EP3507413A1 - Flame retardant treated fabrics with low formaldehyde content - Google Patents

Flame retardant treated fabrics with low formaldehyde content

Info

Publication number
EP3507413A1
EP3507413A1 EP16759771.5A EP16759771A EP3507413A1 EP 3507413 A1 EP3507413 A1 EP 3507413A1 EP 16759771 A EP16759771 A EP 16759771A EP 3507413 A1 EP3507413 A1 EP 3507413A1
Authority
EP
European Patent Office
Prior art keywords
flame
fabric
phosphonium
condensate
hydroxyorgano
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.)
Granted
Application number
EP16759771.5A
Other languages
German (de)
French (fr)
Other versions
EP3507413B1 (en
Inventor
Gary Woodward
Geoffrey Hand
Robert Hicklin
Matthew SEABROOK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Solutions US LLC
Original Assignee
Rhodia Operations SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP3507413A1 publication Critical patent/EP3507413A1/en
Application granted granted Critical
Publication of EP3507413B1 publication Critical patent/EP3507413B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the instant invention relates to textile articles comprising (or consisting in) a fabric treated by flame-retardant polymer polymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt (also referred as "THP + salt”) ; and (ii) urea and/or thiourea (herein referred as "(thio)urea”) ; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate.
  • a fabric treated by flame-retardant polymer polymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt (also referred as “THP + salt”) ; and (ii) urea and/or thiourea (herein referred as "(thio)urea”) ; followed by an oxidation
  • the fabric to be treated is generally impregnated with the condensate of the THP + salt and (thio)urea (optionally together with an amine as described in EP 0 709 518, such as an aliphatic amine having 12 carbon atoms or more, such as n-dodecylamine; n-octadecylamine, n- hexadecylamine, and/or n-eicosylamine) and, typically, the fabric is then dried and then cured with ammonia (NH 3 ) whereby a phosphonium-based polymer is produced within the fibers of the fabric, which is mechanically fixed to the fabric.
  • an amine such as an aliphatic amine having 12 carbon atoms or more, such as n-dodecylamine; n-octadecylamine, n- hexadecylamine, and/or n-eicosylamine
  • the obtained polymer is oxidized in order to convert at least a part of the trivalent phosphorus (carried by the phosphonium group) into a pentavalent phosphorous (an phosphine oxide group).
  • fabrics treated according to this process and textile articles and garments made thereof are those sold under the trademark PROBAN ® .
  • the inventors have now found that a fabric treated according to the above-mentioned process tends to generate formaldehyde over the time. Concretely, in many cases, the free HCOH content increase with the time and, generally, becomes greater than 100 ppm or even greater than 300 ppm over a few years.
  • the term "free HCOH content” as used in the instant description refers to the content of free formaldehyde (HCOH) in the fabric as measured according to the European standard No. EN ISO 14184-1 .
  • a fabric intended to be in contact with the human skin should have a very low content of HCOH, typically of less than 300 ppm, more preferably less than 200 ppm for an indirect contact (with another piece of clothes between the fabric and the skin) and of less than 100 ppm, preferably less than 75 ppm.
  • the instant invention aims at providing a flame retardant treatment process making use of the materials which lead to a low content of formaldehyde that remains low over the time.
  • the instant invention proposes to make use of the above mentioned process but in specific conditions, that have been found inhibit the formaldehyde formation over the time.
  • the inventors have now shown that when a fabric has a content of trivalent phosphorous, i.e.
  • one subject matter of the instant invention is a textile article, such as an item of clothing for example, comprising at least one flame- retardanttreated fabric including an oxidizedpolymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii)urea and/or thiourea; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate, wherein said flame-retardant treated fabric :
