-resistant properties.
- an innovated ply-twisted yarn can provide the mentioned overall protections against arc-, cut-, heat-and flame-hazards; in which this ply-twisted yarn comprises:
- a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn;
- a third yarn comprising cut, heat and flame-resistant polymeric fibers.
- This invention also relates to a woven or knitted fabric comprising the ply-twisted yarn of the invention.
- This invention also relates to an article comprising the woven or knitted fabric of the invention.
- This invention relates to yarns and fabrics, suitable for use in articles of protective apparels that have arc-resistant, heat-resistant and flame-resistant properties, and additionally provide cut protection.
- the unique combination is created by ply-twisted yarn comprising at least two yarns having sheath/core construction and a further yarn having non-sheath/core construction.
- this invention relates to a ply-twisted yarn suitable for use in arc, cut, heat and flame protection articles, the ply-twisted yarn comprising:
- a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn;
- the ply-twisted yarn of this invention is made by twisting together individual single yarns. It is well known in the art to twist single yarns together to make ply-twisted yarns.
- twisting together individual single yarns it is meant the individual single yarns are twisted together without one yarn fully covering any of the others. This distinguishes ply-twisted yarns from covered or wrapped yarns where a single yarn is completely wrapped around another single yarn so that the surface of the resulting ply-twisted yarn only exposes the first single yarn.
- the ply-twisted yarns of this invention are made up of at least three different single yarns. More preferably, the ply-twisted yarns of this invention are made up of three different single yarns.
- the first yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers.
- the first yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath made from cut, heat and flame resistant polymeric fibers.
- the second yarn is a yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers.
- the second yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath made from cut, heat and flame resistant polymeric fibers.
- the third yarn is a yarn comprising cut, heat and flame resistant polymeric fibers.
- the third yarn is a yarn made from cut, heat and flame resistant polymeric fibers.
- a sheath/core construction is used so that because the sheath fibers cover and shield the core filament from direct contact with other materials, which also may give fabrics containing the yarn improved performance.
- the sheath fiber can be wrapped or spun around the core fiber.
- core fiber can be wrapped or spun around the core fiber.
- conventional ring spinning including improvements to the conventional process such as those utilizing COTSON technology; core-spun spinning such as DREF spinning; air-jet spinning using so-called core insertion with Murata (now Muratec) jet-like spinning; open-end spinning, vortex spinning and the like.
- core-spun spinning such as DREF spinning
- open-end spinning vortex spinning and the like.
- the sheath fiber is consolidated around the core filament at a density sufficient to cover the core filament. The degree of coverage depends on the process used to spin the yarn; for example, core-spun spinning such as DREF spinning (disclosed, for example, in U.S. Patent Nos.
- continuous glass filament is used as the core of the first yarn; for example 240 dtex (220 denier) glass filament.
- Glass filament is an inorganic nonmetallic material with excellent performances, with the advantages of good insulation, strong heat resistance, good corrosion resistance and high mechanical strength. It is usually made from pyrophyllite, quartz sand, limestone, dolomite, boracite, and brucite as raw materials through high-temperature melting, drawing, and other processes.
- the diameter of glass filament is from several microns to more than 20 microns, and each bundle of fiber precursor is composed of hundreds or even thousands of monofilaments. Glass fiber can be used in fabrics or textile to improve its strength, flame retardance and, especially, cutting performance.
- a number of commercially available glass filament can be used in the present invention without specific limitation; for example, those commercially available as SC8-24 ⁇ 1Z55 FE-5 from Sinoma.
- the first yarn comprises, based on the weight of the first yarn, at least 30%by weight of glass filament; more specifically, from 30 to 50%by weight of glass filament; more preferably, from 35 to 45%by weight of glass filament.
- continuous elastic glass filament is used as the core of the second yarn.
- Continuous elastic filament as used herein means a core formed from elastomer material, the core preferably having the ability to return to its original length rapidly after repeated stretching, even to at least twice its original length.
- Preferred elastic core include polyurethane based yarns such as Spandex or Elastane filament; Suitable well-known elastic yarns also include the products sold under the trade name of Lycra.
- the preferred at least one continuous elastic filament is spandex fiber.
- spandex fiber has its usual definition, that is, a manufactured fiber in which the fiber-forming substance is a long chain synthetic polymer composed of at least 85 %by weight of a segmented polyurethane.
- segmented polyurethanes of the spandex type are those described in, for example, U.S. Pat. Nos. 2,929,801; 2,929,802; 2,929,803; 2,929,804; 2,953,839; 2,957,852; 2,962,470; 2,999,839; and 3,009,901.
- the elastic filament of the second yarn is stretched.
- Typical stretch ratios are 1.5 to 5.0 with 1.5 to 3.50 being preferred, and 3.2 being most preferred.
- Low stretch ratios yield less elastic recovery while very high stretch ratios make the single yarns difficult to process and the fabric too tight and uncomfortable.
