• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to an aqueous composition of inorganic or hybrid binder comprising (in% by weight of solids) - 55 to 100% of at least one alkali metal silicate having an Si / alkali metal mass ratio which varies from 0 , 3 to 2, 0 to 35% of at least one plasticizer, and 0 to 10% of one or more additives. The subject of the invention is also the fibrous products obtained, in particular based on mineral fibers, such as mats, grids, fabrics, in particular canvases to be painted, and knits.
    公开号:FR3030550A1
    申请号:FR1463064
    申请日:2014-12-22
    公开日:2016-06-24
    发明作者:Alexandre Garcia；Louis Garnier
    申请人:Saint Gobain Adfors SAS；
    IPC主号:
    专利说明:

    [0001] The present invention relates to aqueous binder compositions for fibers and to the fibrous products thus obtained. The invention relates more particularly to an aqueous composition of inorganic or hybrid binder for the manufacture of products in the form of mats or fabrics comprising mineral fibers, in particular glass or rock fibers. The mats are used in particular for producing asphalt membranes and as a surface element for acoustic and / or thermal insulation products based on mineral wool. The fabrics are intended to form wall coverings, especially paintings to be painted.
    [0002] The mineral fiber mats (also referred to as "non-woven" or "sails") may be manufactured by known methods operating dry or wet. In the dry process, molten mineral matter contained in an oven is fed to a set of dies from which filaments flow by gravity and are drawn by a gaseous fluid. The mineral filaments are harvested on a conveyor where they intermingle forming a mat. On the upper face of the mat thus formed, an organic binder is applied using a suitable device, most often operating by curtain deposition, and the excess organic binder is removed by suction at the opposite side. . The mat then enters a device containing hot air whose temperature, of the order of 200 to 250 ° C, is adapted to remove the water and crosslink the organic binder in a very short time, of the order from ten seconds to 1 minute, then the mat of mineral fibers is collected in the form of a coil. In the wet process, the mat is obtained from an aqueous dispersion of cut mineral fibers which is deposited by means of a forming head on a conveyor provided with perforations and the water is extracted through the conveyor through to a suction box. The cut mineral fibers remaining on the conveyor form a mat which is treated under the same thermal conditions as those described for the dry process. In the abovementioned processes, the function of the organic binder is to bind the mineral fibers together and to give the mat which contains them mechanical properties suited to the desired use, in particular a rigidity sufficient to allow it to be handled easily without risk of tearing. The organic binder applied to the mineral fibers is generally in the form of an aqueous solution containing at least one thermosetting resin and additives such as a crosslinking catalyst of the resin, a silane (coupling agent), a water repellent, The most commonly used thermosetting resins are ureaformaldehyde, melamine-formaldehyde and phenol-formaldehyde resins which have the advantage of efficiently binding the fibers while being inexpensive. However, these resins are likely to emit formaldehyde during the manufacture of the fiber mat (during the heat treatment) but also after their final introduction. Because of its proven harmful effects, formaldehyde regulations are becoming more stringent and require manufacturers to offer alternative compositions free of formaldehyde.
    [0003] Due to their organic nature, the aforementioned binders can be consumed in contact with a flame and therefore the fire resistance of the fiber mat that contains it is low. The addition of flameproofing agents in the binder has already been proposed to improve the fire resistance of the mat. Such flame retardants include halogenated compounds and metal oxides. However, halogenated compounds generate emissions of volatile organic compounds, some of which may be toxic, and metal oxides degrade the mechanical performance of the binders that contain them. These flame retardants are also relatively expensive. Hybrid compositiotif combinations of organic and inorganic compounds with good fire resistance are known. US 2012/0277381 discloses a hybrid polyester resin applicable to synthetic textiles, such as polyester fabric. The resin is obtained by reaction of a polyester resin, silica particles and an alkoxysilane.
