EP2597980B1 - Fluorescent fibres and their use - Google Patents
Fluorescent fibres and their use Download PDFInfo
- Publication number
- EP2597980B1 EP2597980B1 EP20110748870 EP11748870A EP2597980B1 EP 2597980 B1 EP2597980 B1 EP 2597980B1 EP 20110748870 EP20110748870 EP 20110748870 EP 11748870 A EP11748870 A EP 11748870A EP 2597980 B1 EP2597980 B1 EP 2597980B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibres
- flame
- resistant
- cellulosic regenerated
- regenerated fibre
- 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.)
- Not-in-force
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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/16—Addition of dyes to the spinning solution
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3976—Including strand which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous composition, water solubility, heat shrinkability, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
- Y10T442/45—Knit fabric is characterized by a particular or differential knit pattern other than open knit fabric or a fabric in which the strand denier is specified
- Y10T442/456—Including additional strand inserted within knit fabric
- Y10T442/463—Warp knit insert strand
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/696—Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]
Definitions
- the present invention relates to fluorescent cellulosic regenerated fibres for use in reflective clothing such as are for example described in standard EN 471, EN 1150, CAN/CSA Z96-02, ANSI/ISEA 207-2006 and BS EN 471:2003, their use for the production of yarns and textile farbrics and a process for the production of these fibres.
- EN 471 deals exclusively with the reflective effect of personal protective equipment, in particular with reflective clothing.
- reflective clothing comprises a fluorescent background material and a retro-reflective material.
- a material is described as a fluorescent material in accordance with the definition in EN 471 which emits rather than absorbs rays at a longer wave length; in the text which follows the term high-visibility material is also used.
- the present invention refers to the fluorescent background material but not to the retro-reflective materials.
- EN 1150 deals with reflective clothing for non-professional use.
- the difference between standard EN 1150 in comparison to standard EN 471 is the defined area of the fluorescent material in the clothing.
- 8 different fluorescent colours are allowed in EN 1150 (in EN 471 only yellow, orange and red fluorescent colours are allowed).
- the CAN/CSA Z96-02 standard is the Canadian standard for high-visibility reflective clothing.
- the clothing is divided into three categories depending on the application.
- the demands of the area of the fluorescent material and the colour coordinates after radiation correspond to standard EN 471.
- the American standard ANSI/ISEA 207-2006 defines the requirements for protective clothing depending on the application. I.e. the requirements for protective clothing for the police, rescue forces and construction workers are different. The clothing for these three groups differs in terms of the requirements for the high-visibility background material.
- Cellulosic regenerated fibres can indeed be dyed with fluorescent dyestuffs using the conventional bath process. But the fibres dyed in this way do not satisfy the light fastness requirements (greater than 4, measured according to ISO 105-B02). Following xenon exposure, they are considerably bleached and display a marked change in the colour shade and a considerable reduction in the colour intensity which for example can be depicted as a change in the coordinates of the colour space.
- the task was to make a fibre available which on the one hand satisfies the requirements of protective and reflective clothing, as for example are described in EN 471 and CAN/CSA Z96-02, and which on the other hand increases the wear comfort and safety aspects of this clothing with a justifiable economic effort. It should, therefore, be possible to produce the protective and reflective clothing from a fibre of this kind without adding any other fibre types.
- fluorescent pigment in particular a fluorescent pigment is to be understood which reveals a separate colour which can be discerned by the human eye in the daylight. If this were not the case, the purpose of the invention - the warning effect - would naturally not be attained. In this respect the pigments would clearly have to differ from purely optical brighteners.
- the cellulosic regenerated fibres in accordance with the invention reveal a light density factor, measured according to EN IS0 471 of more than 0.7 for yellow fibres, more than 0.4 for orange fibres and more than 0.25 for red fibres and only slightly changed colour coordinates following xenon test exposure. In the same way they reveal a light density factor, measured according to CAN/CSA Z96-02 of more than 0.38 for fluorescent yellow-green fibres, more than 0.20 for fluorescent orange-red fibres and more than 0.125 for fluorescent red fibres and only a few changed colour coordinates after xenon test exposure.
- the fibres also satisfy the other values demanded by EN 471 and similar norms with regard to rub fastness, perspiration fastness, wash fastness, dry cleaning fastness, hypochlorite bleaching fastness and fastness to ironing.
- the spun-dyed cellulosic regenerated fibres in accordance with the invention can for example be produced according to a viscose process, a modified viscose process (e.g. the Modal process, a zinc-free viscose process with al-sulphate, the polynosic process etc.) as well as according to a solvent spinning process which is produced with organic solvents such as melted aqueous amine oxides or what are known as ionic liquids.
- the fibres can be designated accordingly as viscose, Modal, polynosic respectively Lyocell.
- other alternative processes such as the Carbamat or the Cupro process are in principle possible.
- colour pigments In general the products known to the expert for the spin dyeing of corresponding fibres are suitable as colour pigments.