  • - is intended to be used as a stable substrate in which the formation of formaldehyde over the time is inhibited , for example for a long term contact with the skin ;
  • the molar ratio P3:P5 of the trivalent phosphorus (as present in the phosphonium groups) to the pentavalent phosphorus (as present in the phosphine amide groups) is typically of less than 60%, for example of about 50%.
  • the total content of phosphorus in a fabric according to the invention is typically of around 2% based on the total weight of the flame-retardant treated fabric.
  • Another subject matter of the instant invention is a process for preparing the above mentioned textile article, comprising :
  • a flame retardant treatment of the fabric including :
  • Step (b) an analysis of the content of the phosphonium groups in the fabric, followed by a repetition of the sequence of the steps (a3) and(b) if the analysis shows that the fabric contains 1 % or more of phosphorus present in phosphonium groups, based on the total weight of the flame- retardant treated fabric.
  • Step (a3) may be followed by a washing of the oxidized fabric obtained in step (a3), typically by immersion within at least one (for example 2 or 3) washing bath, typically a water-containing washing bath.
  • step (b) comprises an analysis wherein the content of trivalent phosphorus is checked and adapted if needed.
  • the analysis may for example be made by 31 P NMR, that allows to distinguish a phosphonium peak at around 25 ppm and an amine oxide peak at around 47 ppm
  • sequence of the steps (a3) and (b) are repeated many times until the sought trivalent phosphonium content is not below the sought value.
  • sequence of the steps (a3) and (b) may be repeated even after having obtained a content below the sought value (for example if a very low content of trivalent phosphonium is sought.
  • step (b) the analysis is followed by a repetition of the sequence of steps (a3) and (b) if the analysis shows that the oxidized polymer contains 0.9% or more of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated ffabric
  • the invention relates to the use of a flame-retardant treated fabric containing less than 1 % by weight, preferably less than 0.9% by weight and even more preferably less than 0.8% by weight of phosphorus present in phosphonium groups (trivalent phosphorus), based on the total weight of the flame- retardant treated fabric, as a substrate stabilized against formation of formaldehyde, for example for a long term contact with the skin.
  • long term contact with the skin especially include a contact with the skin, preferably more than one year, more preferably more than 2 years, and even more preferably at least 3 years, after the synthesis of the oxidized polymer.
  • step (a) systematically allows to obtain the sought content of trivalent phosphorous, i.e. of the phosphorus present in phosphonium groups, of less than 1 % of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.
  • step (a3) when the oxidation step (a3) is carried out in the presence of a metabisulfite salt used a pH of less than 4 (typically when the oxidation using H 2 0 2 is followed by a treatment using a metabisulfite salt at a pH of less than 4, contrary to the usual conditions wherein metabisulfite salt is used as a scavenger but at a pH of at least 5, typically of at least 6), then the step (a) systematically leads to a trivalent phosphorous content of less than 1 % (with sodium metabisulfite at a pH of about 2, this content is of about 0.8%). Therefore, when step (a) is conducted in these specific conditions, there is no need of step (b).
  • another specific subject matter of the instant invention is a process that directly allows to obtain a flame-retardant treated fabric according to the present invention, that contains less than 1 % by weight, generally less than 0.9% by weight and in most cases less than 0.8% by weight of phosphorus present in phosphonium groups (trivalent phosphorus), based on the total weight of the flame-retardant treated fabric.
  • This specific process that do not need the implementation of a "checking" step (b) as defined above, contains a flame retardant treatment, including the following steps:
  • ⁇ step 1 an impregnation of said fabric with the condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea , preferably followed by a drying
