EP2769009A1 - Brush containing mono-filaments containing polyamide-410 - Google Patents

Brush containing mono-filaments containing polyamide-410

Info

Publication number
EP2769009A1
EP2769009A1 EP12772338.5A EP12772338A EP2769009A1 EP 2769009 A1 EP2769009 A1 EP 2769009A1 EP 12772338 A EP12772338 A EP 12772338A EP 2769009 A1 EP2769009 A1 EP 2769009A1
Authority
EP
European Patent Office
Prior art keywords
mono
polyamide
filaments
filament
brush
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
EP12772338.5A
Other languages
German (de)
French (fr)
Other versions
EP2769009B1 (en
Inventor
Sanjay Mathur
DE Jan KROON
Godefridus Bernardus Wilhelmus Leonardus LIGTHART
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.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to EP12772338.5A priority Critical patent/EP2769009B1/en
Publication of EP2769009A1 publication Critical patent/EP2769009A1/en
Application granted granted Critical
Publication of EP2769009B1 publication Critical patent/EP2769009B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A46D1/02—Bristles details
    • A46D1/0207—Bristles characterised by the choice of material, e.g. metal
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers

Definitions

  • This invention relates to a brush containing mono-filaments containing polyamide, especially a toothbrush containing these mono-filaments.
  • a brush containing mono-filaments containing polyamide, also known as nylon, is known and is for example described in GB800610A.
  • GB800610A describes a brush containing nylon mono-filaments and mentions mono-filaments of nylon-66 and nylon-610 for this application.
  • so-called "wet bend recovery” is an essential feature for a mono-filament.
  • "Wet bend recovery” is the ability of a material to return to its original shape after deformation while being wet. If the wet bend recovery is high, this means that the mono-filaments easily return to its original shape, which allows for example longer use of a brush containing these mono-filaments.
  • An object of the present invention is to thus to provide a brush containing mono-filaments of polyamide, which mono-filaments exhibit high wet bend recovery.
  • Polyamide-410 is here understood to be a polyamide containing monomer units derived from a dicarboxylic acid with 10 carbon atoms and a diamine with 4 carbon atoms.
  • the dicarboxylic acid 1 ,10 decandioic acid is used.
  • the diamine preferably 1 ,4-butanediamine is used.
  • PA-410 may comprise up to 30 wt. % of further monomeric units, for example dicarboxylic acids with less than 10 carbon atoms or diamines with more than 4 carbon atoms, with respect to the total amount of polyamide.
  • the PA-410 used in the mono-filament used in the brush according to the invention comprises at least 80 wt.
  • % with respect to the total amount of polyamide of the dicarboxylic acid with a chain of 10 carbon atoms between the carboxylic acid groups and a the diamine with 4 carbon atoms, more preferably at least 90 wt. % with respect to the total amount of polyamide, even more preferably at least 95 wt. % with respect to the total amount of polyamide, even more preferably at least 99 wt. %, most preferably at least 99.9 wt. %, with respect to the total amount of polyamide.
  • the mono-filament used in the brush according to the invention preferably is produced from a polyamide comprising at least 40 wt% of polyamide-410 with respect to the total amount of polyamide, more preferably at least 50 wt % of polyamide-410, and most preferred at least 60 wt% of polyamide-410.
  • the polyamide consists essentially of PA-410.
  • the monofilament containing the polyamide contains no further polymer.
  • the mono-filament according to the invention is no longer fully based on fossil carbon, since polyamide-410 may be at least partly based on renewable resources. This is especially an advantage, even if the polyamide of the mono-filament only contains a fraction of polyamide-410 and also a further polymer.
  • Employing PA410 in mono-filaments which is at least partly based on monomers originating from natural resources already provides an important decrease in the production of green house gases and C0 2 in particular for mono-filament industry and its applications thereof.
  • a further advantage of the mono-filament used in the brush according to the invention is that the stiffness retention when wet is good.
  • “Stiffness retention when wet” is here understood to be the ability to retain stiffness, usually measured as tensile modulus in MPa under humid conditions, i.e. under 50% relative humidity, compared to dry conditions, such as for example 0% relative humidity according to IS05271A.
  • a high stiffness retention when wet allows for pleasant brushing experience when applied in a toothbrush, as this is usually performed under wet conditions.
  • the mono-filament can thus advantageously be employed in bristles for toothbrushes, as it combines very good wet bend recovery with good stiffness retention when wet.
  • Polyamide-410 can be prepared as for example described in the examples.
  • the viscosity number (VN) of polyamide-410 is at least 100 ml/g, more preferably at least 1 10 ml/g, even more preferably at least 120 ml/g and most preferred at least 140 ml/g. Higher viscosities will lead to improved mechanical properties of the mono-filaments.
  • the viscosity number is at most 200 ml/g. If the viscosity number is too high, the throughput of the spinning machine is limited.
  • the viscosity number is measured according to ISO 307, version 2007 in formic acid (90 wt%) in a concentration of 0.005 g/ml at 25 °C.
  • the mono-filaments used in the brush according to the invention preferably have an average diameter of between 1 micrometer and 1.5 mm.
  • the mono-filaments have an average diameter of between 15 micrometer and 1 .2 mm.
  • Mono-filaments can be prepared by melting the polyamide and subsequently pushing it through a die. After leaving the die, the mono-filament is cooled down, preferably in a quench bath. In order to produce high quality mono-filaments, it is desirable to keep the threads separated from each other. This may be effected by a separating guide or a comb.