    [0004] DE 2007007318 describes a coating composition for textiles having a direct or indirect biological effect on organisms. The composition comprises a) a soil of a film-forming agent in the form of nanoparticles formed by hydrolysis or co-hydrolysis of silica and / or metal compounds and b) a bioactive compound such as an oil, a natural substance in the form of a thick liquid or solid in water or an organic solvent miscible with water. WO -2011 / 128526 discloses a hydraulic binder for agglomerating or consolidating solid particles of any shape, including fibers. The binder comprises an alkali silicate in aqueous solution, a surfactant and a natural triglyceride. The object of the present invention is to provide an alternative solution to conventional binder compositions for fibers, in particular mineral fibers, based on thermosetting resins containing formaldehyde, which makes it possible to confer a better fire resistance on the fibrous product obtained, while retaining good mechanical properties, including acceptable stiffness and tensile strength. This object is achieved by means of an aqueous inorganic or hybrid binder composition which comprises (in% solids) - 55 to 100% by weight of at least one alkali metal silicate having an Si / alkali metal mass ratio which varies from 0.3 to 2, - 0 to 35% by weight of at least one plasticizer, and - 0 to 10% by weight of one or more additives. In the present invention, the term "aqueous composition of inorganic binder" means a composition essentially containing an alkali metal silicate and water. In the same way, an "aqueous hybrid binder composition" is a composition containing the alkali metal silicate, the plasticizer, or the reaction product of these two compounds, and water. The alkali silicate according to the invention is preferably selected from potassium, sodium and lithium silicates, advantageously potassium. It has been found that the Si / alkali metal mass ratio has a direct impact on the rigidity of the fibrous product: the higher the ratio, the greater the rigidity. In general, the weight ratio Si / alkali metal varies from 0.3 to 2.0, preferably is greater than 0.5, and more preferably varies from 1.2 to 1.6. The alkali silicate is generally in the form of an aqueous solution having a pH ranging from 9 to 13, preferably 10 to 12.
    [0005] The function of the plasticizing agent is to insert into the silica network formed from the alkali silicate and to reduce its rigidity, thus giving a more flexible binder. The plasticizer is preferably selected from the group consisting of styrene-butadiene copolymers, alkyl (met) acrylate homopolymers and copolymers, especially poly (butyl acrylate), copolymers of (meth) alkyl acrylate and styrene, copolymers of (meth) acrylic acid and styrene, polyvinyl acetate and silicones such as poly (dimethylsiloxane). The plasticizer generally has a glass transition temperature (Tg) of less than 0 ° C. It must be soluble in the aqueous solution of alkali silicate and be stable at the pH of the latter. As indicated above, the amount of plasticizer in the binder composition is at most 35% by weight of the solids. Beyond this value, there is a decrease in the mechanical properties of the fibrous product, including rigidity (the product is too flexible and can not be handled properly) and a decrease in fire resistance. Preferably, the amount of plasticizer is at most equal to 25% by weight of the solids. When the binder composition contains a poly (dimethylsiloxane), the latter is present in a proportion of at most 2% by weight of the solids so as not to reduce the rigidity of the fibrous product too much. Preferably, the amount is at most 1%. The binder composition according to the invention may also comprise up to 10% by weight of the solids of one or more conventional additives, for example a coupling agent between the alkali metal silicate and the plasticizer, an agent antifoam, a pigment, a mineral filler, a dispersing agent, in particular for the mineral filler, a thickener and a biocide.
    [0006] A coupling agent of particular interest, particularly for coupling the alkali metal silicate and a copolymer of styrene and butadiene, is bis (3-triethoxysilylpropyl) tetrasulfide. The binder composition is generally in the form of an aqueous solution or dispersion. The inorganic or hybrid binder can be applied to fibers to form fibrous products, which products are another object of the present invention. The fibers may be of any kind, for example mineral fibers made of glass or rock, in particular basalt; organic fibers such as synthetic fibers, especially polyester and polyolefin fibers such as polypropylene; and natural fibers such as cellulosic fibers, especially cotton, linen, sisal and hemp fibers, and animal fibers such as wool and silk. The fibers may be a mixture of several fibers of different nature. Preferably, the fibers are mineral fibers, in particular glass fibers. The fibers may be fibers of variable length depending on their chemical nature. In particular, the fibers may be continuous or cut. The fibrous product may be in the form of a mat of mineral fibers.
    [0007] Conventionally, to prepare mineral fiber mats the inorganic or hybrid binder is deposited on the mineral fiber mat (formed by the dry process or the wet process), then the mat is treated at a temperature allowing the formation of a infusible binder. The treatment is carried out at a temperature which generally varies from 180 to 250 ° C, preferably from 200 to 220 ° C, and for a very short time, of the order of a few seconds to a few minutes. The length of the mineral fibers is at most equal to 150 mm, preferably varies from 20 to 100 mm and advantageously from 50 to 70 mm. Their diameter can vary to a large extent, for example from 5 to 30 μm.