  • ⁇ step 2 a curing with ammonia of the impregnated condensate ;
  • ⁇ step 3 an oxidation of the polymer resulting from the curing, typically with
  • H 2 0 2 said oxidation including and/or being followed by a treatment with a metabisulfite salt, preferably sodium metabisulfite, at a pH of below 4, preferably below 3, for example at a pH of 1 .5 to 2.5, (e.g. from 1 .8 to 2.2, typically of about 2).
  • a metabisulfite salt preferably sodium metabisulfite
  • an oxidation is first carried out using hydrogen peroxide H 2 0 2 or another oxidant, and then the treated fabric is treated with a metabisulfite salt, preferably sodium metabisulfite, at a pH of below 4, preferably 3, for example at a pH of 1 .5 to 2.5, typically with SMBS at a pH of about 2.
  • a metabisulfite salt preferably sodium metabisulfite
  • the textile article of the invention is intended to be in indirect contact with the skin (namely with a layer of clothing between the treated surface and the skin). In that case, it is advantageous that it comprises less than 300 ppm, preferably less than 200 ppm of free formaldehyde, as measured according to the European standard No. EN ISO 14184-1 .
  • the textile article of the invention is a intended for direct contact with the skin. Then, it is highly preferable that it comprises less than 75 ppm of free formaldehyde , as measured according to the European standard No. EN ISO 14184-1 .
  • the tetrakis (hydroxyorgano) phosphonium salt is tetrakis (hydroxyorgano) phosphonium chloride (THPC).
  • THPC tetrakis (hydroxyorgano) phosphonium chloride
  • THPS tetrakis (hydroxyorgano) phosphonium sulfate
  • the treated fabric advantageously comprises cellulosic fibers, for example natural cellulosic fibers such as fibers of cotton, linen, jute, or hessian ; or regenerated cellulosic material.
  • the treated fabric essentially comprises (typically for at least 95%) cellulosic fibers.
  • the fabric may comprise a mixture of cellulosic fibers together with non cellulosic fibers, said non cellulosic fibers being for example natural fibers such as wool or silk, or synthetic fibers such as polyester, polyamide, or aramid.
  • the fabric may comprise a mixture of 60% cotton and 40% polyester.
  • Example 1 Two treated fabrics having a total content of phosphorus of 2% based on the total weight of the flame-retardant treated fabric have been compared :
  • the PERFORM CC treated fabric was then subjected to an ammonia atmosphere for 15 seconds by passing through an ammonia cure unit. After sampling this resulted in 577g of impregnated and cured fabric.
  • the 577g of cured fabric was then immersed for 10 minutes in a bath with the following composition: 2L of 35% hydrogen peroxide in 8L of water as a solvent.
  • the fabric was then immersed for 15 minutes in another bath with the following composition: 100g of soda ash in 10L of water as a solvent.
  • the fabric was then immersed for 45 minutes in another bath with the following composition: 10L of water.
  • the fabric was then immersed for 5 minutes in another bath with the following composition: 10L of water, whereby a bulk oxidised fabric (BOF) is obtained.
  • BOF bulk oxidised fabric
  • a first sample (Sample 1 ) of the BOF as obtained after the treatment steps as defined above was treated at a pH of 5.
  • Sample 1 was then immersed for 5 minutes in a bath with the following composition: 1 L of water at 20°C.
  • Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at ⁇ 80°C Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at ⁇ 80°C
  • Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at 20°C.
  • the free content of HCOH remains very low and stable over the time (Sample 2), when it increases with the time with the standard conditions of treatment (sample 1 ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The instant invention relates to a textile article comprising a flame-retardant treated fabric including an oxidized polymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate, wherein said flame-retardant treated fabric : - is intended to be used as a stable substrate in which the formation of formaldehyde over the time is inhibited; and - contains less than 1 % by weight of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.

