Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
  • D04H1/4218—Glass fibres
• • 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
  • Y10T428/2933—Coated or with bond, impregnation or core
• • 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
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Definitions

• the present invention relates to the field of sizing compositions for mineral fibers. It relates more specifically to an aqueous sizing which comprises a polycarboxylic acid and a polyamine, to the process for its preparation and products based on mineral fibers coated with this sizing.
• thermal and / or acoustic insulating products containing mineral fibers require the use of a bonding which binds the fibers and provides the mechanical strength adapted to the use for which they are intended.
• the products must also have sufficient cohesion and rigidity to withstand the various manipulations before final implementation.
• the sizing is applied to fibers obtained in different ways depending on the nature of the mineral used (glass, rock, etc.), in particular by the known technique of internal or external centrifugal fiberization.
• Internal centrifugation involves introducing the molten material into a centrifugal device comprising a multitude of small orifices, the material being projected towards the peripheral wall of the device in the form of filaments of variable length.
• the filaments are drawn and driven to a high temperature and high velocity gas stream to a receiving member to form a randomly distributed fiber web.
• the sizing composition containing the thermosetting resin is sprayed onto the fibers at the outlet of the centrifugal device.
• the layer of fibers coated with the sizing is then heat-treated at a temperature generally greater than 100 ° C., to effect the crosslinking of the resin and thus to obtain a cured product having the properties required to form a thermal insulation product and / or phonic, including stability dimensional, tensile strength, thickness recovery after compression and a homogeneous color.
• the sizing operation must be carried out under conditions making it possible to obtain a homogeneous distribution of the sizing on the fibers.
• This operation aims to ensure that the fibers are bonded together by sufficiently strong junction points to ensure good cohesion and ensure that the product does not tear in use.
• the cohesion must nevertheless not be too high so that the bond remains flexible and that the final product retains a certain aptitude for deformation.
• the junctions between the fibers must provide a sufficiently stable and rigid network to resist the compression imposed for storage and transport, and meet the specifications announced by the supplier at the time of installation.
• the sizing Under the conditions of the process, the sizing is as previously indicated sprayed on the fibers being formed. Therefore, the sizing should have a low viscosity in the uncrosslinked state and quickly tend to a more viscous state before giving a polymeric network under the action of heat. If the viscosity in the uncrosslinked state is too high, the sizing tends to be sticky and may form deposits on the receiving members during heat treatment of the fiber web.
• heat-crosslinkable polymers are capable of satisfying the conditions set forth above.
• most of the market is represented by everyday consumer goods for which price is decisive.
• heat-curable polymers such as high-cost polyurethanes and epoxies are not currently selected for industrial use even though they are technically acceptable.
• thermosetting polymers most commonly used in sizing are in the form of phenoplast (phenol-formaldehyde) or aminoplast (melamine-formaldehyde or urea-formaldehyde) type resins.
• the resin is generally associated with water as a diluting agent, urea which serves to reduce the level of free formaldehyde and also acts as a binder, and various additives such as oil, ammonia, dyes and possibly fillers.
• Sizing containing such resins are not entirely satisfactory because they are likely to generate undesirable gases, including formaldehyde, methyl isocyanate (MIC) and / or isocyanic acid (ICA), when they are brought to more than 150 ° C during the crosslinking step to form the product, or up to 700 ° C in some uses such as household ovens.
• undesirable gases including formaldehyde, methyl isocyanate (MIC) and / or isocyanic acid (ICA)
• inorganic sizing for example containing aluminum phosphate.
• these sizing are satisfactory for a temperature up to 500 ° C or 700 ° C, they have other disadvantages: sensitive to moisture, they tend to swell during storage and delaminate what increases the risk of tearing portions of the product during handling.
• Another way to limit unwanted emissions is based on the use of organic resin sizing other than phenol-formaldehyde resins.
• a sizing comprising a polycarboxylic acid and a polyol, preferably combined with a catalyst of the alkali metal salt type of phosphorus organic acid (see EP-A - 0 990 727, EP-A-0 990 728 and EP-A-0 990 729).
• the polycarboxylic acid is an oligomer or a polymer preferably having a mass less than 10,000 containing more than one carboxylic group and the polyol contains at least two hydroxyl groups.