- the second yarn comprises, based on the weight of the second yarn, at most 15%by weight of elastic filament; preferably, from 10 to 15%by weight of elastic filament; more preferably, from 12 to 14%by weight of elastic filament.
- the cut, heat and flame resistant polymeric fibers used therein include para-aramid, meta-aramid, modacrylic, FR-treated rayon, FR-treat cotton, polybenzoxazole, polybenzimidazole, pre-oxidized fiber, or mixtures thereof.
- the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from para-aramid, meta-aramid, modacrylic, FR-treated rayon, FR-treat cotton, polybenzoxazole, polybenzimidazole and pre-oxidized fibers. More preferably, the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from para-aramid, meta-aramid and modacrylic fibers.
- modified fiber acrylic synthetic fiber made from a polymer comprising primarily acrylonitrile.
- the polymer is a copolymer comprising 30 to 70 weight percent of a acrylonitrile and 70 to 30 weight percent of a halogen-containing vinyl monomer.
- the halogen-containing vinyl monomer is at least one monomer selected, for example, from vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, etc.
- copolymerizable vinyl monomers are acrylic acid, methacrylic acid, salts or esters of such acids, acrylamide, methylacrylamide, vinyl acetate, etc.
- the preferred modacrylic fibers of this invention are copolymers of acrylonitrile combined with vinylidene chloride, the copolymer having in addition an antimony oxide or antimony oxides for improved fire retardancy.
- Such useful modacrylic fibers include, but are not limited to, fibers disclosed in U.S. Pat. No. 3,193,602 having 2 weight percent antimony trioxide, fibers disclosed in U.S. Pat. No. 3,748,302 made with various antimony oxides that are present in an amount of at least 2 weight percent and preferably not greater than 8 weight percent, and fibers disclosed in U.S. Pat. Nos. 5,208,105 &5,506,042 having 8 to 40 weight percent of an antimony compound.
- modacrylic fiber includes, for example, A from Kaneka Corporation, Japan.
- aramid is meant a polyamide wherein at least 85%of the amide (-CONH-) linkages are attached directly to two aromatic rings. Additives can be used with the aramid and, in fact, it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid.
- Suitable aramid fibers are described in Man-Made Fibers-Science and Technology, Volume 2, Section titled Fiber-Forming Aromatic Polyamides, page 297, W.Black et al., Interscience Publishers, 1968.
- Aramid fibers are, also, disclosed in U.S. Pat. Nos. 4,172,938; 3,869,429; 3,819,587; 3,673,143; 3,354,127; and 3,094,511.
- M-aramids are those aramids where the amide linkages are in the meta-position relative to each other, and p-aramids are those aramids where the amide linkages are in the para-position relative to each other.
- the aramid as most often used are poly (para-phenylene terephthalamide) , i.e., meta-aramid or p-aramid; and poly (meta-phenylene isophthalamide) , i.e., meta-aramid, or m-aramid.
- M-aramid fiber provides additional tensile strength to the yarn and fabrics formed from the yam.
- Modacrylic and m-aramid fiber combinations are highly flame resistant but do not provide adequate tensile strength to a yarn or fabric made from the yam to offer the desired level of breakopen resistance when exposed to an electrical arc.
- p-aramid fibers provide a high tensile strength fiber which when added in adequate amounts improves the breakopen resistance of fabrics formed from the yam. Large amounts of p-aramid fibers in the yams make garments comprising the yarns uncomfortable to the wearer.
- aramid fibers for example, comprise K series from DuPont Corporation, the U.S.A. as p-aramid fibers, and N series from DuPont Corporation, the U.S.A. as m-aramid fibers.
- the cut, heat and flame resistant polymeric fibers in the first yarn are 20%to 40%by weight of para-aramid and 20%to 40%by weight of modacrylic, more preferably, 25%to 35%by weight of para-aramid and 25%to 35%by weight of Modacrylic, calculated based on the total weight of the first yarn; and the remaining of the first yarn is the core material of glass filament; which is, at least 30%by weight of the total weight of second yarn.
- the cut, heat and flame resistant polymeric fibers in the second and third yarns are para-aramid, meta-aramid and modacrylic.
- the cut, heat and flame resistant polymeric fibers in the second yarn are 30%to 50%by weight of para-aramid, 0%to 35%by weight of meta-aramid, and 20%to 55%by weight modacrylic, more preferably, 33%to 40%by weight of para-aramid, 20%to 35%by weight of meta-aramid, and 25%to 55%by weight of modacrylic, calculated based on the total weight of sum of the cut, heat and flame resistant polymeric fibers in the second yarn; and the remaining of the second yarn is the core material of elastic filament; which is, at most 15%by weight of the total weight of second yarn.
- the cut, heat and flame resistant polymeric fibers of the third yarn are 30%to 50%by weight of para-aramid, 0%to 40%by weight of meta-aramid, and 20%to 65%by weight modacrylic; more preferably, 35%to 45%by weight of para-aramid, 25%to 35%by weight of meta-aramid, and 30%to 60%by weight of modacrylic, calculated based on the total weight of the third yarn.