- the colour pigments Aquamarine Blue 3G from Messrs. Tennents Textile Colors (Cu-phthalocyanide complexes in the form of chromophores), Aquarine Yellow 10G (Messrs. Tennants Textile Colors, Monoazo dye) and Aquis Orange 0341 (Messrs. Heubach, diarylid pyrazolon dyestuff) are suitable for blue, yellow respectively orange fluorescent fibres.
- the luminous pigments preferably contain amino-modified benzoguanamines as chromophore groups.
- the yellow pigment Lunar Yellow 27 and the orange pigment Blaze 5 from the RTS series of Messrs. Swada are suitable with particle diameters of 3 - 4 ⁇ m. These substances are sufficiently stable in spin dyeing conditions i.e. spinning solutions respectively spinning baths with a very high respectively very low pH value or of a high temperature.
- the light fastnesses of the fibres in accordance with the invention can be further improved by the addition of stabilisers.
- stabilisers In principle there are two types of stabilisers which can be used in fluorescent fibres and the efficiency mechanism of which is different.
- UV absorbers and radical quenchers.
- the UV absorbers With the UV absorbers, the light energy is converted into heat and is then drawn off as heat.
- these substances are either organic, conjugated aromatic compounds (benzophenone, triazine, triazole and oxal-anilide) or anorganic substances (for example nano-Zn0 and nano-Ti0 2 ) which have an effect via the mechanism of light dispersion.
- Radical quenchers are e.g. so-called HALS products (Hindered Amine Light Stabiliser).
- the flame-resistant fibre is produced by the additional incorporation of a pigment-shaped flame-resistant agent.
- organophosphorous compounds come into question as pigment-shaped flame-resistant agents apart from other types.
- the highly suitable and well-known 2,2'-oxybis [5,5 dimethyl-1,3,2, dioxaphosphorinan] 2,2' disulfide available under the trade name of Exolit respectively Sandoflam.
- the cellulosic regenerated fibre is finished in an antibacterial form. In this respect the expert can use the substances known to him.
- a yarn of this kind in accordance with the invention can also contain fibres of another origin such as for example (flame-resistant) polyester, Modacryl, para- and meta-aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®)), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stable polyacrylnitrile fibres (PANOX®) and electrically conductive fibres as well as blends of these fibres.
- the blending partners can likewise have a high-visibility finish.
- this textile can also contain other fibres, for example (flame-resistant) polyester, Modacryl, para- and meta- aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stabilised polyacrylnitrile fibres (PANOX®) and electrically conductive fibres and blends of these fibres.
- PPS polyphenylensulfide
- PTFE polytetrafluorethylene
- the other fibres can likewise have a high-visibility finish.
- the textile fabric is preferably a woven, knitted or warp knitted fabric but can basically also be a fleece (non-woven).
- the blend of the fibres in accordance with the invention is with other fibres either by blending prior to the production of yarns, the so-called intimate blend, or by the joint use of respectively pure yarns of the different fibre types when weaving, knitting or knitting is possible.
- a spun-dyed viscose fibre 1.7 dtex was produced with a content of 10.5 weight percentage of luminous pigment orange (Messrs. SWADA, RTS series, Blaze 5) and 1.7 weight percentage colour pigment orange Aquis Orange 0341 (Messrs. Heubach, diarylide- pyrazolon (in relation to the cellulose mass).
- the luminous fibres with the incorporated colour pigments and luminous pigments remain stable following xenon test exposure (table 1).
- the colour coordinates remain within the given range.
- the colour density factor drops slightly.
- the light stability is high and the colour remains intact after washing.
- the friction fastnesses (dry and wet) comply with the values in the standard. From this we can conclude that these luminous fibres for protective textiles satisfy standard EN 471 in all categories.
- a spun-dyed viscose fibre 1.7 dtex contains 12% luminous pigment orange (Messrs. SWADA, RTS series blaze 5) (in relation to the cellulose mass). In this case no colour pigments were used.
- Example 2 shows (table 1) that the luminous fibres, which only contain luminous pigment, with spun-in luminous pigments cannot satisfy standard EN 471 since the colour coordinates lie outside the given range and the light density factor drops significantly following UV exposure.
- table 1 the light fastnesses are also given. The measured value of 2 for the light fastness of a fibre in accordance with the state of the art of technology is, therefore, too low to satisfy the standard.
- the yellow flame-resistant high-visibility fibres reveal excellent results.
- the light density factor of the flame-resistant high-visibility fibres is extremely high (0.98) and the value remains much higher after exposure (0.81) than is demanded in the standard (0.7 for yellow fibres).
- the colour coordinates after exposure are almost the same as before exposure which indicates a high-quality luminous fibre. All the fastness tests reveal excellent results which meet all the demands of standard EN ISO 471.
- a spun-dyed viscose fibre with an individual titre of 1.7 dtex was produced with a content of 11.0 weight percentage luminous pigment blue (Cornet blue 60, Messrs. SWADA) and 3.2 weight percentage colour pigment blue (Aquarine Blue 3G, Messrs. Tennents Textile Colors, chromophore groups are Cu-phthalocyanide complexes).
- the fastnesses are listed in table 1.