• the examples use poly (acrylic acid) and triethanolamine.
• crosslinked mineral fibers are described by means of a sizing comprising one or more compounds containing a carboxylic function and / or a ⁇ -hydroxyalkylamide function.
• the exemplary embodiments proceed by reaction of carboxylic acid anhydride and diethanolamine or triethanolamine.
• EP-A-1 164 163 a glass wool manufacturing process which comprises a step of reacting a sizing containing either a carboxylic acid and an alkanolamine, or a resin previously synthesized from a carboxylic acid and an alkanolamine, and a polymer containing a carboxylic group.
• EP-A-1 170 265 it has been proposed to prepare two-step sizing of mixing an anhydride and an amine under reactive conditions until the anhydride is substantially solubilized in the amine and / or reacted with it, then add water and finish the reaction.
• EP-A-1 086 932 a sizing is proposed for mineral wool which contains a resin comprising the non-polymeric reaction product of an amine with a first anhydride and a second anhydride different from the first.
• the above-mentioned sizing still remains less efficient than those containing the conventional phenol-formaldehyde resins. If the polyacrylic and ⁇ -hydroxyalkylamide-based sizing leads to good mechanical properties before aging, the latter degrade strongly when the product is exposed to a temperature above 40 ° C in a highly humid atmosphere.
• the crosslinking of polyacrylic-based sizing generally starts at a temperature of the order of 180.degree. C. and it reaches the final stage only if the treatment time is prolonged to that temperature or the temperature is raised. temperature up to about 240 ° C.
• these conditions are more restrictive and more expensive because they require increasing the length of the oven and / or using more powerful heating means.
• Polyacrylics also tend to stiffen the fibers in the web before crosslinking with the result that the fibers are more difficult to come together and have fewer bonding points.
• polyester-based sizing is more difficult to implement because they form sticky bits on the conveyors of the web.
• the present invention aims to overcome the aforementioned drawbacks by providing a new sizing composition capable of coating mineral fibers to form, in particular, thermal and / or acoustic insulation products. It also aims to provide a method for preparing said composition which makes it possible to obtain an advantageous, more efficient or less expensive sizing.
• the subject of the invention is also the use of said composition for bonding mineral fibers in order to form thermal and / or acoustic insulating products and the products thus obtained.
• the sizing composition according to the invention intended to be applied to mineral fibers is characterized in that it contains at least one polycarboxylic acid and at least one polyamine.
• the polycarboxylic acid according to the invention has a functionality, expressed as the number of carboxylic groups capable of reacting with the polyamine, equal to or greater than 2, preferably less than 5000, advantageously less than 2000, or even less than 500.
• the molecular weight of the polycarboxylic acid varies from 50 to 10 5 g / mol and preferably is less than 10 4 g / mol. Maintaining the molecular weight within the limits indicated does not increase the rigidity of the final crosslinked product.
• polycarboxylic acids of low molecular weight mention may be made of carboxylic acids of functionality equal to 2 such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid. , tartaric acid, phthalic acid and tetrahydrophthalic acid, carboxylic acids of functionality equal to 3 such as citric acid and trimellitic acid, and carboxylic acids of functionality equal to 4 such as the acid butan-1, 2,3,4-tetraoic (BTCA).
• carboxylic acids of functionality such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid.
• tartaric acid, phthalic acid and tetrahydrophthalic acid carboxylic acids of functionality equal to 3
• citric acid and trimellitic acid such as citric acid and trimellitic acid
• carboxylic acids of functionality such as the acid butan-1, 2,3,4-tetraoic (BTCA).
• the higher-molecular-weight polycarboxylic acids may in particular be chosen from oligomers and polymers obtained by homopolymerization of unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and acid.
• unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and acid.
• the polycarboxylic acid can also be obtained by copolymerization of one or more of the abovementioned monomers and of one or more other unsaturated, hydrophilic and / or hydrophobic monomers, for example selected from olefins such as ethylene, propylene, butylene, isobutylene, styrene and its derivatives, and macromonomers (oligomers containing one or more reactive unsaturated functional groups) having terminal unsaturation.