- Woven and/or knit fabric can comprise the ply twisted yarns described herein.
- the preferred fabric is a knit fabric, and any appropriate knit pattern is acceptable.
- Articles can comprise the ply -twisted yarns described herein or articles can be made from the aforementioned fabrics comprising the ply-twisted yarns described herein.
- Especially useful articles include gloves, sleeves, and aprons.
- test specimens are knit fabrics manufactured preferred by a 13G knitting machine.
- Cut resistance performance is determined according to ANSI/ISEA 105-2016 “American National Standard For Hand Protection Classification” , specifically the requirements outlined in section of 5.1.1. When tested in accordance with ASTM F2992-15, the glove’s cut resistance shall be classified against the levels from A1 to A9.
- the finally obtained glove liner was tested to ANSI/ISEA 105-2016, ASTM F2675/F2675M-21, EN ISO 15025: 2016 and EN ISO 12127-1: 2015 and got consistent excellent A5 cut level, arc rating of ATPV 11.9 Cal/cm 2 , excellent fire resistance, conductive and contact heat performance.
- Example A was comparative. Compared with Example 1 and 2, the first yarn was a sheath/core construction, but the second yarn was a none-core ring spun yarn without a Spandex core, and the third yarn was also a non-core ring spun yarn. Finally, the same tests were conducted, results were summarized.
- Example B was comparative. Compared with Example 1 and 2, the first yarn was a sheath/core yarn with low glass filament content, the second yarn was a sheath/core yarn similar to examples 1 and 2; but the third yarn was a sheath/core yarn, the same as the first yarn; thus the whole glass contents in the finally obtained ply-twisted yarn was even higher than those in Example 1 and 2. The same tests were conducted, obtaining overall result inferior than that of Example 1, let alone the best results of Example 2; but better than Example A.
- Example A From the results of Example A, it can be seen that a Spandex core for the second yarn is firsthand critical for overall performances; and from the results of Example B, it can be concluded that a glass filament core in the first yarn is secondhand critical for overall performances.
- inventive Examples 1 and 2 when para-aramid, meta-aramid and modacrylic are all combined together, the best overall performance could be obtained.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Knitting Of Fabric (AREA)
- Woven Fabrics (AREA)
Abstract
Disclosed herein is ply-twisted yarn for use in arc, cut, heat and flame protection articles, the ply-twisted yarn comprising: a) a first yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers, the glass filament accounting for at least 30%by weight of the total weight of the first yarn, b) a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn; and c) a third yarn comprising cut, heat and flame resistant polymeric fibers. Also disclosed herein is a woven or knitted fabric comprising the ply-twisted yarn, and An article comprising the woven or knitted fabric.
Description
- This invention relates to yarns and fabrics suitable for use in articles of protective apparels that have arc-resistant, cut-resistant, heat-resistant and flame-resistant properties. Particularly, this invention relates to ply-twisted yarn for use in arc, cut, heat and flame protection articles.
- Workers in multiple industries, e.g. utility, oil &gas, mining, electrical and etc. are facing not only cut injury but also heat &flame and arc hazards.
- Gloves/sleeves made with DuPont fiber only can provide medium cut &heat /flame protection but very marginal arc protection.
- Glove/sleeves made with generic aramid /glass/modacrylic blends CANNOT provide either consistent high cut &arc rating performance or good dexterity /comfort.
- Yarns comprising modacrylic fiber, p-aramid fiber, and m-aramid fiber that are useful for the production of fabrics which possess arc and flame protective properties are disclosed, for example, in U.S. Pat. Nos. 7,065,950 and 7,348,059. These yarns may further comprise, as an optional component, 2 to 15 weight percent of an abrasion –resistant fiber such as nylon and/or 1 to 5 weight percent of an antistatic component.
- Yarns and fabrics having a combination of fire resistance and elastic recovery properties are described, for example, in U.S. Pat. Nos. 5,069,957; 5,527,597; and 5,694,981. These existing solutions utilize yarns made by covering elastic core yarns with a substantial protective fiber outer covering made from a fire -resistant fiber. In other words, these references describe protecting the elastic core by structurally shielding the elastic core from flame by use of another fiber that is in the same yarn.
- A ply-twisted yarn suitable for used in a flame-retardant, cut-resistant fabric is disclosed, for example in US 2022/0325443 A1. The ply -twisted yarn comprises (a) at least one first yarn comprising at least 50 weight percent heat -resistant polymeric fiber, wherein at least 30 weight percent of the polymeric fiber present in the at least one first yarn is cut -resistant heat –resistant polymeric fiber having a cut resistance of 500 grams force or higher per ASTM F2992-15 ; and (b) at least one second yarn having a sheath/core construction with a sheath of halogenated self-extinguishing staple fibers and a core comprising at least one continuous elastic filament.
- However, the current references provide technical solution to some of the protective aspects; and it has always been highly desired to provide a yarn and/or fabric having overall protections of arc-resistant, cut-resistant, heat-resistant and flame-resistant properties.