    [0008] The mineral fibers are both filaments and yarns composed of a multitude of filaments bonded together, in particular by a sizing (base yarn). The mineral fibers can also be assemblies of the aforementioned basic son in the form of rovings ("rovings" in English). The base yarns and the rovings may be non-twisted yarns or twisted yarns (or textile yarns), preferably without torsion. The linear density of the mineral fibers consisting of the aforementioned son can range from 34 to 1500 tex.
    [0009] The glass entering the constitution of the filaments can be of any type, for example C, E, R, AR (alkali-resistant). C-glass and E-glass are preferred. The fiber mat may, where appropriate, be reinforced by continuous fibers which are generally deposited on the mat conveying device in the direction of the mat and distributed over all or part of the width of the mat. These fibers are generally deposited in the thickness of the mat of fibers, in particular mineral, before the application of the inorganic or hybrid binder. Reinforcing fibers are usually made of glass. The fiber mat according to the invention generally has a surface mass which varies from 10 to 1100 g / m 2, preferably from 30 to 350 g / m 2, and advantageously from 35 to 80 g / m 2. The fiber mat, in particular mineral, according to the invention generally contains 5 to 50% by weight of inorganic or hybrid binder, preferably 10 to 45%. The mineral fiber mat obtained according to the present invention can be used in particular for making roofing elements, for example bitumen membranes or shingles, and as a surfacing element for thermal and / or acoustic insulation products. based on mineral wool. The binder composition according to the invention may also be applied to grids, fabrics or knits made of all or part of mineral threads, in particular glass. Especially intended are fabrics for forming wall coverings, particularly in the form of a painting fabric comprising glass threads consisting of a plurality of glass filaments coated with an organic sizing composition. The application of the binder composition to the paintable fabric makes it possible to form a coating layer which adheres to the organic sizing and has good fire resistance. The paintings to be painted are preferably made of glass son having a linear density which varies from 50 to 500 tex, advantageously from 100 to 350 tex, and have a weight per unit area which varies from 30 to 1000 g / m2, preferably 50 to 300 g / m 2 and advantageously from 75 to 200 g / m 2. The amount of binder according to the present invention applied to the fabric to be painted represents 5 to 50% of the total weight of the fabric to be painted, preferably 10 to 45%. The following examples illustrate the invention without limiting it. In these examples, the fibrous product is subjected to the following tests: the tensile strength of the fiber product, expressed as N, is measured under the conditions of the NF EN ISO 13934-1 standard. The measurement is carried out on 10 samples 25 cm long and 5 cm wide, and the rigidity of the fibrous product is measured by means of a Lorentzen & Wetter apparatus, at 23 ° C. and 50% relative humidity on a rectangular sample (3.8 cm x 8.0 cm). When it comes to canvas to paint, the sample 15 is cut in the machine direction (relative to the direction of weaving). The sample is held vertically at one end in the smallest dimension between two jaws and a horizontal force is applied on the free end (useful length: 5.0 cm). The applied force (in mN) is measured to reach a bending angle of 30 °. This force characterizes the rigidity of the fibrous product. - the fire resistance is measured under the conditions of the NF EN ISO 11925-2 standard. The propagation time (in seconds) over a distance of 15 cm and the propagation distance (in mm) are determined for a flame applied on the surface or on the edge of the sample. EXAMPLES 1-6 These examples illustrate the manufacture of glass fiber mats. Potassium silicate in aqueous solution, a styrene-butadiene resin latex and optionally a polydimethylsiloxane are mixed in the proportions shown in Table 1, expressed as% by weight of solids. The pH of the mixture is adjusted to 11 with sodium hydroxide. Water is added to the mixture so as to obtain a solid content of 15%.
    [0010] A glass fiber mat C (GF / C Grade Glass Microfiber Filter Binder Free marketed by Watman) is impregnated by immersion in the aforementioned aqueous binder composition. After removing the excess binder, the mat is placed in an oven at 200 ° C for 3 minutes.