• olefins such as ethylene, propylene, butylene, isobutylene, styrene and its derivatives
• macromonomers oligomers containing one or more reactive unsaturated functional groups having terminal unsaturation.
• polycarboxylic acids whether in the form of a monomer, an oligomer or a polymer, can be obtained in a known manner from the aforementioned acids or the corresponding anhydrides, when they exist.
• succinic anhydride glutaric anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, maleic anhydride and methacrylic anhydride.
• the polycarboxylic acid is chosen from citric or tartaric acid, butan-1,2,3,4-tetraic acid (BTCA), polyacrylics such as poly (acrylic acid), ethylene copolymers and acrylic acid and copolymers of acrylic acid and maleic acid.
• BTCA butan-1,2,3,4-tetraic acid
• polyacrylics such as poly (acrylic acid), ethylene copolymers and acrylic acid and copolymers of acrylic acid and maleic acid.
• tartaric acid, BTCA, poly (acrylic acid) and copolymers of acrylic acid and maleic acid are selected.
• the polyamine according to the invention has a functionality, expressed as the number of amine functions, which is equal to or greater than 2, preferably less than 200.
• these functions are primary and / or secondary amine functions.
• the polyamine may be chosen from a wide range of polyamines, for example straight chain, branched or cyclic aliphatic, saturated or unsaturated, which may contain one or more heteroatoms, especially N and / or O, and aromatic.
• the polyamine has a molecular weight of less than 1000 g / mol and more preferably less than 500 g / mol.
• DETA diethylenetriamine
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• Polyamines of higher molecular weight include polyethyleneimines, poly (aminostyrene) and chitin degradation products in basic medium (chitosan).
• polyamines may be very insoluble in water. To avoid having to use the polyamine in the form of a highly diluted solution and therefore having to handle and store large amounts of water, it is advantageous to transform at least partially into a more soluble salt .
• the polyamine is solubilized in water containing an organic or inorganic acid, for example sulphamic acid or hydrochloric acid.
• the amount of acid to be used depends on the solubility of the polyamine and the nature of the salt to be formed. In general, a solution containing 1 to 10 molar equivalents, preferably of the order of 1 molar equivalent, of amide salt and 1 to 10 molar equivalents, preferably of the order of 5 equivalents, should be obtained. molars, of polyamine.
• aqueous polyamine solutions useful in the context of the invention have a solids content by weight which varies between 10 and 50%, preferably of the order of 25%, especially 18%.
• the sizing composition is generally obtained by diluting or emulsifying in water the polycarboxylic acid and the polyamine, optionally with the additives defined below.
• the sizing is formed by mixing the polybasic carboxylic acid in solution or in aqueous dispersion, preferably at more than 10% by weight, and the polyamine in aqueous solution, preferably at more than 10% by weight. , if necessary with the additives.
• a premix is carried out by introducing the polyamine directly into the solution or the aqueous dispersion of the polybasic carboxylic acid, preferably to more than 10% by weight, and then the optional additives are added later.
• This embodiment makes it possible to prevent the polycarboxylic acid reacting with the polyamine by forming products which precipitate and render the sizing unusable.
• the premixing is generally carried out in a device equipped with a cooling system making it possible to control the temperature of the mixture at approximately 75 ° C., preferably of the order of 70 ° C., in order to avoid any uncontrolled reaction between the polycarboxylic acid and polyamine (strongly exothermic reaction).
• the premix is stable and can be stored especially at 20 ° C for several days before being used in the sizing. It may be advantageous to subject the premix to a heat treatment in order to at least partially react the polyacid and the polyamine. This way of proceeding makes it possible to shorten the residence time and / or to lower the temperature in the oven and consequently to reduce the cost of the final product.
• the heat treatment is carried out at a moderate temperature, of the order of 50 to 100 ° C., in order to be able to control the degree of progress of the reaction, in particular to avoid a significant increase in the viscosity preventing the proper application of the binder. on the fibers.
• the sizing composition thus formed generally comprises, expressed as parts of dry matter, from 20 to 80 parts by weight of polybasic carboxylic acid and from 80 to 20 parts by weight of polyamine.