- Glove or sleeve or clothing made with innovated yarn could effectively protect workers from being harmed from the mentioned multiple hazards with an integrated technical solution.
- Brief Summary of the Invention
- This invention relates to yarns and fabrics suitable for use in articles of protective apparels that have arc-resistant, cut-resistant, heat-resistant and flame-resistant properties.
- Surprisingly, the inventor finds that an innovated ply-twisted yarn can provide the mentioned overall protections against arc-, cut-, heat-and flame-hazards; in which this ply-twisted yarn comprises:
- a) a first yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers, the glass filament accounting for at least 30%by weight of the total weight of the first yarn,
- b) a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn; and
- c) a third yarn comprising cut, heat and flame-resistant polymeric fibers.
- This invention also relates to a woven or knitted fabric comprising the ply-twisted yarn of the invention.
- This invention also relates to an article comprising the woven or knitted fabric of the invention.
- This invention relates to yarns and fabrics, suitable for use in articles of protective apparels that have arc-resistant, heat-resistant and flame-resistant properties, and additionally provide cut protection. The unique combination is created by ply-twisted yarn comprising at least two yarns having sheath/core construction and a further yarn having non-sheath/core construction.
- Specifically, this invention relates to a ply-twisted yarn suitable for use in arc, cut, heat and flame protection articles, the ply-twisted yarn comprising:
- a) a first yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers, the glass filament accounting for at least 30%by weight of the total weight of the first yarn,
- b) a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn; and
- c) a third yarn comprising cut, heat and flame-resistant polymeric fibers.
- “Ply-twisted yarn”
- The ply-twisted yarn of this invention is made by twisting together individual single yarns. It is well known in the art to twist single yarns together to make ply-twisted yarns.
- By the phrase “twisting together individual single yarns” , it is meant the individual single yarns are twisted together without one yarn fully covering any of the others. This distinguishes ply-twisted yarns from covered or wrapped yarns where a single yarn is completely wrapped around another single yarn so that the surface of the resulting ply-twisted yarn only exposes the first single yarn.
- The ply-twisted yarns of this invention are made up of at least three different single yarns. More preferably, the ply-twisted yarns of this invention are made up of three different single yarns.
- According to the invention, the first yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers.
- In a preferred embodiment of the invention, the first yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath made from cut, heat and flame resistant polymeric fibers.
- According to the invention, the second yarn is a yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers.
- In a preferred embodiment of the invention, the second yarn is a yarn having a sheath/core construction with a core of continuous glass filament and a sheath made from cut, heat and flame resistant polymeric fibers.
- According to the invention, the third yarn is a yarn comprising cut, heat and flame resistant polymeric fibers.
- In a preferred embodiment of the invention, the third yarn is a yarn made from cut, heat and flame resistant polymeric fibers.
- “Sheath/core construction”
- A sheath/core construction is used so that because the sheath fibers cover and shield the core filament from direct contact with other materials, which also may give fabrics containing the yarn improved performance.
- The sheath fiber can be wrapped or spun around the core fiber. These can be achieved by known means, such as, conventional ring spinning including improvements to the conventional process such as those utilizing COTSON technology; core-spun spinning such as DREF spinning; air-jet spinning using so-called core insertion with Murata (now Muratec) jet-like spinning; open-end spinning, vortex spinning and the like. Preferably the sheath fiber is consolidated around the core filament at a density sufficient to cover the core filament. The degree of coverage depends on the process used to spin the yarn; for example, core-spun spinning such as DREF spinning (disclosed, for example, in U.S. Patent Nos. 4,107,909; 4,249,368; &4,327,545) provides better coverage than ring spinning. Conventional ring spinning provides only partial coverage of the center core but even partial coverage is assumed a sheath/core structure for the purposes of this invention. The sheath can also include some fibers of other materials to the extent that decreased cut resistance, due to that other material, can be tolerated.
- Glass Filament
- According to the invention, continuous glass filament is used as the core of the first yarn; for example 240 dtex (220 denier) glass filament. Glass filament is an inorganic nonmetallic material with excellent performances, with the advantages of good insulation, strong heat resistance, good corrosion resistance and high mechanical strength. It is usually made from pyrophyllite, quartz sand, limestone, dolomite, boracite, and brucite as raw materials through high-temperature melting, drawing, and other processes. The diameter of glass filament is from several microns to more than 20 microns, and each bundle of fiber precursor is composed of hundreds or even thousands of monofilaments. Glass fiber can be used in fabrics or textile to improve its strength, flame retardance and, especially, cutting performance.
- A number of commercially available glass filament can be used in the present invention without specific limitation; for example, those commercially available as SC8-24×1Z55 FE-5 from Sinoma.
- According to the invention, the first yarn comprises, based on the weight of the first yarn, at least 30%by weight of glass filament; more specifically, from 30 to 50%by weight of glass filament; more preferably, from 35 to 45%by weight of glass filament.