    [0011] The properties of the mats obtained are given in Table 1 by comparison with a mat treated with a melamine-formaldehyde resin (reference) under the same conditions, except that the duration of treatment in the oven is equal to 5 minutes. Examples 1 and 3 exhibit good tensile strength in combination with higher rigidity than that of the Reference. The addition of plasticizer makes it possible to reduce the stiffness of the mat (Examples 2 and 4 to compare with Examples 1 and 3) without degrading the tensile strength at break (Example 4). Example 4 represents a good compromise between the tensile strength and the stiffness of the mat, close to the performance of the reference. The presence of polydimethylsiloxane in Example 5 makes it possible to reduce the stiffness of the mat by 74.7% compared with Example 4 while maintaining an acceptable tensile strength. The rigidity of the mat of Examples 1, 3 and 6 decreases as the Si / P ratio decreases. The choice of the Si / P ratio makes it possible to control the properties of the mat, both its tensile strength and rigidity. EXAMPLES 7 TO 14 A mat was made under the conditions of Examples 1 to 6 modified in that the binder composition had the composition given in Table 2. The mats of Examples 7, 8, 10 to 12 and 14 were subjected to as well as the reference mat to the fire resistance test. The results are shown in Table 2. Examples 7 to 10 and 14 according to the invention exhibit a tensile strength of rupture close to the Reference at equivalent binder rate. The fire performance of the mats according to these examples is better than the reference, whether in terms of distance propagation or propagation time to 15 cm. EXAMPLES 15 TO 17 These examples illustrate the manufacture of paintings to be painted.
    [0012] The binder composition is prepared by mixing the compounds shown in Table 3 in proportions expressed as% by weight of the solids. The solids content in the aqueous binder composition is 13%. A painting fabric made of dip-woven glass yarns is impregnated into the aforementioned binder composition. The canvas to be painted is a satin weave fabric consisting of 4.5 voluminized threads of 330 tex per cm, in weft, and 7.9 threads of 68 tex per cm, in warp. The mass per unit area of the fabric is 200 g / m. After removing the excess binder, the impregnated paint cloth is placed in an oven at 200 ° C. for 90 seconds. The amount of binder represents 20% of the weight of the painting to be obtained. The properties of the paintings to be obtained obtained appear in Table 3 by comparison with a painting cloth treated under the same conditions with a melamine-formaldehyde resin (Reference). The fire resistance measurements for Examples 15, 16 and Reference are given in Table 3. Examples 15 and 16 show a stiffness comparable to that of the Reference. The addition of a coupling agent (Example 17) makes it possible to obtain a higher tensile strength and rigidity than that of the reference. The fire resistance properties of Examples 15 and 16 are far superior to those of the Reference.
    [0013] Table 1 Example 1 2 3 4 5 6 Ref. - Potassium silicate (1) 100 75 - - - - - - Potassium silicate (2) - - 100 75 73 - - - Potassium silicate (3) - - - - - 100 - - Styrene-butadiene copolymer) - 25 - 25 - - - Polydimethylsiloxane (5) - - - - 2 - - Binder content (% by weight) 47.2 47.0 43.1 47.6 43.8 45.0 45.0 Tensile strength (N) 86.7 n / a 90.0 96.5 68.1 33.3 109.0 Stiffness (mN) 98.9 53.2 89.3 60.0 15.2 33.0 65.4 (1) Reference Betole K42T marketed by the company Woellner (weight ratio Si / P = 1.9) (2) Betole K5020T reference sold by the company Woellner (weight ratio Si / P = 1.6) (3) Betol® K57M reference marketed by the company Woellner (weight ratio Si / P = 0.6) (4) Lipatone SB 29Y46 reference sold by the company Synthomer (latex) (5) Betoline AH250 reference sold by the company Woellner n / a: not determined Table 2 Example 7 8 9 10 11 12 13 14 Ref. (camp.) (camp.) (comp.) - Potassium silicate (1) - - - 100 - - Potassium silicate (2) 100 90 80 70 60 50 25 - - - Styrene-butadiene copolymer (4) - 10 20 30 40 50 75 - - Binder content (% by weight) 47.4 48.5 47.3 47.4 47.1 47.8 44.0 47.2 45.0 Tensile strength (N) 120 , 4 100.0 105.9 107.4 109.2 105.6 85.5 86.7 109.0 Distance spread (mm) Tranche 15 40 nd
    [0014] Total Totale n.e.