- the polyester overdyeing fastness of the blue high-visibility fibres produced in accordance with the invention for non-professional use displays very good values;.the colour fastness is > 4 (table 1).
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Knitting Of Fabric (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
- Woven Fabrics (AREA)
Description
- The present invention relates to fluorescent cellulosic regenerated fibres for use in reflective clothing such as are for example described in standard EN 471, EN 1150, CAN/CSA Z96-02, ANSI/ISEA 207-2006 and BS EN 471:2003, their use for the production of yarns and textile farbrics and a process for the production of these fibres.
- EN 471 deals exclusively with the reflective effect of personal protective equipment, in particular with reflective clothing. As a rule reflective clothing comprises a fluorescent background material and a retro-reflective material. For the purpose of the present invention, a material is described as a fluorescent material in accordance with the definition in EN 471 which emits rather than absorbs rays at a longer wave length; in the text which follows the term high-visibility material is also used. The present invention refers to the fluorescent background material but not to the retro-reflective materials.
- EN 1150 deals with reflective clothing for non-professional use. The difference between standard EN 1150 in comparison to standard EN 471 is the defined area of the fluorescent material in the clothing. In addition 8 different fluorescent colours are allowed in EN 1150 (in EN 471 only yellow, orange and red fluorescent colours are allowed).
- The CAN/CSA Z96-02 standard is the Canadian standard for high-visibility reflective clothing. The clothing is divided into three categories depending on the application. The demands of the area of the fluorescent material and the colour coordinates after radiation correspond to standard EN 471.
- The American standard ANSI/ISEA 207-2006 defines the requirements for protective clothing depending on the application. I.e. the requirements for protective clothing for the police, rescue forces and construction workers are different. The clothing for these three groups differs in terms of the requirements for the high-visibility background material.
- Until now high-visibility materials were made solely on the basis of synthetic fibres and in particular polyester which, however, has disadvantages with regard to the wear comfort and safety. The disadvantages of textiles of this kind reside in particular in an unpleasant skin climate and in the development of smells after wearing for longer periods due to the insufficient moisture-regulating material properties as well as in the danger typical for synthetic fibres i.e. electrostatic charging. Complex textile structures represent an alternative. In these the outer side contains the high-visibility component and the inner side mainly comprises cellulosic fibres to improve the wear comfort such as are described in
WO 2006/017709 . Today fibres according to the viscose process and Lyocell process are in particular known as cellulose regenerated fibres. These are used all over the world for standard applications in textile and nonwoven fields with an individual fibre titre of between 0.8 and 15 dtex. - Cellulosic regenerated fibres can indeed be dyed with fluorescent dyestuffs using the conventional bath process. But the fibres dyed in this way do not satisfy the light fastness requirements (greater than 4, measured according to ISO 105-B02). Following xenon exposure, they are considerably bleached and display a marked change in the colour shade and a considerable reduction in the colour intensity which for example can be depicted as a change in the coordinates of the colour space.
- For decades it has been known that viscose fibres can be dyed in a permanent manner by adding pigments. Corresponding fibres are available on the market. In comparison to spun-dyed synthetic fibres, it has, however, not been possible to date, to produce spun-dyed regenerated fibres which satisfy the requirements of EN 471.
- Compared to the state of the art, the task was to make a fibre available which on the one hand satisfies the requirements of protective and reflective clothing, as for example are described in EN 471 and CAN/CSA Z96-02, and which on the other hand increases the wear comfort and safety aspects of this clothing with a justifiable economic effort. It should, therefore, be possible to produce the protective and reflective clothing from a fibre of this kind without adding any other fibre types.
- It is particularly important that the textiles made from these fibres pass the following requirements for background materials in accordance with EN 471 (and other standards):
- Minimum light density factor (standard values in accordance with CIE publication no. 15.2) and colour space
- Colour following exposure to xenon: the sample is illuminated according to ISO 105-B02, process 3
- Rub fastness dry and wet (ISO 105-A02)
- Another important criterion is the light fastness of fibres according to ISO 105-B02, process 2
- Moreover, the task was to make a suitable manufacturing process available for these fibres.
- Surprisingly it was possible to solve this task with cellulosic regenerated fibres which contain an incorporated fluorescent pigment - in the following also called the "luminous pigment" and a colour pigment incorporated into the spinning dope.
- In this respect for the purpose of the present invention by fluorescent pigment, in particular a fluorescent pigment is to be understood which reveals a separate colour which can be discerned by the human eye in the daylight. If this were not the case, the purpose of the invention - the warning effect - would naturally not be attained. In this respect the pigments would clearly have to differ from purely optical brighteners.
- Surprisingly it was found that as a result of the colour pigment, a clear improvement in the light fastness of the cellulosic regenerated fibres in accordance with the invention can be obtained compared to another fibre which only contains a colour pigment. This is higher than 4, measured according to ISO 105-B02.