  • the length of the air gap i.e. the distance between the spinning plate and water surface, can influence the surface of the mono-filaments and the mechanical properties.
  • either at least a single or at least a two stage drawing step can be performed in for example a hot water bath or in a hot air or infra-red oven.
  • the second stage of a two stage drawing process usually takes place in a hot air oven and requires temperatures which are higher than the temperature in the first stage. It is preferable to use a water bath for the first stage if very close tolerances are required.
  • the drawing ratio and the applied temperatures influence the physical structure of the molecules in a mono-filament.
  • properties such as tensile strength, elongation, e-modulus, heat resistance and dyeability with non- reactive dyestuffs, depend on the physical structure, the drawing process has a wide and varying influence on the properties of the mono-filament.
  • mono-filament properties such as, heat stability, tensile strength, elongation at break and dyeability can be trimmed to the desired level by fixation or relaxation.
  • the percentage of relaxation allowed and the applied temperatures strongly depend on the final property requirements.
  • the temperature of the mono-filament during the third step should at least equal, but more usually exceed, the temperature acquired during drawing. Temperature setting for the oven are very dependent on line speed, monofilament diameter, oven length, and air velocity.
  • the mono-filament used in the brush according to the invention preferably comprises pigments, such as titanium oxide, to give the mono-filament a white appearance.
  • the mono-filament according to the invention may also comprise lubricants, such as ethylene bis stearylamine (EBA), for higher transparancy.
  • EBA ethylene bis stearylamine
  • the mono-filament can be advantageously employed for bristles, preferably bristles for toothbrushes.
  • the invention thus also relates to a toothbrush comprising the mono-filaments.
  • the toothbrush combines good wet bend recovery and stiffness retention when wet. This allows longer use of the toothbrush before it needs to be discarded.
  • it also is advantageous in C0 2 -reduction, both from a longer use, as well as at least part of the toothbrush is made of renewable sources. Examples
  • a 45% 410-salt solution was prepared. At 65 °C 230 ml of a 67.5% 1 ,4-diaminobutane solution was added to 540 ml of water prior to adding 348.2 g of solid 1 ,10-decanedioic acid. The maximum pressure of the reactor was set to 2 barA. The salt solution was heated up to 153 °C in 60 minutes. During this process the excess of water was distilled off until a water concentration of 10% was reached at 153 °C. The pressure of the reactor was set at 12 barA. The 410-salt solution was heated up in 15 minutes to reach a pressure of 12 barA, thereby polymerizing the salt solution.
  • the reactor While maintaining 12 barA, more water is distilled off until a polymer melt was obtained and the temperature reached 250 °C.
  • the reactor was depressurized to 1.02 barA while heating up to 265 °C in 60 minutes, while further polymerizing the polymer melt.
  • the polymer melt was further heated to 290 °C and kept at that temperature and 1 .02 barA for 16 hours.
  • the water of the polymer melt was stripped off with a small nitrogen flow.
  • the reactor was emptied into a water bath to get a polymer strand, which was off-line cut into granules.
  • the PA-410 polymer had a solution viscosity of 179 ml/g in 90% formic acid.
  • Mono-filaments with a diameter of 0.2 mm were obtained by melting the PA-410 to a temperature of 270 °C and subsequently pressing it through a die.
  • Viscosity number VN
  • Bend recovery tests were performed on various mono filaments with the so called pinch hole bend recovery method.
  • This method uses metal plates holes of various sizes (plates A, B and C with holes of 1 .5 mm, 2.5 mm and 3.5 mm,
  • the metal plate including the mono-filament was immersed in water at of 50 ⁇ 2 °C for 2 minutes, then in water at of 20 ⁇ 2 °C for 30 seconds. The plate was removed from the water and the mono-filament from the hole. The mono-filament was placed in a petri dish full of water at of 20 ⁇ 2 °C. After 15 minutes of immersion, the mono-filament was removed and the included angle was measured, while ensuring that the mono-filament was lying flat on a smooth surface.
  • Results are shown in Table 1 .
  • Table 1 surprisingly shows that PA-410 exhibits high percentage of recovery for all three diameters, especially compared to PA-610 and PA-612, which are usually employed in filaments for tooth brushes. Mandrel bend recovery tests
  • mandrel bend recovery tests were performed, in which a filament was attached to and wound ten times around a mandrel with a diameter of 2.5 mm. After this the filament around the mandrel was left in this position for 1 hour at room temperature, after which the filament was cut off from the mandrel and allowed to recover in a dish of water for one hour.
  • the mandrel bend recovery expressed in %, is the number of turns wrapped on the mandrel versus the number of turns in the fiber at the end of recovery period. Results are shown in Table 2. Table 2 Mandrel bend recovery tests
  • Stiffness retention is calculated by dividing tensile modulus conditioned and tensile modulus dry x 100%.
  • Stiffness retention for PA-410 is shown to be higher than for PA-6 and PA-66. Due to the intrinsically higher stiffness of PA-410 however, the stiffness under wet conditions of PA-410 is also higher than the stiffness of PA-610- and PA-612. These data, combined with the wet bend recovery results show that mono-filaments according to the invention exhibit best combination of these properties, as required for applications in for example bristles for tooth brushes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Brushes (AREA)
  • Artificial Filaments (AREA)