    [0015] Total Area 30 50 n.e.
    [0016] 70 Total Total n. 30 n. Propagation time to 15 cm (s) Slice p.p. p.d.p. p.d.p. 6 p.d.p.
    [0017] 3 Surface p.d.p. p.d.p. p.d.p. 10 n.p. nd (1) Betole K42T reference sold by the company Woellner (weight ratio Si / P = 1.9) (2) Betole K5020T reference marketed by the company Woellner (weight ratio Si / P = 1.6) (4) Lipatone reference SB 29Y46 sold by the company Synthomer (latex) nd: not determined pdp no flame propagation Table 3 Example 15 16 17 Reference - Potassium silicate (2) 100 75 75 - - Styrene-butadiene copolymer) - 25 24 - - Coupling agent) - - 1 - Tensile strength (N ) 202.7 219.4 542.1 465.4 Stiffness (mN) 58.4 59.5 90.1 64.8 Propagation distance (mm) Slice 30 50 nd Total Area 30 60 nd Total Propagation time to 15 cm (s) Slice pdp p.d.
    [0018] 9 Surface p.d.p. pdp nd 18 (2) Betole K5020T reference sold by the company Woellner (weight ratio Si / P = 1.6) (4) Lipatone SB 29Y46 reference sold by the company Synthomer (latex) (6) Si69 reference sold by the company Evonick Industries AG nd not determined pdp : no flame spread
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. An aqueous composition of inorganic or hybrid binder, characterized in that it comprises (in% by weight of solids) - 55 to 100% of at least one alkali metal silicate having an Si / alkali metal mass ratio which varies from 0 , 3 to 2, 0 to 35% of at least one plasticizer, and 0 to 10% of one or more additives.
    [0002]
    2. Composition according to claim 1, characterized in that the alkali metal silicate is a potassium, sodium or lithium silicate, preferably potassium.
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the alkali metal silicate has a weight ratio Si / alkali metal which varies from 0.3 to 2.0, preferably greater than 0.5 and advantageously varies from 1.2 to 1.6.
    [0004]
    4. Composition according to one of claims 1 to 3, characterized in that the plasticizer is selected from the group consisting of copolymers of styrene and butadiene, homopolymers and copolymers of (meth) acrylate alkyl, copolymers of alkyl (meth) acrylate and styrene, copolymers of (meth) acrylic acid and styrene, poly (vinyl acetate) and silicones such as poly (dimethylsiloxane).
    [0005]
    5. Composition according to one of claims 1 to 4, characterized in that the plasticizer has a glass transition temperature below 0 ° C.
    [0006]
    6. Composition according to one of claims 1 to 5, characterized in that the proportion of plasticizer is at most equal to 25%.
    [0007]
    7. Composition according to one of claims 1 to 6, characterized in that the plasticizer is a polydimethylsiloxane and in that its content is at most equal to 2%.
    [0008]
    8. Composition according to one of claims 1 to 7, characterized in that the additive is bis (3-triethoxysilylpropyl) tetrasulfide.
    [0009]
    9. Fibrous product coated with a binder composition according to one of claims 1 to 8.
    [0010]
    10. Product according to claim 9, characterized in that it is in the form of a mat, a grid, a fabric or a knit.
    [0011]
    11. Product according to claim 10, characterized in that it is a mat of mineral fibers, in particular glass.
    [0012]
    12. Product according to claim 11, characterized in that the fibers have a length at most equal to 150 mm, preferably ranging from 20 to 100 mm and advantageously from 50 to 70 mm.
    [0013]
    13. Product according to claim 11 or 12, characterized in that it has a weight per unit area which varies from 10 to 1100 g / m2, preferably from 30 to 350 g / m2, and advantageously from 35 to 80 g / m2.
    [0014]
    14. Product according to claim 10, characterized in that it is a fabric in the form of a canvas to be painted comprising glass strands consisting of a plurality of glass filaments coated with an organic sizing composition.
    [0015]
    15. Product according to claim 14, characterized in that the glass strands have a linear density which varies from 50 to 500 tex and in that it has a surface density which varies from 30 to 1000 g / m2.