- In this respect the necessary high light density factor is attained by the fluorescent pigment. The cellulosic regenerated fibres in accordance with the invention reveal a light density factor, measured according to EN IS0 471 of more than 0.7 for yellow fibres, more than 0.4 for orange fibres and more than 0.25 for red fibres and only slightly changed colour coordinates following xenon test exposure. In the same way they reveal a light density factor, measured according to CAN/CSA Z96-02 of more than 0.38 for fluorescent yellow-green fibres, more than 0.20 for fluorescent orange-red fibres and more than 0.125 for fluorescent red fibres and only a few changed colour coordinates after xenon test exposure.
- The fibres also satisfy the other values demanded by EN 471 and similar norms with regard to rub fastness, perspiration fastness, wash fastness, dry cleaning fastness, hypochlorite bleaching fastness and fastness to ironing.
- The spun-dyed cellulosic regenerated fibres in accordance with the invention can for example be produced according to a viscose process, a modified viscose process (e.g. the Modal process, a zinc-free viscose process with al-sulphate, the polynosic process etc.....) as well as according to a solvent spinning process which is produced with organic solvents such as melted aqueous amine oxides or what are known as ionic liquids. The fibres can be designated accordingly as viscose, Modal, polynosic respectively Lyocell. In the same way other alternative processes such as the Carbamat or the Cupro process are in principle possible.
- Fine spinning was performed at 1.1 - 25, preferably 0.2. - 5.0 weight percentage colour pigment and 0.1 - 22, preferably 7.0 - 17.0 weight percentage of luminous pigment (always in relation to cellulose).
- In general the products known to the expert for the spin dyeing of corresponding fibres are suitable as colour pigments. Among other things the colour pigments Aquamarine Blue 3G from Messrs. Tennents Textile Colors (Cu-phthalocyanide complexes in the form of chromophores), Aquarine Yellow 10G (Messrs. Tennants Textile Colors, Monoazo dye) and Aquis Orange 0341 (Messrs. Heubach, diarylid pyrazolon dyestuff) are suitable for blue, yellow respectively orange fluorescent fibres.
- The luminous pigments preferably contain amino-modified benzoguanamines as chromophore groups. For example the yellow pigment Lunar Yellow 27 and the orange pigment Blaze 5 from the RTS series of Messrs. Swada are suitable with particle diameters of 3 - 4 µm. These substances are sufficiently stable in spin dyeing conditions i.e. spinning solutions respectively spinning baths with a very high respectively very low pH value or of a high temperature.
- Luminous pigments are basically suitable with other chromophore groups, for example sulfonamide groups, provided that they have the stabilisers named.
- In the case of fluorescent fibres for non-professional use, 8 different colours are allowed such as are described in standard EN 1150. In sports textiles the polyester overdyeing fastness plays an important role for the practical application since many sports textiles are produced from a blend of viscose, Modal or Lyocell with synthetic fibres. If only fluorescent pigments are spun into the cellulosic fibres, the light fastnesses are, also according to this standard, too low. Thus the incorporation of dyestuff pigments in accordance with the invention is also necessary in this case to attain sufficient light fastnesses.
- The light fastnesses of the fibres in accordance with the invention can be further improved by the addition of stabilisers. In principle there are two types of stabilisers which can be used in fluorescent fibres and the efficiency mechanism of which is different.
- In this respect these are UV absorbers and radical quenchers. With the UV absorbers, the light energy is converted into heat and is then drawn off as heat. In chemical terms these substances are either organic, conjugated aromatic compounds (benzophenone, triazine, triazole and oxal-anilide) or anorganic substances (for example nano-Zn0 and nano-Ti02) which have an effect via the mechanism of light dispersion. Radical quenchers are e.g. so-called HALS products (Hindered Amine Light Stabiliser).
- The cellulosic regenerated fibre can contain other additives. In one special embodiment of the invention, the cellulosic regenerated fibre is additionally equipped with a flame-resistant agent.
- One preferred embodiment of the flame-resistant fibre is produced by the additional incorporation of a pigment-shaped flame-resistant agent. In particular organophosphorous compounds come into question as pigment-shaped flame-resistant agents apart from other types. For viscose for example the highly suitable and well-known 2,2'-oxybis [5,5 dimethyl-1,3,2, dioxaphosphorinan] 2,2' disulfide, available under the trade name of Exolit respectively Sandoflam.
In a further preferred embodiment of the invention, the cellulosic regenerated fibre is finished in an antibacterial form. In this respect the expert can use the substances known to him. - The object of the present invention is also the use of the fibre in accordance with the invention to produce a yarn. To be able to have suitable properties for the respective application, a yarn of this kind in accordance with the invention can also contain fibres of another origin such as for example (flame-resistant) polyester, Modacryl, para- and meta-aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®)), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stable polyacrylnitrile fibres (PANOX®) and electrically conductive fibres as well as blends of these fibres. In a preferred embodiment of the invention, the blending partners can likewise have a high-visibility finish.