Abstract

This invention relates to a brush containing mono-filaments containing a polyamide which comprises polyamide-410. Preferably, the brush is a toothbrush.

Description

BRUSH CONTAINING MONO-FILAMENTS CONTAINING POLYAMIDE-410
This invention relates to a brush containing mono-filaments containing polyamide, especially a toothbrush containing these mono-filaments.
A brush containing mono-filaments containing polyamide, also known as nylon, is known and is for example described in GB800610A. GB800610A describes a brush containing nylon mono-filaments and mentions mono-filaments of nylon-66 and nylon-610 for this application. For application in a brush and especially in a toothbrush, so-called "wet bend recovery" is an essential feature for a mono-filament. "Wet bend recovery" is the ability of a material to return to its original shape after deformation while being wet. If the wet bend recovery is high, this means that the mono-filaments easily return to its original shape, which allows for example longer use of a brush containing these mono-filaments.
An object of the present invention is to thus to provide a brush containing mono-filaments of polyamide, which mono-filaments exhibit high wet bend recovery.
This object surprisingly has been achieved by providing a brush containing mono-filaments containing a polyamide which comprises polyamide-410. Monofilaments containing a polyamide which comprises PA-410 are known from WO 00/09586. However in WO 00/09586 nothing is said about the properties of the filaments under wet conditions, nor about their use in brushes.
Polyamide-410
Polyamide-410 is here understood to be a polyamide containing monomer units derived from a dicarboxylic acid with 10 carbon atoms and a diamine with 4 carbon atoms. Preferably as the dicarboxylic acid 1 ,10 decandioic acid is used. As the diamine preferably 1 ,4-butanediamine is used. PA-410 may comprise up to 30 wt. % of further monomeric units, for example dicarboxylic acids with less than 10 carbon atoms or diamines with more than 4 carbon atoms, with respect to the total amount of polyamide. Preferably the PA-410 used in the mono-filament used in the brush according to the invention comprises at least 80 wt. % with respect to the total amount of polyamide of the dicarboxylic acid with a chain of 10 carbon atoms between the carboxylic acid groups and a the diamine with 4 carbon atoms, more preferably at least 90 wt. % with respect to the total amount of polyamide, even more preferably at least 95 wt. % with respect to the total amount of polyamide, even more preferably at least 99 wt. %, most preferably at least 99.9 wt. %, with respect to the total amount of polyamide.
The mono-filament used in the brush according to the invention preferably is produced from a polyamide comprising at least 40 wt% of polyamide-410 with respect to the total amount of polyamide, more preferably at least 50 wt % of polyamide-410, and most preferred at least 60 wt% of polyamide-410. Most preferably the polyamide consists essentially of PA-410. In a preferred embodiment the monofilament containing the polyamide contains no further polymer.
Another important improvement is that the mono-filament according to the invention is no longer fully based on fossil carbon, since polyamide-410 may be at least partly based on renewable resources. This is especially an advantage, even if the polyamide of the mono-filament only contains a fraction of polyamide-410 and also a further polymer. Employing PA410 in mono-filaments which is at least partly based on monomers originating from natural resources already provides an important decrease in the production of green house gases and C02 in particular for mono-filament industry and its applications thereof. A further advantage of the mono-filament used in the brush according to the invention is that the stiffness retention when wet is good. "Stiffness retention when wet" is here understood to be the ability to retain stiffness, usually measured as tensile modulus in MPa under humid conditions, i.e. under 50% relative humidity, compared to dry conditions, such as for example 0% relative humidity according to IS05271A. A high stiffness retention when wet allows for pleasant brushing experience when applied in a toothbrush, as this is usually performed under wet conditions. The mono-filament can thus advantageously be employed in bristles for toothbrushes, as it combines very good wet bend recovery with good stiffness retention when wet.