Description

FLAME RETARDANT TREATED FABRICS
WITH LOW FORMALDEHYDE CONTENT
The instant invention relates to textile articles comprising (or consisting in) a fabric treated by flame-retardant polymer polymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt (also referred as "THP+ salt") ; and (ii) urea and/or thiourea (herein referred as "(thio)urea") ; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate.
Flame retardant treatments of this type are well known and has been described e.g. in the European patent application EP 0 709 518. In these treatment, the fabric to be treated is generally impregnated with the condensate of the THP+ salt and (thio)urea (optionally together with an amine as described in EP 0 709 518, such as an aliphatic amine having 12 carbon atoms or more, such as n-dodecylamine; n-octadecylamine, n- hexadecylamine, and/or n-eicosylamine) and, typically, the fabric is then dried and then cured with ammonia (NH3) whereby a phosphonium-based polymer is produced within the fibers of the fabric, which is mechanically fixed to the fabric. After the curing, the obtained polymer is oxidized in order to convert at least a part of the trivalent phosphorus (carried by the phosphonium group) into a pentavalent phosphorous (an phosphine oxide group). Examples of fabrics treated according to this process and textile articles and garments made thereof are those sold under the trademark PROBAN® . In the scope of the instant invention, the inventors have now found that a fabric treated according to the above-mentioned process tends to generate formaldehyde over the time. Concretely, in many cases, the free HCOH content increase with the time and, generally, becomes greater than 100 ppm or even greater than 300 ppm over a few years. The term "free HCOH content" as used in the instant description refers to the content of free formaldehyde (HCOH) in the fabric as measured according to the European standard No. EN ISO 14184-1 .
This identified formation of formaldehyde constitutes a potential bar, because of the toxicity of formaldehyde. Especially, a fabric intended to be in contact with the human skin should have a very low content of HCOH, typically of less than 300 ppm, more preferably less than 200 ppm for an indirect contact (with another piece of clothes between the fabric and the skin) and of less than 100 ppm, preferably less than 75 ppm.
The instant invention aims at providing a flame retardant treatment process making use of the materials which lead to a low content of formaldehyde that remains low over the time.
To this end, the instant invention proposes to make use of the above mentioned process but in specific conditions, that have been found inhibit the formaldehyde formation over the time. Namely, the inventors have now surprisingly found that a limitation of the content of trivalent phosphorus (i.e. phosphorus of phosphonium groups by opposition of pentavalent phosphorus of the phosphine oxide groups >P=0) in the treated fabric leads to a strong decrease of the formation of formaldehyde. Especially, the inventors have now shown that when a fabric has a content of trivalent phosphorous, i.e. of the phosphorus present in phosphonium groups, of less than 1 % by weight based on the total weight of the flame-retardant treated fabric, then substantially no formaldehyde HCOH is generated over the time. The inhibition of the formation of HCOH is even more efficient when the content of trivalent phosphorous is lower than 0.9%, and even more when lower than 0.8%.
On this basis, according to a first aspect, one subject matter of the instant invention is a textile article, such as an item of clothing for example, comprising at least one flame- retardanttreated fabric including an oxidizedpolymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii)urea and/or thiourea; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate, wherein said flame-retardant treated fabric :
- is intended to be used as a stable substrate in which the formation of formaldehyde over the time is inhibited , for example for a long term contact with the skin ; and
- contains less than 1 % by weight, preferably less than 0.9% by weight and even more preferably less than 0.8% by weight of phosphorus present in phosphonium groups (trivalent phosphorus), based on the total weight of the flame-retardant treated fabric. In a textile article according to the invention, the molar ratio P3:P5 of the trivalent phosphorus (as present in the phosphonium groups) to the pentavalent phosphorus (as present in the phosphine amide groups) is typically of less than 60%, for example of about 50%. The total content of phosphorus in a fabric according to the invention is typically of around 2% based on the total weight of the flame-retardant treated fabric.
Another subject matter of the instant invention is a process for preparing the above mentioned textile article, comprising :
(a) a flame retardant treatment of the fabric, including :
(a1 ) an impregnation of said fabric with the condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea
(a2) a curing with ammonia of the impregnated condensate ;
(a3) an oxidation of the polymer resulting from the curing, typically with
H202