- Likewise the object of the present invention is the use of the fibre in accordance with the invention for the production of a textile fabric. Apart from the fibres in accordance with the invention, this textile can also contain other fibres, for example (flame-resistant) polyester, Modacryl, para- and meta- aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stabilised polyacrylnitrile fibres (PANOX®) and electrically conductive fibres and blends of these fibres. In one preferred embodiment of the invention the other fibres can likewise have a high-visibility finish. The textile fabric is preferably a woven, knitted or warp knitted fabric but can basically also be a fleece (non-woven). In the event of a woven or knit fabric, the blend of the fibres in accordance with the invention is with other fibres either by blending prior to the production of yarns, the so-called intimate blend, or by the joint use of respectively pure yarns of the different fibre types when weaving, knitting or knitting is possible.
- In the same way the object of the present invention is also the use of fibres in accordance with the invention for the production of reflective clothing whereby normally the above named yarns or textile fabrics are intermediate steps within the textile chain. Different designs of articles of clothing of this kind are well known to the expert and do not, therefore, have to be described in greater detail.
- The invention will now be explained on the basis of examples. These are to be understood as possible forms of the embodiment of the invention. In no way is the invention to be restricted to the scope of these examples.
- The colour coordinates and the luminous density factor before and after xenon exposure were measured on a fibre sheet. The fibre sheets are produced in four steps: 10g of fibres are mixed with water, then swirled in a sheet former apparatus in accordance with ISO 3688: 1999 (E) and then finally dewatered. The wet fibre sheet is then finally dried at 92° C for 20 min. The weight per surface area of the fibre sheet obtained in this way equals 285 g/m2 and the diameter is 20 cm.
- A spun-dyed viscose fibre 1.7 dtex was produced with a content of 10.5 weight percentage of luminous pigment orange (Messrs. SWADA, RTS series, Blaze 5) and 1.7 weight percentage colour pigment orange Aquis Orange 0341 (Messrs. Heubach, diarylide- pyrazolon (in relation to the cellulose mass).
- The luminous fibres with the incorporated colour pigments and luminous pigments remain stable following xenon test exposure (table 1). The colour coordinates remain within the given range. The colour density factor drops slightly. The light stability is high and the colour remains intact after washing. The friction fastnesses (dry and wet) comply with the values in the standard. From this we can conclude that these luminous fibres for protective textiles satisfy standard EN 471 in all categories.
- A spun-dyed viscose fibre 1.7 dtex contains 12% luminous pigment orange (Messrs. SWADA, RTS series blaze 5) (in relation to the cellulose mass). In this case no colour pigments were used.
- Example 2 shows (table 1) that the luminous fibres, which only contain luminous pigment, with spun-in luminous pigments cannot satisfy standard EN 471 since the colour coordinates lie outside the given range and the light density factor drops significantly following UV exposure. In table 1 the light fastnesses are also given. The measured value of 2 for the light fastness of a fibre in accordance with the state of the art of technology is, therefore, too low to satisfy the standard.
- From the examples provided 1 and 2 it is, therefore, clear that the incorporation of colour pigments together with the luminous pigments is necessary to use the fibres in protective clothing.
- A spun-dyed, flame-resistant viscose fibre with an individual titre of 1.7 dtex contains 21 weight percentage 2,2'-oxybis[5,5-dimethyl-1,3,2-dioxaphosphorinan]2,2'disulfide (Exolit 5060, Messrs. Clariant), 13.2 % luminous pigment yellow (Lunar Yellow 27, Messrs, SWADA) and 2.6 % colour pigment yellow (Aquarine Yellow 10G of Messrs. Tennants Textile Colors, chromophore groups are Monoazo groups), always in relation to the cellulose. The high-visibility fibres were illuminated in the xenon test and then the colour coordinates were measured before and after the exposure. The fastnesses were determined according to the test process ISO 105-B02.
- The yellow flame-resistant high-visibility fibres reveal excellent results. The light density factor of the flame-resistant high-visibility fibres is extremely high (0.98) and the value remains much higher after exposure (0.81) than is demanded in the standard (0.7 for yellow fibres). The colour coordinates after exposure are almost the same as before exposure which indicates a high-quality luminous fibre. All the fastness tests reveal excellent results which meet all the demands of standard EN ISO 471.
- A spun-dyed viscose fibre with an individual titre of 1.7 dtex was produced with a content of 11.0 weight percentage luminous pigment blue (Cornet blue 60, Messrs. SWADA) and 3.2 weight percentage colour pigment blue (Aquarine Blue 3G, Messrs. Tennents Textile Colors, chromophore groups are Cu-phthalocyanide complexes). The fastnesses are listed in table 1.
- The polyester overdyeing fastness of the blue high-visibility fibres produced in accordance with the invention for non-professional use displays very good values;.the colour fastness is > 4 (table 1).