    [0016]
    16. Product according to one of claims 10 to 15, characterized in that it contains 5 to 50% by weight of inorganic binder or hybrid, preferably 10 to 45%.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2007086574A1|2006-01-30|2007-08-02|Oji Paper Co., Ltd.|Hybrid, process for production of the same, and coating material for the production|
    DE102007007318A1|2007-02-14|2008-08-21|Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V.|Coating composition for bioactive textile materials, useful e.g. for producing wound dressings, comprises layer-forming inorganic nanoparticulate sol and active component, e.g. natural oil|
    JP2008239856A|2007-03-28|2008-10-09|Gantsu Kasei Kk|Flame-retardant resin aqueous emulsion and method for producing the same|
    WO2009093002A2|2008-01-25|2009-07-30|Microtherm N.V.|Liquid formulation of microporous thermal insulation material, method of manufacture, and use thereof|
    WO2010070248A2|2008-12-19|2010-06-24|Saint-Gobain Technical Fabrics Europe|Painter's canvas including an agent capable of trapping formaldehyde and manufacturing process|
    CH703166A2|2010-05-17|2011-11-30|Josef Scherer|Reinforcement mat for fire protection mortar and flowline mortar, comprises contains carbon fibers in the form of rovings, where the carbon fibers are equipped with a latex-like aqueous coating of styrene-butadiene rubber|FR3063998A1|2017-03-20|2018-09-21|Saint-Gobain Adfors|GRID OF GLASS FIBERS FOR THE RENOVATION OF FACADES|DE2110059C3|1971-03-03|1979-11-29|Henkel Kgaa, 4000 Duesseldorf|Binder based on alkali silicates|
    DE2946500A1|1979-11-17|1981-05-27|Henkel KGaA, 4000 Düsseldorf|Binder based on alkali metal silicate solutions and their use|
    JPS5964582A|1982-10-04|1984-04-12|Nissan Chemical Ind Ltd|Reformation of cementitious material|
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    GB2385856A|2002-01-15|2003-09-03|Hubdean Ltd|Water-based, fire retarding coating composition|
    US20090304938A1|2005-10-26|2009-12-10|Thorsten Gurke|Polyisocyanate-Based Binder for Mineral Wool Products|
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    WO2011052677A1|2009-11-02|2011-05-05|互応化学工業株式会社|Hybrid-type polyester resin, resin composition for formation of film, and polyester film and textile|
    FR2958930B1|2010-04-14|2014-08-01|Techme Sarl|NEW HYDRAULIC BINDING SYSTEM BASED ON ALKALI SILICATE IN AQUEOUS SOLUTION|
    FR3001236B1|2013-01-22|2015-06-26|Emin Leydier|AQUEOUS COMPOSITION FOR THE PRODUCTION OF FIBROUS SHEET CARRIERS WITH IMPROVED MECHANICAL STRENGTH PROPERTIES, PROCESS, USE, FIBROUS CARRIERS AND MANUFACTURED ARTICLES THEREOF|CN109485274B|2018-12-27|2022-02-01|巨石集团有限公司|Impregnating compound for high-speed jet molding of glass fiber and preparation method and application thereof|
    CN110294600B|2019-07-04|2022-02-01|巨石集团有限公司|Glass fiber impregnating compound and preparation method and application thereof|
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    法律状态:
    2015-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-12-16| PLFP| Fee payment|Year of fee payment: 3 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-13| PLFP| Fee payment|Year of fee payment: 6 |
    2020-12-16| PLFP| Fee payment|Year of fee payment: 7 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463064A|FR3030550B1|2014-12-22|2014-12-22|AQUEOUS BINDER COMPOSITION FOR FIBERS AND FIBROUS PRODUCTS OBTAINED.|
    FR1463064|2014-12-22|FR1463064A| FR3030550B1|2014-12-22|2014-12-22|AQUEOUS BINDER COMPOSITION FOR FIBERS AND FIBROUS PRODUCTS OBTAINED.|
    US15/538,105| US10457814B2|2014-12-22|2015-12-22|Aqueous binder composition for fibres and fibrous products produced|
    EP15828352.3A| EP3237549A1|2014-12-22|2015-12-22|Aqueous binder composition for fibres and fibrous products produced|
    PCT/FR2015/053701| WO2016102875A1|2014-12-22|2015-12-22|Aqueous binder composition for fibres and fibrous products produced|
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