- Elastic Filament
- According to the invention, continuous elastic glass filament is used as the core of the second yarn. Continuous elastic filament as used herein means a core formed from elastomer material, the core preferably having the ability to return to its original length rapidly after repeated stretching, even to at least twice its original length. Preferred elastic core include polyurethane based yarns such as Spandex or Elastane filament; Suitable well-known elastic yarns also include the products sold under the trade name of Lycra.
- The preferred at least one continuous elastic filament is spandex fiber. As used herein, “spandex” has its usual definition, that is, a manufactured fiber in which the fiber-forming substance is a long chain synthetic polymer composed of at least 85 %by weight of a segmented polyurethane. Among the segmented polyurethanes of the spandex type are those described in, for example, U.S. Pat. Nos. 2,929,801; 2,929,802; 2,929,803; 2,929,804; 2,953,839; 2,957,852; 2,962,470; 2,999,839; and 3,009,901.
- The elastic filament of the second yarn is stretched. Typical stretch ratios are 1.5 to 5.0 with 1.5 to 3.50 being preferred, and 3.2 being most preferred. Low stretch ratios yield less elastic recovery while very high stretch ratios make the single yarns difficult to process and the fabric too tight and uncomfortable.
- According to the invention, the second yarn comprises, based on the weight of the second yarn, at most 15%by weight of elastic filament; preferably, from 10 to 15%by weight of elastic filament; more preferably, from 12 to 14%by weight of elastic filament.
- Commercially available elastic filament, for example, comprises Spandex H350 from Kolon, Korea.
- Cut, heat and flame resistant polymeric fibers
- According to the invention, the cut, heat and flame resistant polymeric fibers used therein include para-aramid, meta-aramid, modacrylic, FR-treated rayon, FR-treat cotton, polybenzoxazole, polybenzimidazole, pre-oxidized fiber, or mixtures thereof.
- According to the invention, the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from para-aramid, meta-aramid, modacrylic, FR-treated rayon, FR-treat cotton, polybenzoxazole, polybenzimidazole and pre-oxidized fibers. More preferably, the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from para-aramid, meta-aramid and modacrylic fibers.
- Modacrylic fiber
- By “modacrylic fiber” it is meant acrylic synthetic fiber made from a polymer comprising primarily acrylonitrile. Preferably the polymer is a copolymer comprising 30 to 70 weight percent of a acrylonitrile and 70 to 30 weight percent of a halogen-containing vinyl monomer. The halogen-containing vinyl monomer is at least one monomer selected, for example, from vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, etc. Examples of copolymerizable vinyl monomers are acrylic acid, methacrylic acid, salts or esters of such acids, acrylamide, methylacrylamide, vinyl acetate, etc.
- The preferred modacrylic fibers of this invention are copolymers of acrylonitrile combined with vinylidene chloride, the copolymer having in addition an antimony oxide or antimony oxides for improved fire retardancy. Such useful modacrylic fibers include, but are not limited to, fibers disclosed in U.S. Pat. No. 3,193,602 having 2 weight percent antimony trioxide, fibers disclosed in U.S. Pat. No. 3,748,302 made with various antimony oxides that are present in an amount of at least 2 weight percent and preferably not greater than 8 weight percent, and fibers disclosed in U.S. Pat. Nos. 5,208,105 &5,506,042 having 8 to 40 weight percent of an antimony compound.
- Commercially available modacrylic fiber includes, for example, A from Kaneka Corporation, Japan.
- Aramid fibers
- As used herein, “aramid” is meant a polyamide wherein at least 85%of the amide (-CONH-) linkages are attached directly to two aromatic rings. Additives can be used with the aramid and, in fact, it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid. Suitable aramid fibers are described in Man-Made Fibers-Science and Technology, Volume 2, Section titled Fiber-Forming Aromatic Polyamides, page 297, W.Black et al., Interscience Publishers, 1968. Aramid fibers are, also, disclosed in U.S. Pat. Nos. 4,172,938; 3,869,429; 3,819,587; 3,673,143; 3,354,127; and 3,094,511. M-aramids are those aramids where the amide linkages are in the meta-position relative to each other, and p-aramids are those aramids where the amide linkages are in the para-position relative to each other. In the practice of this invention the aramid as most often used are poly (para-phenylene terephthalamide) , i.e., meta-aramid or p-aramid; and poly (meta-phenylene isophthalamide) , i.e., meta-aramid, or m-aramid.
- M-aramid fiber provides additional tensile strength to the yarn and fabrics formed from the yam. Modacrylic and m-aramid fiber combinations are highly flame resistant but do not provide adequate tensile strength to a yarn or fabric made from the yam to offer the desired level of breakopen resistance when exposed to an electrical arc.
- Within yams of this invention p-aramid fibers provide a high tensile strength fiber which when added in adequate amounts improves the breakopen resistance of fabrics formed from the yam. Large amounts of p-aramid fibers in the yams make garments comprising the yarns uncomfortable to the wearer.