These results confirm that high-visibility cellulose fibres can satisfy the standard EN 1150 and are well suited for clothing for non professional use e.g. leisure sport activities.Table 1 Example 1 2 3 4 Colour Orange Orange Yellow, FR Blue Light density factor Before exposure 0.47 0.47 0.98 After exposure 0.41 0.31 0.81 Colour coordinates before Exposure X 0.565 0.537 0.400 Y 0.377 0.417 0.528 Colour coordinates after Exposure X 0.520 0.423 0.398 Y 0.384 0.427 0.488 Rub fastness dry ISO 105-A02 4 41 Wet 2 2 Light fastness ISO 105-B02 4 2 4.5 6 Wash fastness 60 °C ISO 105-C06 Change in colour 5 5 Dyeing Viscose 5 5 Dyeing Wool 4-5 4-5 Polyesterwerdyeing Change in colour 5 4-5 4-5 Dyeing Viscose 4 2-3 4-5 Dyeing Polyester 1-2 2 4-5 Perspiration acidic ISO-E04 Change in colour 5 Dyeing Viscose 5 Dyeing Wool 4-5 Perspiration Alkali Change in colour 5 Dyeing Viscose 5 Dyeing Wool 4-5
Claims (16)
- Cellulosic regenerated fibre which contains an incorporated colour pigment and an incorporated fluorescent pigment descernable by the human eye in daylight and which shows a light fastness of higher than 4, measured according to ISO 105-B02.
- Cellulosic regenerated fibre according to claim 1 characterized in that it contains 0.1 - 25 weight percentage, preferably 0.2 - 5 weight percentage colour pigment and 0.1 - 22 weight percentage preferably 7.0 -17.0 weight percentage of fluorescent pigment, always in relation to the cellulose.
- Cellulosic regenerated fibre according to claim 1 characterised in that the fluorescent pigments contain amino-modified benzoguanamines as the chromophore groups.
- Cellulosic regenerated fibre according to claim 1 which is produced according to a viscose, Modal, Lyocell, Cupro or carbamate process.
- Cellulosic regenerated fibre according to claim 1 which contains additional light stabilisers (UV absorber, HALS and anorganic light stabilisers.
- Cellulosic regenerated fibre according to claim 1 which is in addition finished in a flame-resistant way.
- Cellulosic regenerated fibre according to claim 6 whereby the flame-resistant agent is an incorporated organophosphorous compound.
- Cellulosic regenerated fibre according to claim 1 which is in addition finished with an antibacterial agent.
- Use of fibres according to claims 1 to 8 for the production of a yarn.
- Use of fibres according to claim 9, wherein the yarn additionally contains fibres of another origin.
- Use of fibres according to claim 10, wherein the fibres of another origin are chosen from the group consisting of (flame-resistant) polyester, Modacryl, para- and meta-aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®)), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stable polyacrylnitrile fibres (PANOX®) and electrically conductive fibres as well as blends of these fibres.
- Use of fibres according to claims 1 to 8 for the production of a textile fabric.
- Use of fibres according to claims 12, wherein the textile fabric is a woven, knitted or warp knitted fabric or a non-woven.
- Use of fibres according to claims 12, wherein the fabric additionally contains fibres of another origin.
- Use of fibres according to claims 12, wherein the fibres of another origin are chosen from the group consisting of (flame-resistant) polyester, Modacryl, para- and meta-aramides, polyamidimide (Kermel®), (flame-resistant) wool, polybenzimidazole (PBI), polyimide (P84®)), polyamides, (flame-resistant) polyamides, flame-resistant acrylic fibres, melamine fibres, polyphenylensulfide (PPS), polytetrafluorethylene (PTFE), glass fibres, cotton, silk, carbon fibres, oxidised thermally stable polyacrylnitrile fibres (PANOX®) and electrically conductive fibres as well as blends of these fibres.
- Use of fibres according to claims 1 to 8 for the production of an article of reflective clothing for professional and non-professional use.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA1256/2010A AT510229B1 (en) | 2010-07-27 | 2010-07-27 | FLUORESCENT FIBER AND ITS USE |
PCT/AT2011/000297 WO2012012813A1 (en) | 2010-07-27 | 2011-07-11 | Fluorescent fibres and their use |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2597980A1 EP2597980A1 (en) | 2013-06-05 |
EP2597980B1 true EP2597980B1 (en) | 2015-01-07 |
Family
ID=44512453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20110748870 Not-in-force EP2597980B1 (en) | 2010-07-27 | 2011-07-11 | Fluorescent fibres and their use |
Country Status (8)
Country | Link |
---|---|
US (1) | US20130149933A1 (en) |
EP (1) | EP2597980B1 (en) |
JP (1) | JP2013537588A (en) |
CN (1) | CN103002760A (en) |
AT (1) | AT510229B1 (en) |
RU (1) | RU2013108378A (en) |
TW (1) | TW201219616A (en) |
WO (1) | WO2012012813A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT513426A1 (en) * | 2012-09-17 | 2014-04-15 | Chemiefaser Lenzing Ag | Spun-dyed modal fiber, its use and process for its preparation |
AT514469B1 (en) * | 2013-01-11 | 2015-04-15 | Chemiefaser Lenzing Ag | Flame retardant fabric for protective clothing and upholstery fabrics applications and its use |
CN103437038A (en) * | 2013-09-05 | 2013-12-11 | 苏州巨旺纺织有限公司 | Fluorescent polyacrylonitrile fiber fabric |
CN103498262A (en) * | 2013-09-05 | 2014-01-08 | 苏州巨旺纺织有限公司 | Fluorescent viscose fiber fabric |
CN103437036A (en) * | 2013-09-05 | 2013-12-11 | 苏州巨旺纺织有限公司 | Insulated copper ammonia fiber fabric |