• the sizing composition additionally comprises the following additives, per 100 parts by weight of polyacrylic acid and polyamine solids:
• water has a role of lubricant, makes it possible to adjust the viscosity to the spraying conditions, to cool the fibers and to limit the phenomena of pregelling,
• the oil ensures the lubrication of the fibers, reduces the dust that can be generated during the handling of finished products (insulating layers for example) and improves the feeling to the touch. It is generally inert with respect to the other constituents and capable of being emulsified in water. Most often, it is an oil consisting of hydrocarbons extracted from petroleum, the silane provides the bond between the mineral fiber and the crosslinking product of the polycarboxylic acid and the polyamine. It makes it possible to reinforce the mechanical properties and improves the resistance to aging.
• the silane is generally an aminosilane, preferably ⁇ -aminopropyltriethoxysilane
• the catalyst makes it possible to accelerate the reaction rate of the polycarboxylic acid and of the polyamine and thus to reduce the residence time of the sheet in the oven.
• the plasticizer makes it possible to limit the phenomena of pre-gelling and to reduce rigidity of the final product.
• alcohols preferably polyols such as glycerol, and triethanolamine.
• the mineral fibers treated with the sizing composition according to the invention are coated and bonded together under the action of heat, at a temperature which varies from 150 to 250 ° C, preferably 180 to 220 ° C.
• the binder In its crosslinked form, the binder is solid, infusible and insoluble in water, and it represents on the order of 1 to 15% of the total weight of the fibers.
• the products obtained may have a variable appearance, for example a sheet or a veil of fibers.
• the web of mineral fibers in particular glass fibers, generally has a basis weight of between 10 and 300 m 2 / g, and preferably it comprises at least 1%, even 2% and even more than 4% by weight of sizing. . Although it can be used alone, the web is particularly intended to coat at least one outer face of an insulating web as described above.
• the products obtained in the context of the present invention are in particular intended to form thermal and acoustic insulators, in particular for building and household ovens. They can also be used as substrates for soil-less cultivation.
• DMA Dynamic Mechanical Analysis
• the procedure is as follows: a sample of Whatmann paper impregnated with the sizing solution is fixed horizontally between two fixed jaws and an oscillating element applied to the upper face of the sample, provided with a device for measuring the stress in According to the deformation applied, it is possible to calculate the modulus of elasticity E.
• the sample is heated to a temperature ranging from 20 to 300 ° C. at a rate of 5 ° C./min.
• A (E 220 -E TR ) x V in which E 22u and V have the meaning given above and E T R represents the module E at the temperature TR.
• Table 1 is the ratio of the area A for each example to the area of Example 8 chosen as reference (A ref ).
• the emission of formaldehyde is measured by placing about 3 to 4 g of the sizing solution to be tested (at about 30% solids content) in an oven at 180 ° C. for 1 hour under an air sweep ( 1 l / min). The vapors that emanate from the oven are directed to 2 bubblers in series containing water. The entrapped formaldehyde is determined by spectrocolorimetry and its content is given in mg / g of crosslinked binder.
• BTCA butan-1,2,3,4-tetraolic acid
• a clear solution containing 23.9% by weight of solids is obtained.
• the polycarboxylic acid / polyamine weight ratio is 81/19.
• BTCA butan-1,2,3,4-tetraic acid
• a clear solution containing 25% by weight of solids is obtained.
• the polycarboxylic acid / polyamine weight ratio is 44/56.
• a container In a container is poured 8 g of a solution of tartaric acid at 30% by weight in water and 2 g of a solution of tetraethylenepentamine (TEPA) at 30% by weight in water. The mixture is stirred for about 15 minutes.
• TEPA tetraethylenepentamine
• a clear, yellow to pale orange solution containing 30% by weight of solids is obtained.
• the polycarboxylic acid / polyamine weight ratio is equal to 80/20.
• the measurements relating to the reactivity and to the mechanical properties are given in Table 1.
• the measurements relating to the reactivity of the solution obtained and to the mechanical properties of the binder are given in Table 1.
• a clear solution containing 30% by weight of solids is obtained.
• the polycarboxylic acid / polyamine weight ratio is 55/45.