- Commercially available aramid fibers, for example, comprise K series from DuPont Corporation, the U.S.A. as p-aramid fibers, and N series from DuPont Corporation, the U.S.A. as m-aramid fibers.
- In an even more preferred embodiment of the invention, the cut, heat and flame resistant polymeric fibers in the first yarn are 20%to 40%by weight of para-aramid and 20%to 40%by weight of modacrylic, more preferably, 25%to 35%by weight of para-aramid and 25%to 35%by weight of Modacrylic, calculated based on the total weight of the first yarn; and the remaining of the first yarn is the core material of glass filament; which is, at least 30%by weight of the total weight of second yarn..
- In a more preferred embodiment of the invention, the cut, heat and flame resistant polymeric fibers in the second and third yarns are para-aramid, meta-aramid and modacrylic.
- In an even more preferred embodiment of the invention, the cut, heat and flame resistant polymeric fibers in the second yarn are 30%to 50%by weight of para-aramid, 0%to 35%by weight of meta-aramid, and 20%to 55%by weight modacrylic, more preferably, 33%to 40%by weight of para-aramid, 20%to 35%by weight of meta-aramid, and 25%to 55%by weight of modacrylic, calculated based on the total weight of sum of the cut, heat and flame resistant polymeric fibers in the second yarn; and the remaining of the second yarn is the core material of elastic filament; which is, at most 15%by weight of the total weight of second yarn.
- In an even more preferred embodiment of the invention, the cut, heat and flame resistant polymeric fibers of the third yarn are 30%to 50%by weight of para-aramid, 0%to 40%by weight of meta-aramid, and 20%to 65%by weight modacrylic; more preferably, 35%to 45%by weight of para-aramid, 25%to 35%by weight of meta-aramid, and 30%to 60%by weight of modacrylic, calculated based on the total weight of the third yarn.
- Woven or Knit Fabric &Articles
- Woven and/or knit fabric can comprise the ply twisted yarns described herein.
- The preferred fabric is a knit fabric, and any appropriate knit pattern is acceptable.
- Articles can comprise the ply -twisted yarns described herein or articles can be made from the aforementioned fabrics comprising the ply-twisted yarns described herein. Especially useful articles include gloves, sleeves, and aprons.
- The following examples are provided to illustrate the instant invention. However, the present invention is by no means limited by these examples.
- Test Method
- The test specimens are knit fabrics manufactured preferred by a 13G knitting machine.
- Cut Resistance: Cut resistance performance is determined according to ANSI/ISEA 105-2016 “American National Standard For Hand Protection Classification” , specifically the requirements outlined in section of 5.1.1. When tested in accordance with ASTM F2992-15, the glove’s cut resistance shall be classified against the levels from A1 to A9.
- ARC Rating: Arc Thermal Performance Value (ATPV) is measured by ASTM F2675 /F2675M-21 “Standard Test Method for Determining Arc Ratings of Hand Protective Products Developed and Used for Electrical Arc Flash Protection” . The test specimen used for the testing are knitted glove liners with example yarns.
- Flame Resistance: Flame Resistance is rated per EN407: 2020 “Protective gloves and other hand protective equipment’s against thermal risks (heat and /or fire) ” , specific test procedures are outlined in clause of 6.2, herein, Test method is according to EN ISO 15025: 2016, method B with modification for the complete glove.
- Heat Resistance: The determination of contact heat is achieved by the use of EN ISO 12127-1: 2015 “Clothing for protection against heat and flame -Determination of contact heat transmission through protective clothing or constituent materials -Part 1: Contact heat produced by heating cylinder” .
- Raw Materials used in the Examples
- Table 1 below lists the raw materials used in all Examples.
- Table 1
- Note: K29 differs fromK100 mainly in color.
- Examples
- Ply-twisted yarns and knits made from the yarns are exemplified in Examples 1 and 2; Comparative Examples A and B, and summarized in Table 2, and performances thereof are summarized in Table 3.
- Example 1
- Ply-twisted yarn and knits made with the produced yarns were detailed below
- A stretchable ply-twisted yarn was constructed by doubling and twisting a first yarn, a second and a third yarn.
- The first yarn was a 10 cotton count sheath-core yarn have a para-aramid and modacrylic fiber blended sheath and a 220D multi-filament glass core yarn by vortex spinning. Both The para-aramid and modacrylic fiber were 1.5dpf with 38 mm length.
- The second yarn was a 20 cotton count sheath spandex core yarn constructed by core-spinning on ring spinning frame. The sheath is a blend of para-aramid and modacrylic fiber and the core is a 105D spandex with multifilament. The spandex is stretched 3.0 X while spun into the core yarn.
- The third yarn was a 20 cotton count none-core ring spun yarn with para aramid and modacrylic fiber blends.
- The resulting ply-twisted stretchable yarn has a total cotton count 15/3 or 117 tex. The ingredients of each single yarn are shown in 1.