(b) an analysis of the content of the phosphonium groups in the fabric, followed by a repetition of the sequence of the steps (a3) and(b) if the analysis shows that the fabric contains 1 % or more of phosphorus present in phosphonium groups, based on the total weight of the flame- retardant treated fabric. Step (a3) may be followed by a washing of the oxidized fabric obtained in step (a3), typically by immersion within at least one (for example 2 or 3) washing bath, typically a water-containing washing bath.
In the process of the invention, step (b) comprises an analysis wherein the content of trivalent phosphorus is checked and adapted if needed. The analysis may for example be made by 31 P NMR, that allows to distinguish a phosphonium peak at around 25 ppm and an amine oxide peak at around 47 ppm
If needed, the sequence of the steps (a3) and (b) are repeated many times until the sought trivalent phosphonium content is not below the sought value. According to a specific embodiment, the sequence of the steps (a3) and (b) may be repeated even after having obtained a content below the sought value (for example if a very low content of trivalent phosphonium is sought. According to a possible embodiment, in step (b), the analysis is followed by a repetition of the sequence of steps (a3) and (b) if the analysis shows that the oxidized polymer contains 0.9% or more of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated ffabric According to yet another aspect, the invention relates to the use of a flame-retardant treated fabric containing less than 1 % by weight, preferably less than 0.9% by weight and even more preferably less than 0.8% by weight of phosphorus present in phosphonium groups (trivalent phosphorus), based on the total weight of the flame- retardant treated fabric, as a substrate stabilized against formation of formaldehyde, for example for a long term contact with the skin.
The expression "long term" contact with the skin, especially include a contact with the skin, preferably more than one year, more preferably more than 2 years, and even more preferably at least 3 years, after the synthesis of the oxidized polymer.
In the scope of the instant invention, the inventors have now shown that, in some specific conditions, step (a) systematically allows to obtain the sought content of trivalent phosphorous, i.e. of the phosphorus present in phosphonium groups, of less than 1 % of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric. More precisely, it has now been found that, surprisingly, when the oxidation step (a3) is carried out in the presence of a metabisulfite salt used a pH of less than 4 (typically when the oxidation using H202 is followed by a treatment using a metabisulfite salt at a pH of less than 4, contrary to the usual conditions wherein metabisulfite salt is used as a scavenger but at a pH of at least 5, typically of at least 6), then the step (a) systematically leads to a trivalent phosphorous content of less than 1 % (with sodium metabisulfite at a pH of about 2, this content is of about 0.8%). Therefore, when step (a) is conducted in these specific conditions, there is no need of step (b). Accordingly, another specific subject matter of the instant invention is a process that directly allows to obtain a flame-retardant treated fabric according to the present invention, that contains less than 1 % by weight, generally less than 0.9% by weight and in most cases less than 0.8% by weight of phosphorus present in phosphonium groups (trivalent phosphorus), based on the total weight of the flame-retardant treated fabric. This specific process, that do not need the implementation of a "checking" step (b) as defined above, contains a flame retardant treatment, including the following steps:
■ step 1 : an impregnation of said fabric with the condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea , preferably followed by a drying
■ step 2 : a curing with ammonia of the impregnated condensate ; ■ step 3 : an oxidation of the polymer resulting from the curing, typically with
H202 , said oxidation including and/or being followed by a treatment with a metabisulfite salt, preferably sodium metabisulfite, at a pH of below 4, preferably below 3, for example at a pH of 1 .5 to 2.5, (e.g. from 1 .8 to 2.2, typically of about 2).
Typically, in step 3, an oxidation is first carried out using hydrogen peroxide H202 or another oxidant, and then the treated fabric is treated with a metabisulfite salt, preferably sodium metabisulfite, at a pH of below 4, preferably 3, for example at a pH of 1 .5 to 2.5, typically with SMBS at a pH of about 2.
Different features and specific embodiments of the invention are described in more details herein-after :
According to a first variant, the textile article of the invention is intended to be in indirect contact with the skin (namely with a layer of clothing between the treated surface and the skin). In that case, it is advantageous that it comprises less than 300 ppm, preferably less than 200 ppm of free formaldehyde, as measured according to the European standard No. EN ISO 14184-1 . According to a second variant, the textile article of the invention is a intended for direct contact with the skin. Then, it is highly preferable that it comprises less than 75 ppm of free formaldehyde , as measured according to the European standard No. EN ISO 14184-1 . According to a specific embodiment, the tetrakis (hydroxyorgano) phosphonium salt is tetrakis (hydroxyorgano) phosphonium chloride (THPC). Alternatively, it may be advantageous that the tetrakis (hydroxyorgano) phosphonium salt is tetrakis (hydroxyorgano) phosphonium sulfate (THPS)