Polyamide-410 can be prepared as for example described in the examples. For mono-filaments, preferably the viscosity number (VN) of polyamide-410 is at least 100 ml/g, more preferably at least 1 10 ml/g, even more preferably at least 120 ml/g and most preferred at least 140 ml/g. Higher viscosities will lead to improved mechanical properties of the mono-filaments. Preferably the viscosity number is at most 200 ml/g. If the viscosity number is too high, the throughput of the spinning machine is limited. The viscosity number is measured according to ISO 307, version 2007 in formic acid (90 wt%) in a concentration of 0.005 g/ml at 25 °C. Mono-filaments
The mono-filaments used in the brush according to the invention preferably have an average diameter of between 1 micrometer and 1.5 mm. Preferably, the mono-filaments have an average diameter of between 15 micrometer and 1 .2 mm. Mono-filaments can be prepared by melting the polyamide and subsequently pushing it through a die. After leaving the die, the mono-filament is cooled down, preferably in a quench bath. In order to produce high quality mono-filaments, it is desirable to keep the threads separated from each other. This may be effected by a separating guide or a comb. The length of the air gap, i.e. the distance between the spinning plate and water surface, can influence the surface of the mono-filaments and the mechanical properties. Dependent upon the properties required of the mono-filament, either at least a single or at least a two stage drawing step can be performed in for example a hot water bath or in a hot air or infra-red oven. The second stage of a two stage drawing process usually takes place in a hot air oven and requires temperatures which are higher than the temperature in the first stage. It is preferable to use a water bath for the first stage if very close tolerances are required.
The drawing ratio and the applied temperatures influence the physical structure of the molecules in a mono-filament. As a number of properties such as tensile strength, elongation, e-modulus, heat resistance and dyeability with non- reactive dyestuffs, depend on the physical structure, the drawing process has a wide and varying influence on the properties of the mono-filament.
As an optional third step mono-filament properties such as, heat stability, tensile strength, elongation at break and dyeability can be trimmed to the desired level by fixation or relaxation. The percentage of relaxation allowed and the applied temperatures strongly depend on the final property requirements. To achieve proper fixation/relaxation the temperature of the mono-filament during the third step should at least equal, but more usually exceed, the temperature acquired during drawing. Temperature setting for the oven are very dependent on line speed, monofilament diameter, oven length, and air velocity.
The mono-filament used in the brush according to the invention preferably comprises pigments, such as titanium oxide, to give the mono-filament a white appearance. The mono-filament according to the invention may also comprise lubricants, such as ethylene bis stearylamine (EBA), for higher transparancy.
The mono-filament can be advantageously employed for bristles, preferably bristles for toothbrushes. The invention thus also relates to a toothbrush comprising the mono-filaments. The toothbrush combines good wet bend recovery and stiffness retention when wet. This allows longer use of the toothbrush before it needs to be discarded. Moreover, it also is advantageous in C02-reduction, both from a longer use, as well as at least part of the toothbrush is made of renewable sources. Examples
Preparation of PA-410