- The resulting ply-twisted stretchable yarn was knitted into a 13G glove knitting machine. The resulting sleeve had superior comfort and dexterity. The glove liner was tested to ANSI/ISEA 105-2016, ASTM F2675 /F2675M-21, EN ISO 15025: 2016 and EN ISO 12127-1: 2015 and got consistent A4 cut level, arc rating of ATPV 9.3 cal/cm2, excellent fire resistance, conductive and contact heat performance.
- Examples 2
- Example 1 was repeated, with the exception on the ingredients of the second yarn and the third yarn. The sheath of the second yarn was a blend of para-aramid, meta-aramid and modacrylic fiber; and the third yard was a none-core ring spun yarn with para aramid, meta-aramid and modacrylic fiber blends as well.
- The finally obtained glove liner was tested to ANSI/ISEA 105-2016, ASTM F2675/F2675M-21, EN ISO 15025: 2016 and EN ISO 12127-1: 2015 and got consistent excellent A5 cut level, arc rating of ATPV 11.9 Cal/cm2, excellent fire resistance, conductive and contact heat performance.
- Example A
- Example A was comparative. Compared with Example 1 and 2, the first yarn was a sheath/core construction, but the second yarn was a none-core ring spun yarn without a Spandex core, and the third yarn was also a non-core ring spun yarn. Finally, the same tests were conducted, results were summarized.
- Example B
- Example B was comparative. Compared with Example 1 and 2, the first yarn was a sheath/core yarn with low glass filament content, the second yarn was a sheath/core yarn similar to examples 1 and 2; but the third yarn was a sheath/core yarn, the same as the first yarn; thus the whole glass contents in the finally obtained ply-twisted yarn was even higher than those in Example 1 and 2. The same tests were conducted, obtaining overall result inferior than that of Example 1, let alone the best results of Example 2; but better than Example A.
- Table 2: Components of All Examples
- Table 3: Performances of All Examples
- From the results of Example A, it can be seen that a Spandex core for the second yarn is firsthand critical for overall performances; and from the results of Example B, it can be concluded that a glass filament core in the first yarn is secondhand critical for overall performances. Between inventive Examples 1 and 2, when para-aramid, meta-aramid and modacrylic are all combined together, the best overall performance could be obtained.
Claims (18)
- A ply-twisted yarn for use in arc, cut, heat and flame protection articles, the ply-twisted yarn comprising:a) a first yarn having a sheath/core construction with a core of continuous glass filament and a sheath comprising cut, heat and flame resistant polymeric fibers, the glass filament accounting for at least 30%by weight of the total weight of the first yarn,b) a second yarn having a sheath/core construction with a core of continuous elastic filament and a sheath comprising cut, heat and flame resistant polymeric fibers, wherein the elastic filament being stretched, and accounting for at most 15%by weight of the total weight of the second yarn; andc) a third yarn comprising cut, heat and flame resistant polymeric fibers.
- The ply-twisted yarn according to claim 1, wherein the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from the group consisting of para-aramid, meta-aramid, modacrylic, FR-treated rayon, FR-treat cotton, polybenzoxazole, polybenzimidazole, pre-oxidized fibers, and mixture thereof.
- The ply-twisted yarn according to any one of claims 1 to 2, wherein the cut, heat and flame resistant polymeric fibers in the first, the second and the third yarn are at least two selected from the group consisting of para-aramid, meta-aramid, modacrylic fibers, and mixture thereof.
- The ply-twisted yarn according to any one of the preceding claims, wherein the cut, heat and flame resistant polymeric fibers in the first yarn are para-aramid and modacrylic fibers.
- The ply-twisted yarn according to any one of the preceding claims, wherein the cut, heat and flame resistant polymeric fibers in the second yarn comprise para-aramid and modacrylic fibers.
- The ply-twisted yarn according to any one of the preceding claims, wherein the cut, heat and flame resistant polymeric fibers in the second yarn and the third yarn are para-aramid and modacrylic fibers.
- The ply-twisted yarn according to any one of the preceding claims, wherein the cut, heat and flame resistant polymeric fibers in the second yarn and the third yarn are para-aramid, meta-aramid and modacrylic fibers.
- The ply-twisted yarn according to any one of the preceding claims, wherein the first yarn comprises at least 25%by weight of para-aramid fiber, more preferably, from 28% to 45%by weigh, based on the total weight of the first yarn.
- The ply-twisted yarn according to any one of the preceding claims, wherein the second and third yarns comprise at least 30%by weight of para aramid fiber, more preferably, from 32%to 50%by weight, most preferably, from 33%to 45%by weight, based on the total weight of the second and third yarns separately.
- The ply-twisted yarn according to any one of the preceding claims, wherein the first, second and third yarns comprise 20%to 65%by weight of modacrylic fiber, more preferably, 25%to 60%by weight, based on the total weight of the first, second and third yarns separately.
- The ply-twisted yarn according to any one of the preceding claims, wherein the second and third yarns comprise 0 to 40%by weight of meta-aramid fiber, more preferably, from 20%to 35%by weight, based on the total weight of the second and third yarns separately.