CN103437049A (en) * | 2013-09-05 | 2013-12-11 | 苏州巨旺纺织有限公司 | Fluorescent silk fiber fabric |
CN103519455A (en) * | 2013-11-05 | 2014-01-22 | 吴江市森豪纺织品有限公司 | Multifunctional tear-resisting fabric |
AT515736B1 (en) * | 2014-04-07 | 2016-06-15 | Chemiefaser Lenzing Ag | Colored fiber blends and their use |
KR101596865B1 (en) * | 2014-07-02 | 2016-02-23 | 주식회사 휴비스 | Meta-Aramid Fiber Having Fluorescent Color and Method for Preparing the Same |
JP6437247B2 (en) * | 2014-08-28 | 2018-12-12 | 株式会社クラレ | Flame retardant fabric with high visibility |
CN105420872A (en) * | 2015-12-28 | 2016-03-23 | 苏州东胜化纤纺织有限公司 | High-elasticity viscose acetal fiber |
DE102016001910B4 (en) * | 2016-02-18 | 2019-10-10 | Viscose Faser Gmbh | A method of providing a pigment amount and using the amount of pigment provided therewith |
EP3260595B1 (en) | 2016-06-20 | 2018-05-09 | Viscose Faser GmbH | Method for obtaining highly fire-retarding synthetic fibres from textile scraps |
TWI665348B (en) * | 2018-03-15 | 2019-07-11 | Taiwan Textile Research Institute | Fluorescent fiber and manufacturing method thereof |
CN108589287A (en) * | 2018-04-03 | 2018-09-28 | 四川大学 | A kind of in-situ preparation method of fluorescence cotton fiber |
CN108728978B (en) * | 2018-05-05 | 2021-07-30 | 灵氟隆新材料科技江苏有限公司 | Preparation method of fluorescent polytetrafluoroethylene sewing thread |
CN108703424A (en) * | 2018-05-23 | 2018-10-26 | 苏州凤霓绣叶文化艺术有限公司 | A kind of flame-retardant garment plus material |
TWI693310B (en) * | 2018-12-20 | 2020-05-11 | 財團法人紡織產業綜合研究所 | Intrinsic masterbatch for fluorescent fiber, fluorescent fiber and preparation method thereof |
CN111349319B (en) * | 2018-12-20 | 2022-07-12 | 财团法人纺织产业综合研究所 | Intrinsic fluorescent fiber master batch, fluorescent fiber and preparation method thereof |
CN110485041A (en) * | 2019-09-19 | 2019-11-22 | 界首市远航织带有限公司 | A kind of antibacterial far infrared ribbon preparation method |
CN112981593A (en) * | 2019-12-18 | 2021-06-18 | 财团法人纺织产业综合研究所 | Intrinsic fluorescent green fiber and preparation method thereof |
TWI757669B (en) * | 2019-12-18 | 2022-03-11 | 財團法人紡織產業綜合研究所 | Intrinsic fluorecent green fiber and preparing method thereof |
WO2021199058A1 (en) * | 2020-03-31 | 2021-10-07 | Aditya Birla Science and Technology Company Private Limited | A method of preparing dope dyed lyocell fibre |
CN114775315B (en) * | 2022-04-10 | 2024-03-29 | 青岛大学 | Flexible luminous fabric capable of being used for light quantum information storage and preparation method thereof |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4767807A (en) * | 1985-08-21 | 1988-08-30 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Coloring agent for dope-dyeing viscose rayon |
JPS6297990A (en) * | 1986-10-27 | 1987-05-07 | 株式会社日本触媒 | Fluorescent colorant for raw liquid dyed viscose rayon |
JPH01168911A (en) * | 1987-12-23 | 1989-07-04 | Kuraray Co Ltd | Production of ultraviolet light luminous yarn |
JP2563829B2 (en) * | 1988-08-11 | 1996-12-18 | 正義 武井 | Luminous fiber |
DE19539315A1 (en) * | 1995-10-23 | 1997-04-24 | Hoechst Ag | UV-active regenerated cellulose fibers |
US6001936A (en) * | 1997-10-24 | 1999-12-14 | 3M Innovative Properties Company | Dye enhanced durability through controlled dye environment |
AT407997B (en) * | 1999-08-10 | 2001-07-25 | Chemiefaser Lenzing Ag | COLORED CELLULOSIC SHAPED BODIES |
JP3784609B2 (en) * | 2000-03-31 | 2006-06-14 | 日華化学株式会社 | Antibacterial agent for fiber and antibacterial fiber product |
US6462128B1 (en) * | 2000-07-14 | 2002-10-08 | Clariant International Ltd. | Process of making finely divided opaque particles |
JP2002266221A (en) * | 2001-03-09 | 2002-09-18 | Asahi Kasei Corp | Light-accumulation nonwoven fabric |
US20040001978A1 (en) * | 2002-07-01 | 2004-01-01 | Yves Bader | Molten metal resistant fabrics |
US20060030228A1 (en) | 2004-08-06 | 2006-02-09 | Truesdale Rembert J Iii | High-visibility, flame resistant fabrics and methods for making same |
AT503625B1 (en) * | 2006-04-28 | 2013-10-15 | Chemiefaser Lenzing Ag | WATER-IRRADIZED PRODUCT CONTAINING CELLULASIC FIBERS |
WO2008027454A1 (en) * | 2006-08-31 | 2008-03-06 | Southern Mills, Inc. | Flame resistant fabrics and garments made from same |
JP2008223172A (en) * | 2007-03-13 | 2008-09-25 | Unitica Fibers Ltd | Stainproof spun-dyed fiber |
US20090298370A1 (en) * | 2008-06-03 | 2009-12-03 | Mmi-Ipco, Llc | Flame Retardant Fabrics |
-
2010
- 2010-07-27 AT ATA1256/2010A patent/AT510229B1/en not_active IP Right Cessation
-
2011
- 2011-07-11 WO PCT/AT2011/000297 patent/WO2012012813A1/en active Application Filing
- 2011-07-11 EP EP20110748870 patent/EP2597980B1/en not_active Not-in-force
- 2011-07-11 RU RU2013108378/12A patent/RU2013108378A/en not_active Application Discontinuation
- 2011-07-11 JP JP2013520921A patent/JP2013537588A/en active Pending
- 2011-07-11 US US13/808,419 patent/US20130149933A1/en not_active Abandoned
- 2011-07-11 CN CN201180036491XA patent/CN103002760A/en active Pending
- 2011-07-18 TW TW100125311A patent/TW201219616A/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2012012813A1 (en) | 2012-02-02 |
US20130149933A1 (en) | 2013-06-13 |
JP2013537588A (en) | 2013-10-03 |
AT510229B1 (en) | 2013-08-15 |
RU2013108378A (en) | 2014-09-10 |
EP2597980A1 (en) | 2013-06-05 |
AT510229A1 (en) | 2012-02-15 |
TW201219616A (en) | 2012-05-16 |