The treated fabric advantageously comprises cellulosic fibers, for example natural cellulosic fibers such as fibers of cotton, linen, jute, or hessian ; or regenerated cellulosic material. According to a specific embodiment, the treated fabric essentially comprises (typically for at least 95%) cellulosic fibers.
According to another embodiment, the fabric may comprise a mixture of cellulosic fibers together with non cellulosic fibers, said non cellulosic fibers being for example natural fibers such as wool or silk, or synthetic fibers such as polyester, polyamide, or aramid. As an example, the fabric may comprise a mixture of 60% cotton and 40% polyester.
The invention will now be further illustrated by the following illustrative example.
Example 1 Two treated fabrics having a total content of phosphorus of 2% based on the total weight of the flame-retardant treated fabric have been compared :
Fabric 1 : Comparative
containing trivalent phosphorus at a content more than 1 % of based on the total weight of the flame-retardant treated fabric
Fabric 2 : according to the invention
containing trivalent phosphorus at a content of 0.9% of based on the total weight of the flame-retardant treated fabric
The free HCOH content on the fabric has been measured and are reported in the table below :
Free HCOH content (pppm)
time Fabric 1 Fabric 2
(years) (comparative) invention)
0 100 100
0.5 125 100
1 150 100
2 205 100
3 305 100
Example 2
In order to illustrate the advantages of the succession of step 1 to step 3 of the process of the invention, a comparison test has been conducted on fabric treated with PERFORM chemical, ammonia cured and oxidised with hydrogen peroxide according to the standard industry procedure, using sodium metabisulfite (SMBS) at a pH of 5, and the same but using sodium metabisulfite (SMBS) at a pH of 2 More precisely, a fabric treatment has been carried out as follows :
■ Impregnation
514g of a fabric was immersed in a bath having the following composition: 481 g of PERFORM CC (available at Solvay) in 519 g of water as a solvent.
The fabric was then immediately passed through a pad mangle and into an oven for drying at 120 °C for approximately 1 minute. ■ Ammonia curing
The PERFORM CC treated fabric was then subjected to an ammonia atmosphere for 15 seconds by passing through an ammonia cure unit. After sampling this resulted in 577g of impregnated and cured fabric.
■ HpOp Oxidation
The 577g of cured fabric was then immersed for 10 minutes in a bath with the following composition: 2L of 35% hydrogen peroxide in 8L of water as a solvent.
The fabric was then immersed for 15 minutes in another bath with the following composition: 100g of soda ash in 10L of water as a solvent. The fabric was then immersed for 45 minutes in another bath with the following composition: 10L of water. The fabric was then immersed for 5 minutes in another bath with the following composition: 10L of water, whereby a bulk oxidised fabric (BOF) is obtained.
■ Sodium metabisulfite treatment
As a comparative test, a first sample (Sample 1 ) of the BOF as obtained after the treatment steps as defined above was treated at a pH of 5.
As an illustration of the instant invention, the same treatment has been carried out on a second Sample of the BOF (Sample 2), in exactly the same conditions as for
Sample 1 , but with a treatment at a pH of 2.
Sample 1 (Comparative test)
13.4 g of the BOF (=Sample 1 ) was immersed in a bath with the following composition: 27.4g of 40% sodium metabisulfite in 1 L of water as a solvent, with a resulting pH of 5. for 5 minutes at 70°C.
Sample 1 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at 80°C
Sample 1 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at 80°C
Sample 1 was then immersed for 5 minutes in a bath with the following composition: 1 L of water at 20°C.
Sample 2 (Illustrative )
13.9 g of the BOF (=Sample 2 ) was immersed in a bath with the following composition: 27.4g of 40% sodium metabisulfite plus 40g of 1 M HCI in 1 L of water as a solvent, with a resulting pH of 2 for 5 minutes at ~70°C.
Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at ~80°C Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at ~80°C
Sample 2 was then immersed for 5 minutes in another bath with the following composition: 1 L of water at 20°C.
As a result, a trivalent phosphorus_content content of less than 1 % (0.84%) has been obtained when SMBS is used at pH=2 according to the invention (Sample 2).
On the other hand, a content of more than 1 % (1 .26%) has been obtained in the standard conditions using SMBS is used (sample 1 )
With the content of less than 1 % as obtained according to the invention, the free content of HCOH remains very low and stable over the time (Sample 2), when it increases with the time with the standard conditions of treatment (sample 1 ).