- The ply-twisted yarn according to any one of the preceding claims, wherein the elastic filament is Spandex filament.
- The ply-twisted yarn according to any one of the preceding claims, wherein the meta-aramid fiber is poly-m-phenylene isophthalamide.
- The ply-twisted yarn according to any one of the preceding claims, wherein the para-aramid in each yarn is poly-p-phenylene terephthamide.
- A woven or knitted fabric comprising the ply-twisted yarn of any one of claims 1 to 14.
- The woven or knitted fabric according to claim 15, wherein the fabric has a minimum cut resistance force 15 N per ASTM F2992-15, a minimum ATPV 8 cal/cm2 per ASTM F2675/F2675M-21, limited flame spread Level 4 and contact heat level 1 per EN407 : 2020.
- An article comprising the woven or knitted fabric of any one of claims 15 to 16.
- The article of claim 17 in the form of knitting glove, cutting &sewing glove, sleeve, apron or clothing.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/078460 WO2024178544A1 (en) | 2023-02-27 | 2023-02-27 | Yarns useful in arc, cut, heat & flame-resistant fabrics and articles comprising the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4673594A1 true EP4673594A1 (en) | 2026-01-07 |
Family
ID=92589058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23924525.1A Pending EP4673594A1 (en) | 2023-02-27 | 2023-02-27 | Yarns useful in arc, cut, heat & flame-resistant fabrics and articles comprising the same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP4673594A1 (en) |
| JP (1) | JP2026506805A (en) |
| CN (1) | CN120981617A (en) |
| WO (1) | WO2024178544A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6581366B1 (en) * | 1998-10-22 | 2003-06-24 | World Fibers, Inc. | Cut-resistant stretch yarn fabric and apparel |
| US7127879B2 (en) * | 2002-10-03 | 2006-10-31 | E. I. Du Pont De Nemours And Company | Ply-twisted yarn for cut resistant fabrics |
| US6952915B2 (en) * | 2003-10-29 | 2005-10-11 | E. I. Du Pont De Nemours And Company | Ply-twisted yarns and fabric having both cut-resistance and elastic recovery and processes for making same |
| US7934396B2 (en) * | 2009-01-26 | 2011-05-03 | E. I. Du Pont De Nemours And Company | Cut-resistant gloves containing fiberglass and para-aramid |
| CN104894736A (en) * | 2015-06-25 | 2015-09-09 | 东华大学 | Aramid fiber coated continuous glass fiber cut-resistant fabric and preparation method thereof |
| CN112458582A (en) * | 2019-09-06 | 2021-03-09 | 杜邦安全与建筑公司 | Ply-twisted yarn and fabric with cut resistance |
| CN211814776U (en) * | 2020-01-19 | 2020-10-30 | 常州科旭纺织有限公司 | Different-core short fiber core-spun yarn with elasticity and cutting-resistant capability and product thereof |
-
2023
- 2023-02-27 JP JP2025550450A patent/JP2026506805A/en active Pending
- 2023-02-27 CN CN202380094973.3A patent/CN120981617A/en active Pending
- 2023-02-27 EP EP23924525.1A patent/EP4673594A1/en active Pending
- 2023-02-27 WO PCT/CN2023/078460 patent/WO2024178544A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024178544A1 (en) | 2024-09-06 |
| JP2026506805A (en) | 2026-02-26 |
| CN120981617A (en) | 2025-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8133584B2 (en) | Crystallized meta-aramid blends for flash fire and arc protection having improved comfort | |
| JP5979796B2 (en) | High moisture content yarn, fabric and clothes with excellent arc protection | |
| EP1725704B1 (en) | Modacrylic/cotton/aramid fiber blends for arc and flame protection | |
| EP2181209B1 (en) | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same | |
| EP1649089B1 (en) | Flame retardant fiber blends comprising modacrylic fibers and fabrics and garments made therefrom | |
| US8069642B2 (en) | Crystallized meta-aramid blends for improved flash fire and superior arc protection | |
| CN1875135B (en) | Ply-twisted yarns and fabric having both cut-resistance and elastic recovery and processes for making same | |
| CN101784707A (en) | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antitstatic fibers and fabrics and garments made therefrom and methods for making same | |
| CN101784708B (en) | Spun yarns made from blends of rigid rod fibers and fibers derived from diaminodiphenylsulfone and fabrics and garments made therefrom and methods of making them | |
| CN117716078A (en) | Flame resistant fabric formed with stretchable yarns | |
| WO2024178544A1 (en) | Yarns useful in arc, cut, heat & flame-resistant fabrics and articles comprising the same | |
| CN117377795B (en) | Fabrics and articles with fire resistance, cut resistance and elastic recovery, and methods for manufacturing thereof | |
| EP4323569A1 (en) | Yarns and fabrics having fire-resistance, cut-resistance, and elastic recovery and processes for making same | |
| JP5650571B2 (en) | Cut-resistant spun yarn and fabric including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20250919 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR |