Classifications

• • 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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • 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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
  • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • 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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
  • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C09J161/14—Modified phenol-aldehyde condensates
• • 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

Definitions

• the invention relates to a sizing composition for mineral fibers, especially glass fibers or rock fibers, which has a low content of free formaldehyde.
• the sizing composition comprises a resin obtained by the condensation of phenol, formaldehyde and an amine in the presence of a basic catalyst, and a formaldehyde trap.
• the invention also relates to the insulating products based on mineral fibers treated by said sizing composition.
• the insulating products based on mineral fibers may be formed from fibers obtained by various processes, for example using the known technique of internal or external centrifugal fiberizing.
• Internal centrifugation consists in introducing molten material (in general glass or rock) into a spinner that has a multitude of small holes, the material being projected against the peripheral wall of the spinner under the action of the centrifugal force and escaping therefrom in the form of filaments.
• the filaments are attenuated and entrained by a high-velocity high-temperature gas stream to a receiving member in order to form a web of fibers.
• this consists in pouring the molten material onto the outer peripheral surface of rotary members known as rotors, from which the molten material is ejected under the action of the centrifugal force.
• Means for attenuating via a gas stream and for collecting on a receiving member are also provided.
• the fibers To assemble the fibers together and provide the web with cohesion, the fibers, on leaving the spinner, are sprayed with a sizing composition containing a thermosetting resin.
• the web of fibers coated with the size undergoes a heat treatment (at a temperature generally above 100° C.) so as to polycondense the resin and thus obtain a thermal and/or acoustic insulation product having specific properties, especially dimensional stability, tensile strength, thickness recovery after compression, and uniform color.
• the sizing composition is usually sprayed onto the fibers.
• the sizing composition contains the resin, which customarily takes the form of an aqueous solution, additives, such as urea, silanes, mineral oils, aqueous ammonia and a polycondensation catalyst, and water.
• the properties of the sizing composition depend largely on the characteristics of the resin. From the standpoint of the application, it is necessary for the sizing composition to have good sprayability and be able to be deposited on the surface of the fibers so as to bond them effectively.
• the sprayability is directly related to the capability that the resin possesses of being able to be diluted in a large amount of water and to remain stable over time.
• the dilution capability is characterized by the “dilutability”, which is defined as the volume of deionized water that it is possible, at a given temperature, to add to a unit volume of the aqueous resin solution before the appearance of permanent cloudiness.
• a resin is considered to be able to be used as a size when its dilutability at 20° C. is 1000% or higher.
• the sizing composition is generally prepared at the time of use by mixing the resin and the abovementioned additives. It is important that the resin remains stable for a given period of time before being used in the sizing composition, in particular for at least 8 days at a temperature of around 12 to 18° C. and that its dilutability at the end of this period is, at 20° C., 1000% or higher, preferably 2000% or higher (infinite dilutability).
• the sizing compositions are subject to strict regulations which mean that the resin must contain—and generate during the sizing operation or subsequently during the curing of the insulating product—as few as possible compounds considered to be harmful to human health or to the environment.
• thermosetting resins most commonly used in sizing compositions are phenolic resins belonging to the family of resols. Apart from their good crosslinkability under the aforementioned thermal conditions, these resins are very soluble in water, possess good affinity for mineral fibers, especially glass fibers, and are relatively inexpensive.
• These resins are obtained by the condensation of phenol and formaldehyde, in the presence of a basic catalyst, in a formaldehyde/phenol molar ratio generally greater than 1 so as to promote the reaction between the phenol and the formaldehyde and to reduce the residual phenol content in the resin.
• the resin obtained contains phenol-formaldehyde and urea-formaldehyde condensates, has a free formaldehyde and free phenol content, expressed with respect to the total weight of liquid, of 3% and 0.5%, respectively, or less, and a water dilutability of at least 1000%.
• the resin is not stable under the conditions of the heat treatment to which the sized fibers are subjected in order for the resin to crosslink and effectively bond the fibers in the final insulating product.
• the urea-formaldehyde condensates are degraded and release formaldehyde, which increases the undesirable gas emissions into the atmosphere.
• Formaldehyde may also be released from the end product during its use as thermal and/or acoustic insulation, under the effect of temperature variations and also hygrometric variations linked to climatic cycles.
• EP 0 480 778 A1 has proposed to substitute part of the urea with an amine, which reacts with the free phenol and the free formaldehyde via the Mannich reaction to form a condensation product having improved thermal stability.
• the free phenol and free formaldehyde contents of this resin are 0.20% or less and 3% or less, respectively.
• the objective of the present invention is to provide a sizing composition capable of being sprayed onto mineral fibers which comprises a liquid phenolic resin that has a low content of free formaldehyde and a compound capable of reacting with the formaldehyde.
• One subject of the invention is, more generally, a resin composition that comprises a liquid phenolic resin having a low content of free formaldehyde and a compound capable of reacting with the formaldehyde.
• This resin composition is intended, in particular, to be incorporated into the constitution of the aforementioned sizing composition.
• Another subject of the invention relates to the thermal and/or acoustic insulation products obtained from mineral fibers sized with the aforementioned sizing composition.
• the liquid resin that is incorporated into the constitution of the sizing composition according to the invention has a free formaldehyde content, expressed with respect to the total weight of liquid, of 0.1% or less, preferably of 0.05% or less.
• the free phenol content of the resin is, expressed with respect to the total weight of liquid, 0.5% or less, preferably 0.4% or less.
• the resin is a liquid resin which mainly contains phenol-formaldehyde (P-F) and phenol-formaldehyde-amine (P-F-A) condensates.
• P phenol-formaldehyde
• P-A phenol-formaldehyde-amine
• the “phenol” part, denoted by P, of the condensates may be composed of (i) phenol, or (ii) phenol substituted by at least one functional group (such as halo-, nitro-, alkyl-), or (iii) an optionally substituted phenol group borne by a long-chain molecule, or (iv) a mixture of the aforementioned compounds (I), (ii), (iii).
• the resin has a dilutability, measured at 20° C., at least equal to 1000%, preferably 1200% or higher and advantageously 1400% or higher.
• the resin is thermally stable since it is free of urea-formaldehyde (U-F) condensates known for their aptitude to degrade under the effect of temperature.
• U-F urea-formaldehyde
• P-F-A condensates these are stable under the aforementioned conditions, notably they generate little formaldehyde, in particular during aging of the final insulating product.
• the resin as defined above is obtained according to a process that consists in reacting a phenol as defined previously, preferably phenol, and formaldehyde in the presence of a basic catalyst, in a formaldehyde/phenol molar ratio greater than 1, in cooling the reaction mixture and in introducing into said reaction mixture, during the cooling, an amine that reacts with the free formaldehyde and the free phenol via the Mann ich reaction.
• the cooling is interrupted and the reaction mixture is maintained at the introduction temperature for a time that varies from 10 to 120 minutes, and after the cooling an acid is added in a sufficient amount so that the pH of the resin is less than 7.
• the phenol and the formaldehyde are made to react in a formaldehyde/phenol molar ratio of between 2 and 4, or advantageously less than or equal to 3, to a degree of phenol conversion of greater than or equal to 93%, and cooling of the reaction mixture is started.
• the cooling takes place at a stage in the condensation that corresponds to a resin that can still be diluted with water (dilutability greater than 1000%).
• degree of phenol conversion is understood to mean the percentage of phenol that has participated in the condensation reaction with the formaldehyde relative to the starting phenol content.
• the amine is added progressively during the cooling since the reaction between phenol and formaldehyde is exothermic, and the temperature at the moment of addition of the amine is maintained over the time mentioned above, while taking measures to ensure that the dilutability of the resin remains at least equal to 1000%.
• the amine is chosen from amines that can react with formaldehyde and phenol to form a Mannich base.
• alkanolamines in particular monoethanolamine and diethanolamine
• cyclic amines in particular piperidine, piperazine, and morpholine.
• Monoethanolamine and diethanolamine are preferred.
• the amine is introduced right from the start of the cooling, at a temperature that may vary from 50 to 65° C., preferably of about 60° C.
• the phase during which the temperature is maintained allows the amine to be reacted with almost all of the formaldehyde present in the reaction medium, and consequently allows the free formaldehyde content in the final resin to be lowered down to a value of 0.1% or less.
• the preparation of the resin takes place under a temperature cycle, which comprises three phases: a heating phase; a first temperature hold; and a cooling phase.
• formaldehyde and phenol are made to react in the presence of a basic catalyst, while progressively heating to a temperature between 60 and 75° C., preferably about 70° C.
• the formaldehyde/phenol molar ratio is greater than 1, preferably varies from 2 to 4 and is advantageously equal to 3 or less.
• the catalyst may be chosen from catalysts known to those skilled in the art, for example triethylamine, lime (CaO) and alkali or alkaline-earth metal hydroxides, for example sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide. Sodium hydroxide is preferred.
• the amount of catalyst varies from 2 to 15%, preferably 5 to 9% and advantageously 6 to 8% by weight relative to the initial weight of phenol.
• the third phase is a cooling phase during which the amine is introduced into the reaction mixture so as to start the reaction with the residual formaldehyde and the residual phenol, and thus to form the P-F-A condensates.
• the addition of the amine takes place progressively owing to the exothermic character of the reaction, as indicated above, and may for example be carried out at a rate of from 1 to 5%, preferably 2 to 4%, by weight of the total amount of amine per minute.
• the compound capable of reacting with the formaldehyde is chosen from:
• the sizing composition may also comprise 0 to 40 parts of urea per 100 parts by dry weight of the mixture constituted by the resin and the urea.
• the sizing composition also comprises the following additives, per 100 parts by dry weight of resin and where appropriate of urea:
• the urea makes it possible to adjust the gel time of the sizing composition in order to prevent any pregelling problems;
• the ammonium sulfate serves as a polycondensation catalyst (in the hot oven) after the sizing composition has been sprayed onto the fibers;
• the silane is a coupling agent for coupling between the fibers and the resin and also acts as an anti-ageing agent;
• the oils are hydrophobic anti-dust agents;
• the aqueous ammonia acts, when cold, as a polycondensation retarder.
• the sizing composition may also be prepared by using a resin composition, which may be known as a “premix”, containing the resin and the compound capable of reacting with the formaldehyde, optionally urea, to which the other additives are added.
• the resin composition has a better stability than the resin alone, which enables the dilutability to be maintained at a level compatible with the conditions for application to the mineral fibers over a longer storage time.
• the temperature was reduced to 60° C. over 30 minutes and at the same time 75.3 g of monoethanolamine (1.2 mol) were introduced in a regular manner into the reaction mixture.
• the temperature was maintained at 60° C. for 15 minutes, the mixture was cooled down to about 25° C. over 30 minutes, and sulfamic acid as a 15% solution was added over 60 minutes until the pH was equal to 5.0.
• the resin obtained had the appearance of a clear aqueous composition: it had a free formaldehyde content equal to 0.05%, a free phenol content equal to 0.2% (the contents being expressed with respect to the total weight of liquid) and a dilutability greater than 2000%.
• the solids content of the liquid resin was adjusted to 50% with water, and urea (20 parts by weight per 80 parts by dry weight of the liquid resin) was added. The mixture was kept at 12° C. for 7 days. This mixture was called reference resin composition 1.
• a sizing composition was prepared by mixing 100 parts by dry weight of the aforementioned mixture of resin and urea, 10 parts by weight of acetoacetamide, 3 parts of ammonium sulfate, 1 part of silane (Silquest® A-1100 sold by OSI) and 8 parts of a mineral oil.
• This sizing composition was used to fabricate an insulating product based on mineral wool.
• the sizing composition was sprayed onto glass fibers at the outlet from the fiberizing device in an amount of 4.5% by dry weight of size relative to the weight of the fibers.
• the sized fibers were collected on a belt conveyor where they formed a glass wool blanket, which was then subjected to a heat treatment in an oven in order to obtain a minimum temperature of 200° C. in the middle of the product.
• Table 1 collates the dilutability measurements of the sizing composition according to the invention (with acetoacetamide) and of the reference resin composition (without acetoacetamide), after a storage period of 3, 6, 9 and 12 days at 8° C. and 12° C.
• a liquid resin was prepared under the conditions from example 1, modified in that the solids content of the resin was adjusted to 43.6%.
• urea 20 parts by weight of urea were added to 80 parts by dry weight of the resin in order to obtain a reference resin composition 2, which had a dilutability greater than 2000%.
• the reference resin composition 2 was kept under conditions that simulated aging during storage and led to a reduction in the dilutability.
• Table 2 collates the dilutability measurements of the sizing compositions and of the resin composition that does not contain a compound capable of reacting with the formaldehyde (Reference 2) measured 24 hours after the preparation of the sizes, all the compositions (size and reference) having been kept at 23° C.
• a compound capable of reacting with the formaldehyde makes it possible to increase the dilutability of the sizing composition up to a level that is compatible with the conditions for application to the mineral fibers (dilutability at least equal to 1000%).
• a liquid resin was prepared under the conditions from example 1.
• Two series of sizing compositions were prepared containing 100 parts by dry weight of the resin composition and a variable amount (11.1 parts (series a) or 31.6 parts (series b) by dry weight) of a compound below capable of reacting with the formaldehyde:
• the sizing compositions from series a and from series b had a solids content equal to 35.8% and 27.5% respectively.
• the sizing compositions and the resin compositions were stored at 12° C. and their water dilutability was measured at various intervals.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Geochemistry & Mineralogy (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=39869716

Family Applications (1)

Country Status (11)

Cited By (6)

Families Citing this family (4)

Citations (23)

Family Cites Families (13)

• 2008
  • 2008-04-11 FR FR0802015A patent/FR2929952B1/fr active Active
• 2009
  • 2009-04-10 JP JP2011503485A patent/JP5591791B2/ja not_active Expired - Fee Related
  • 2009-04-10 US US12/937,326 patent/US20110111226A1/en not_active Abandoned
  • 2009-04-10 RU RU2010145928/05A patent/RU2501826C2/ru active
  • 2009-04-10 DK DK09742303.2T patent/DK2268589T3/en active
  • 2009-04-10 ES ES09742303.2T patent/ES2692292T3/es active Active
  • 2009-04-10 AU AU2009245531A patent/AU2009245531B2/en active Active
  • 2009-04-10 EP EP09742303.2A patent/EP2268589B1/fr active Active
  • 2009-04-10 WO PCT/FR2009/050653 patent/WO2009136105A2/fr active Application Filing
  • 2009-04-10 CA CA2720920A patent/CA2720920C/fr active Active
  • 2009-04-10 PL PL09742303T patent/PL2268589T3/pl unknown

Patent Citations (30)

Also Published As

Similar Documents

Legal Events