Claims

CLAIMS 1 . A textile article comprising at least one flame-retardant treated fabric including an oxidized polymer obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt ; and (ii) urea and/or thiourea ; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate, wherein said flame-retardant treated fabric :
- is intended to be used as a stable substrate in which the formation of formaldehyde over the time is inhibited ; and
- contains less than 1 % by weight of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.
2. A textile article according to claim 1 wherein the flame-retardant treated fabric contains less than 0.9% by weight of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.
3. A textile article according to claim 1 or 2 intended to an indirect contact with the skin, with a clothing between the treated surface and the skin, that comprises less than 300 ppm, preferably less than 200 ppm of free formaldehyde.
4. A textile article according to claim 1 or 2 intended to a direct contact with the skin, that comprises less than 75 ppm of free formaldehyde.
5. A textile article according to any of claim 1 to 4, wherein the tetrakis (hydroxyorgano) phosphonium salt is tetrakis (hydroxyorgano) phosphonium chloride (THPC)
6. A textile article according to any of claim 1 to 4, wherein the tetrakis (hydroxyorgano) phosphonium salt is tetrakis (hydroxyorgano) phosphonium sulfate (THPS)
7. A textile article according to any of claim 1 to 4, wherein the oxidized polymer is obtained from an ammonia curing of a condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt ; (ii) urea and/or thiourea, toogether with an an aliphatic amine having 12 carbon atoms or more; followed by an oxidation into phosphine oxide groups of at least one part of the phosphonium groups present on the cured condensate.
8. A process for preparing a textile article as defined in claim 1 , comprising :
(a) a flame retardant treatment of the fabric, including :
(a1 ) an impregnation of said fabric with the condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea, optionally together with an aliphatic amine having 12 carbon atoms or more
(a2) a curing with ammonia of the impregnated condensate ;
(a3) an oxidation of the polymer resulting from the curing, typically with H202
(b) an analysis of the content of the phosphonium groups in the fabric, for example by 31 P NMR, followed by a repetition of the sequence of the steps (a3) and(b) if the analysis shows that the fabric contains 1 % or more of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.
9. The process of claim 8, wherein in step (b), the analysis is followed by a repetition of the sequence of steps (a3) and (b) if the analysis shows that the oxidized polymer contains 0.9% or more of phosphorus present in phosphonium groups, based on the total weight of the flame-retardant treated fabric.
10. A process for preparing a textile article as defined in claim 1 , comprising the following steps :
■ step 1 : an impregnation of said fabric with the condensate of (i) a tetrakis (hydroxyorgano) phosphonium salt; and (ii) urea or thiourea
■ step 2 : a curing with ammonia of the impregnated condensate ; ■ step 3 :
an oxidation of the polymer resulting from the curing, said oxidation including and/or being followed by a treatment with a metabisulfite salt at a pH of below 4, preferably below 3.
1 1 . The use of a flame-retardant treated fabric as defined in any one of claim 1 to 7 or as obtained according to any of claim 6 to 10 as a substrate stabilized against formation of formaldehyde, for example for a long term contact with the skin.
12. Use according to claim 1 1 , wherein the flame-retardant treated fabric is used for a long term contact with the skin, preferably more than one year, more preferably more than 2 years, and even more preferably at least 3 years, after the synthesis of the oxidized polymer
EP16759771.5A 2016-09-01 2016-09-01 Flame retardant treated fabrics with low formaldehyde content Active EP3507413B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/070586 WO2018041351A1 (en) 2016-09-01 2016-09-01 Flame retardant treated fabrics with low formaldehyde content

Publications (2)

Publication Number Publication Date
EP3507413A1 true EP3507413A1 (en) 2019-07-10
EP3507413B1 EP3507413B1 (en) 2023-07-19

Family

ID=56852270

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16759771.5A Active EP3507413B1 (en) 2016-09-01 2016-09-01 Flame retardant treated fabrics with low formaldehyde content

Country Status (6)

Country Link
US (1) US20190242056A1 (en)
EP (1) EP3507413B1 (en)
CN (1) CN109891019B (en)
BR (1) BR112019002870B1 (en)
ES (1) ES2959426T3 (en)
WO (1) WO2018041351A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021077036A1 (en) * 2019-10-17 2021-04-22 Alexium, Inc. Flame retardant polymers and methods of making
CN110983784B (en) * 2019-12-17 2022-07-12 太仓宝霓实业有限公司 Improved environment-friendly flame retardant composition and preparation method thereof
CN118029145B (en) * 2024-02-28 2025-07-11 东华大学 Flame-retardant fabric and preparation method and application thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE610438A (en) * 1960-11-21 1900-01-01
RU2041301C1 (en) * 1986-10-13 1995-08-09 Олбрайт энд Вильсон Лимитед Method of modification of stained cotton fabric
GB9008421D0 (en) * 1990-04-12 1990-06-13 Albright & Wilson Fabric treatment process
GB9222190D0 (en) * 1992-10-22 1992-12-02 Albright & Wilson Flame retardant and water resistant treatment of fabrics
GB9412484D0 (en) * 1994-06-22 1994-08-10 Albright & Wilson Flame-retardant treatment of fabrics
GB9421424D0 (en) * 1994-10-25 1994-12-07 Albright & Wilson Flame-retardent and fabric-softening treatment of textile materials
DE102006040075B4 (en) * 2006-08-28 2015-12-03 Deutsches Textilforschungszentrum Nord-West E.V. Dyeing process for synthetic and cellulosic fibers using ionic liquids
EP1990468A1 (en) * 2007-05-11 2008-11-12 Huntsman Textile Effects (Germany) GmbH Method for flame-retardant finishing of fibre materials
US10202720B2 (en) * 2009-10-21 2019-02-12 Milliken & Company Flame resistant textile
ES2704280T3 (en) * 2012-09-21 2019-03-15 Dow Global Technologies Llc Method for treating fabrics with a dye fixative agent
CN104611928A (en) * 2015-01-07 2015-05-13 广东德美精细化工股份有限公司 Flame-proof treatment method of pure cotton or cotton blended fabric