• the measurements relating to the reactivity of the solution obtained and to the mechanical properties of the binder are given in Table 1.
• a clear solution containing 30% by weight of solids is obtained.
• the polycarboxylic acid / polyamine weight ratio is equal to 39/61.
• the sizing composition comprises varying levels of copolymer acrylic acid-maleic acid (Sokolan ® 12S; BASF) and tetraethylenepentamine (TEPA) as shown in Table 1.
• the sizing composition comprises 5 to 10 parts of glycerol per 100 parts of solids (calculated on the basis of copolymer and TEPA). The measurements relating to the reactivity of the various sizing and to the mechanical properties of the binders are given in Table 1.
• EXAMPLE 7 (COMPARATIVE) A sizing solution comprising 10% by weight of conventional phenolic resin obtained according to example 1 of EP-A-0 148 050 is used.
• the resin is obtained by condensing phenol and formaldehyde in a ratio of molar formaldehyde / phenol equal to 3.5 in the presence of NaOH, adding urea in the cooling phase and neutralizing the resin with sulfuric acid.
• polyester resin obtained by reacting polyacrylic acid (molecular weight about 60000) and triethanolamine (HFO.sub.5, marketed by ROHM and HAAS) is used.
• the sizing according to Example 6 emits a much lower amount of formaldehyde (about 10 times less) than the conventional phenolic resin of Example 7, and of the same order of magnitude as the polyester resin of Example 8 .
• the sizing according to the invention has a crosslinking start temperature TR greater than the phenolic sizing of Example 7 and for the majority of them also lower than the polyester sizing of Example 8.
• the ratio A / Aref always greater than 1 shows that compared to the reference polyester resin, the sizing of the invention have better performance in terms of crosslinking.
• the sizing of Examples 3 to 5 which have a temperature TR of the same order or higher than that of the reference sizing, however, have a higher rate of crosslinking, which is advantageous because it makes it possible to reduce the residence time of the fibers in the curing oven. For sizing whose crosslinking starts at a lower temperature, they have a higher final module E 22 o and therefore have better mechanical properties without increasing the cost.
• the sizing according to Examples 4 and 6 are particularly interesting because they make it possible to quickly reach E 220 module values equal to more than twice those of known sizing.
• glycerol in the sizing makes it possible to adjust the conditions of implementation, in particular by attenuating or even preventing the phenomena of pre-gelling.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Textile Engineering (AREA)
• Materials Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Wood Science & Technology (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Glass Compositions (AREA)
• Reinforced Plastic Materials (AREA)
• Porous Artificial Stone Or Porous Ceramic Products (AREA)
• Nonwoven Fabrics (AREA)

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• 2003
  • 2003-04-16 FR FR0304750A patent/FR2853903B1/fr not_active Expired - Fee Related
• 2004
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  • 2004-04-16 DK DK04742522.8T patent/DK1618238T4/da active
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  • 2004-04-16 AU AU2004233418A patent/AU2004233418A1/en not_active Abandoned
  • 2004-04-16 WO PCT/FR2004/000941 patent/WO2004094714A2/fr not_active Ceased
  • 2004-04-16 US US10/553,467 patent/US20070173588A1/en not_active Abandoned
  • 2004-04-16 ES ES04742522.8T patent/ES2353600T5/es not_active Expired - Lifetime
  • 2004-04-16 KR KR1020057019787A patent/KR101127485B1/ko not_active Expired - Fee Related
  • 2004-04-16 JP JP2006505800A patent/JP4718448B2/ja not_active Expired - Fee Related
  • 2004-04-16 BR BRPI0409455-7A patent/BRPI0409455A/pt not_active Application Discontinuation
  • 2004-04-16 CA CA2522642A patent/CA2522642C/fr not_active Expired - Fee Related
  • 2004-04-16 EP EP04742522.8A patent/EP1618238B2/fr not_active Expired - Lifetime
  • 2004-04-16 DE DE602004029350T patent/DE602004029350D1/de not_active Expired - Lifetime
• 2010
  • 2010-06-21 US US12/819,456 patent/US8329817B2/en not_active Expired - Fee Related
  • 2010-08-24 AU AU2010212523A patent/AU2010212523B2/en not_active Ceased

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