In an inert 2L autoclave reactor a 45% 410-salt solution was prepared. At 65 °C 230 ml of a 67.5% 1 ,4-diaminobutane solution was added to 540 ml of water prior to adding 348.2 g of solid 1 ,10-decanedioic acid. The maximum pressure of the reactor was set to 2 barA. The salt solution was heated up to 153 °C in 60 minutes. During this process the excess of water was distilled off until a water concentration of 10% was reached at 153 °C. The pressure of the reactor was set at 12 barA. The 410-salt solution was heated up in 15 minutes to reach a pressure of 12 barA, thereby polymerizing the salt solution. While maintaining 12 barA, more water is distilled off until a polymer melt was obtained and the temperature reached 250 °C. At 250 °C, the reactor was depressurized to 1.02 barA while heating up to 265 °C in 60 minutes, while further polymerizing the polymer melt. The polymer melt was further heated to 290 °C and kept at that temperature and 1 .02 barA for 16 hours. The water of the polymer melt was stripped off with a small nitrogen flow. After the polycondensation phase the reactor was emptied into a water bath to get a polymer strand, which was off-line cut into granules. The PA-410 polymer had a solution viscosity of 179 ml/g in 90% formic acid.
Mono-filaments with a diameter of 0.2 mm were obtained by melting the PA-410 to a temperature of 270 °C and subsequently pressing it through a die.
Measurements
Viscosity number (VN).
The viscosity number was determined according to ISO 307, version 2007, by dissolving the PA-410 samples in formic acid (90 wt. %) in a concentration of 0.005 g/ml and determining of the viscosity number by an Ubelohde viscometer by measuring at 25 °C the times of flow of the solvent (tO) and of the solution (t1 ) and calculating the viscosity number by the formulae VN = [(t1/t0) - 1 ] x 200 ml/gram.
Pinch bend recovery tests
Bend recovery tests were performed on various mono filaments with the so called pinch hole bend recovery method. This method uses metal plates holes of various sizes (plates A, B and C with holes of 1 .5 mm, 2.5 mm and 3.5 mm,
respectively). The following procedure was applied: Mono-filaments were immersed in water at a temperature of 20±1 °C for 18 hours. The mono-filament was centrally laid across the hole and gently pressed into the hole using a blunt instrument, on order not to kink the mono-filament. The mono-filament was positioned in such a way that it did not protrude by more than the radius of the hole.
The metal plate including the mono-filament was immersed in water at of 50±2 °C for 2 minutes, then in water at of 20±2 °C for 30 seconds. The plate was removed from the water and the mono-filament from the hole. The mono-filament was placed in a petri dish full of water at of 20±2 °C. After 15 minutes of immersion, the mono-filament was removed and the included angle was measured, while ensuring that the mono-filament was lying flat on a smooth surface.
The percentage recovery was calculated using formula [1 ]:
Recovery = Included angle x 100/180 % [formula 1 ]
Results are shown in Table 1 .
Table 1 Pinch bend recovery tests
Table 1 surprisingly shows that PA-410 exhibits high percentage of recovery for all three diameters, especially compared to PA-610 and PA-612, which are usually employed in filaments for tooth brushes. Mandrel bend recovery tests
Also mandrel bend recovery tests were performed, in which a filament was attached to and wound ten times around a mandrel with a diameter of 2.5 mm. After this the filament around the mandrel was left in this position for 1 hour at room temperature, after which the filament was cut off from the mandrel and allowed to recover in a dish of water for one hour. The mandrel bend recovery, expressed in %, is the number of turns wrapped on the mandrel versus the number of turns in the fiber at the end of recovery period. Results are shown in Table 2. Table 2 Mandrel bend recovery tests
Also these tests show that mono-filaments from PA-410 show very high recovery, especially compared to polyamide-610 and polyamide-612, which are usually employed in filaments for tooth brushes.
Tensile modulus was measured according to ISO 527 1A for PA-410 plates and compared to other polyamides. Results are shown in Table 3. Table 3 Tensile modulus and stiffness retention
* at 50% relative humidity at 23 °C; Stiffness retention is calculated by dividing tensile modulus conditioned and tensile modulus dry x 100%.
Stiffness retention for PA-410 is shown to be higher than for PA-6 and PA-66. Due to the intrinsically higher stiffness of PA-410 however, the stiffness under wet conditions of PA-410 is also higher than the stiffness of PA-610- and PA-612. These data, combined with the wet bend recovery results show that mono-filaments according to the invention exhibit best combination of these properties, as required for applications in for example bristles for tooth brushes.