Also Published As

Publication number Publication date
BR112019002870A2 (en) 2019-05-14
BR112019002870B1 (en) 2022-05-17
CN109891019A (en) 2019-06-14
CN109891019B (en) 2023-05-02
ES2959426T3 (en) 2024-02-26
EP3507413B1 (en) 2023-07-19
US20190242056A1 (en) 2019-08-08
WO2018041351A1 (en) 2018-03-08

Similar Documents

Publication Publication Date Title
BR112012011350B1 (en) FLAME RESISTANT TEXTILE
EP0709518B1 (en) Flame retardant and fabric softening treatment of textile materials
PT90877B (en) PROCESS FOR THE TREATMENT OF FINISHING COTTON FABRICS WITH POLYCARBOXYLIC ACIDS FREE OF FORMAL ALDEIDE, FOR THE END OF THEM CONFERING RESISTANCE TO WRINKLE FORMATION, AND FOR THE MANUFACTURE OF FIBER CELLULOSE TEXTILE MATERIALS
EP2145044A2 (en) Flame-retardant finishing of fiber materials
KR101037810B1 (en) Flame retardant, water repellent, antibacterial processing method of cotton fiber
KR20110108389A (en) Method and treatment composition for imparting durable antimicrobial properties to carpet
PL157688B1 (en) Method of reducing the flammability of a substrate containing fibers PL PL PL PL PL PL PL
EP3507413B1 (en) Flame retardant treated fabrics with low formaldehyde content
US2828228A (en) Textile fire retardant treatment
EP1549796B1 (en) Flame-retardant fabrics
US3374107A (en) Process for the treatment of textiles with aminoplasts
US9074316B2 (en) Method for fireproofing textiles
Blanchard et al. Flame resistant cotton/polyester carpet materials
WO2008116729A2 (en) Process for flame-retardant finishing of cotton
US8580348B2 (en) Treatment of textile materials
US3625738A (en) Process for stabilizing organophosphorus solutions and imparting rot and flame resistance to organic textile materials
JP2016146908A (en) Deodorant, deodorant fiber and deodorant fiber product
GB2497974A (en) Applying acetoacetamide to textiles, to remove formaldehyde by-product of fire retardant treatment
US4111652A (en) Synergistic flame retardant mixtures and products
JPH04352867A (en) Modification of cellulosic fiber
Morris et al. Flame Retardant Finishing of Cotton Fabric With a Methylol Derivative of Tris (2-carbamoylethyl) phosphine Oxide.
US20160281000A1 (en) Method to provide flame retardancy to materials
JPS6375181A (en) Flameproof processing of polyester/cellulose fiber mixed cloth
JPH10251970A (en) Modifyed cellulose fiber, its production and fiber product
PL127951B1 (en) Method of impregnating textile and plastic articles

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: 20190401

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 MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHODIA OPERATIONS

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHODIA OPERATIONS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20221111

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

INTG Intention to grant announced

Effective date: 20230329

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ENERGY SOLUTIONS (US) LLC

AK Designated contracting states

Kind code of ref document: B1

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 MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016081162

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1589568

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231120

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231019

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231119

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231020

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2959426

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20240226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016081162

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230901

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230901

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

26N No opposition filed

Effective date: 20240422

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230901

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230930

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230719

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20240820

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160901

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250929

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20250926

Year of fee payment: 10

Ref country code: IT

Payment date: 20250919

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250929

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250925

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20251001

Year of fee payment: 10