CN103002760A (en) | 2013-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2597980B1 (en) | Fluorescent fibres and their use | |
RU2541062C2 (en) | Fluorescent fibre, use thereof and methods for production thereof | |
EP2940202B1 (en) | Heat-resistant fabric | |
DK3040473T3 (en) | DIMENSIVE WITH ILLUSTRATIVE CHARACTERISTICS AND PROCEDURE FOR COLORING THE CHAIN THREAD USING INDIGO-BLUE COLOR | |
CN105683440B (en) | High visuality fiber fabric and the high visuality clothes for using the cloth and silk | |
JPWO2017047461A1 (en) | Colored fiber fabric and method for producing colored fiber fabric | |
CN105019119A (en) | Flame-retardant anti-static two-faced plush cloth | |
US20140302301A1 (en) | Luminescent cellulose synthetic fiber and method for the production thereof | |
JP2014198916A (en) | Heat-resistant fabric having high aesthetic properties | |
JP2012219418A (en) | Dyed fabric containing aramid fiber and dyeing method | |
JP6556537B2 (en) | High visibility woven / knitted fabric | |
CN108642600B (en) | Stock solution coloring fluorescent ultraviolet-proof polyester fiber and preparation method thereof | |
CN110714256A (en) | Ultraviolet-proof and sun-proof fabric and production method thereof | |
EP4215658A1 (en) | Fabric, method for producing same and clothing item using same | |
CN102373539A (en) | PTT (Polytrimethylene Terephthalate) heavy plain cloth | |
ITFI20110007A1 (en) | VELVET WITH DENIM EFFECT AND PROCESS FOR ITS PRODUCTION. |
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: 20130227 |
|
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: 20131112 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602011012938 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: A41D0013010000 Ipc: D01F0002000000 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: D01F 2/02 20060101ALI20140625BHEP Ipc: D01F 2/16 20060101ALI20140625BHEP Ipc: A41D 13/01 20060101ALI20140625BHEP Ipc: D01F 2/00 20060101AFI20140625BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140805 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
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: 705816 Country of ref document: AT Kind code of ref document: T Effective date: 20150215 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602011012938 Country of ref document: DE Effective date: 20150226 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20150107 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 705816 Country of ref document: AT Kind code of ref document: T Effective date: 20150107 |
|
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: 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: 20150107 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: 20150107 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: 20150107 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: 20150407 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: 20150107 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: 20150107 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: 20150407 |
|
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: 20150408 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: 20150107 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: 20150107 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: 20150507 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: 20150107 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: 20150107 Ref country code: NL 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: 20150107 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602011012938 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20150107 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: 20150107 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: 20150107 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: 20150107 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: 20150107 |
|
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: 20151008 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150107 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602011012938 Country of ref document: DE |
|
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: 20150107 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: 20150107 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150711 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150711 |
|
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: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160202 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150731 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150711 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150731 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150731 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: 20150107 |
|
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: 20150711 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150107 |
|
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: 20110711 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: 20150107 |
|
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 Effective date: 20150107 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20150107 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: 20150107 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: 20150107 |
|
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: 20150107 |