Claims

1 . Brush containing a mono-filament containing a polyamide which comprises polyamide-410.
2. Brush according to claim 1 , wherein the polyamide comprises polyamide-410 in an amount of at least 40 wt% based on the total amount of polyamide.
3. Brush according to claim 1 , wherein the amount of polyamide-410 is at least 50 wt% based on the total amount of polyamide.
4. Brush according to claim 1 wherein the polyamide consists essentially of polyamide-410.
5. Brush according to any of the claims above, wherein the viscosity number of polyamide-410 is at least 100 ml/g.
6. Brush according to any of the claims above, wherein the viscosity number of polyamide-410 is at least 120 ml/g.
7. Brush according to any of the claims above, wherein the viscosity number of polyamide-410 is at least 140 ml/g.
8. Brush according to any one of the claims above, wherein the mono-filaments further comprise titanium oxide.
9. Brush according to any one of the claims above, wherein the brush is a toothbrush.
EP12772338.5A 2011-10-17 2012-10-16 Brush containing mono-filaments containing polyamide-410 Active EP2769009B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12772338.5A EP2769009B1 (en) 2011-10-17 2012-10-16 Brush containing mono-filaments containing polyamide-410

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11185487 2011-10-17
EP12772338.5A EP2769009B1 (en) 2011-10-17 2012-10-16 Brush containing mono-filaments containing polyamide-410
PCT/EP2012/070487 WO2013057102A1 (en) 2011-10-17 2012-10-16 Brush containing mono-filaments containing polyamide-410

Publications (2)

Publication Number Publication Date
EP2769009A1 true EP2769009A1 (en) 2014-08-27
EP2769009B1 EP2769009B1 (en) 2016-12-21

Family

ID=47018229

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12772338.5A Active EP2769009B1 (en) 2011-10-17 2012-10-16 Brush containing mono-filaments containing polyamide-410

Country Status (8)

Country Link
US (1) US20140259487A1 (en)
EP (1) EP2769009B1 (en)
JP (1) JP6236666B2 (en)
CN (1) CN103890248A (en)
BR (1) BR112014009132A8 (en)
CA (1) CA2851766A1 (en)
MX (1) MX2014004568A (en)
WO (1) WO2013057102A1 (en)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2836516A (en) 1955-05-02 1958-05-27 Weco Products Company Method of treating nylon bristles and products produced thereby
JPS61231214A (en) * 1985-04-05 1986-10-15 Toray Monofilament Co Ltd Polyamide monofilament
DE19640726A1 (en) * 1996-10-02 1998-04-23 Braun Ag Bristle for a toothbrush
JPH10201538A (en) * 1997-01-20 1998-08-04 Lion Corp toothbrush
NL1009846C2 (en) * 1998-08-12 2000-02-15 Dsm Nv Polyamide product from polytetramethylene diacid amide.
JP3685758B2 (en) * 2000-03-30 2005-08-24 旭化成せんい株式会社 Monofilament yarn and method for producing the same
US8695148B2 (en) * 2002-08-09 2014-04-15 Colgate-Palmolive Company Toothbrush
CN101048430A (en) * 2004-09-30 2007-10-03 科聚亚公司 Improved bromostyrene polymers with controlled molecular weight
US7550551B2 (en) * 2006-08-22 2009-06-23 Chemtura Corporation Brominated flame retardant
JP5760405B2 (en) * 2009-11-30 2015-08-12 東レ株式会社 Polyamide resin composition and molded article comprising the same
JP2011200352A (en) * 2010-03-25 2011-10-13 Toray Monofilament Co Ltd Tapered bristle and brush
WO2011138397A1 (en) * 2010-05-06 2011-11-10 Dsm Ip Assets B.V. Process for preparing pa-4x, and pa-410 obtainable by the process
US8845934B2 (en) * 2011-09-12 2014-09-30 Sabic Global Technologies B.V. Compatibilized biopolyamide-poly(arylene ether) thermoplastic resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013057102A1 *

Also Published As

Publication number Publication date
US20140259487A1 (en) 2014-09-18
JP2014528338A (en) 2014-10-27
BR112014009132A2 (en) 2017-06-13
CA2851766A1 (en) 2013-04-25
EP2769009B1 (en) 2016-12-21
JP6236666B2 (en) 2017-11-29
BR112014009132A8 (en) 2017-06-20
CN103890248A (en) 2014-06-25
WO2013057102A1 (en) 2013-04-25
MX2014004568A (en) 2014-07-09

Similar Documents

Publication Publication Date Title
US2226529A (en) Synthetic filament
TWI604013B (en) Polyamide resin fiber, manufacturing method of polyamine resin fiber, polyamine resin composition, woven fabric and woven fabric
CN105986327B (en) Delustered polyamide 56 fiber and method for producing same
TWI660978B (en) Polyamide fibers
JP7221386B2 (en) Stain-resistant polyamide polymer obtained through advanced end group capping
EP3945103B1 (en) Polyamide for textile application
JP4769279B2 (en) Polyamide latent crimped yarn
EP2769009B1 (en) Brush containing mono-filaments containing polyamide-410
CN113453573B (en) Core-sheath composite fiber for artificial hair, headwear containing same, and manufacturing method thereof
JPWO2018037706A1 (en) Artificial hair fibers
JP2019065433A (en) Fiber for artificial hair, artificial hair and hair product
US20220372669A1 (en) Core-sheath composite fiber for artificial hair, headwear product including same, and production method for same
TW396216B (en) Longlines
CN113195807B (en) Artificial hair fibers and head accessories
JP2013204176A (en) Thick monofilament made of thermoplastic resin
JP5128986B2 (en) Polyamide fiber
JPH03234809A (en) Aromatic polyamide monifilament
JP2014167184A (en) Crimped yarn
RU2300581C2 (en) Method for producing of copolyamidobenzimidazole-based threads using alkaline processing
KR20140023816A (en) Core-shell filament method, toothbrush having mono filament and method for preparing the same
JPS61231214A (en) Polyamide monofilament
JP2004308020A (en) Core-sheath composite polyamide monofilament
JP2012207347A (en) Monofilament-like article
JPWO2010119756A1 (en) Pseudo monofilament yarn and manufacturing method thereof
WO2024225284A1 (en) Carrier for biological treatment

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20140410

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

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20150513

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160927

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 855607

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012026875

Country of ref document: DE

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

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: 20161221

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: MG4D

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: 20161221

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: 20170322

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: 20161221

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: 20170321

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 855607

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161221

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

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: 20161221

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: 20161221

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: 20161221

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

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: 20161221

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: 20161221

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: 20161221

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: 20170421

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: 20161221

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: 20170321

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: 20161221

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: 20161221

Ref country code: BE

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: 20161221

Ref country code: ES

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: 20161221

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: 20161221

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: 20170421

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012026875

Country of ref document: DE

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

26N No opposition filed

Effective date: 20170922

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

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: 20161221

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

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: 20161221

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

Ref country code: GB

Payment date: 20171011

Year of fee payment: 6

Ref country code: IT

Payment date: 20171024

Year of fee payment: 6

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

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: 20161221

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: LU

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

Effective date: 20171016

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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

Ref country code: MT

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

Effective date: 20171016

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: 20171016

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20181016

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: 20121016

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

Ref country code: IT

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

Effective date: 20181016

Ref country code: CY

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

Effective date: 20161221

Ref country code: GB

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

Effective date: 20181016

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

Ref country code: MK

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: 20161221

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

Ref country code: TR

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: 20161221

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

Ref country code: AL

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: 20161221

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230520

REG Reference to a national code

Ref country code: NL

Ref legal event code: PD

Owner name: ENVALIOR B.V.; NL

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: DSM IP ASSETS B.V.

Effective date: 20250905

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

Ref country code: NL

Payment date: 20250826

Year of fee payment: 14

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602012026875

Country of ref document: DE

Owner name: ENVALIOR B.V., NL

Free format text: FORMER OWNER: DSM IP ASSETS B.V., HEERLEN, NL

REG Reference to a national code

Ref country code: CH

Ref legal event code: U11

Free format text: ST27 STATUS EVENT CODE: U-0-0-U10-U11 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20251101

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

Ref country code: DE

Payment date: 20250930

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20251008

Year of fee payment: 14

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

Ref country code: CH

Payment date: 20251101

Year of fee payment: 14