AU2009245531B2

AU2009245531B2 - Sizing composition for mineral fibers and resulting products

Info

Publication number: AU2009245531B2
Application number: AU2009245531A
Authority: AU
Inventors: Jerome Douce; Boris Jaffrennou; Olivier Pons Y Moll
Original assignee: Saint Gobain Isover SA France
Current assignee: Saint Gobain Isover SA France
Priority date: 2008-04-11
Filing date: 2009-04-10
Publication date: 2014-06-19
Anticipated expiration: 2029-04-10
Also published as: JP2011516389A; FR2929952B1; DK2268589T3; FR2929952A1; WO2009136105A3; CA2720920C; WO2009136105A2; PL2268589T3; CA2720920A1; US20110111226A1; RU2010145928A; ES2692292T3; RU2501826C2; AU2009245531A1; EP2268589A2; JP5591791B2; PL2268589T4; EP2268589B1

Abstract

The present invention relates to a sizing composition for mineral fibers, especially glass fibers or rock fibers, containing a liquid phenolic resin having a free formaldehyde content of less than or equal to 0.1% by total weight of liquid and a compound capable of reacting with the free formaldehyde. The liquid phenolic resin is preferably mainly composed of condensates of phenol-formaldehyde and of phenol-formaldehyde-amine and has a water dilutability, at 20°C, at least equal to 1000%. Another subject of the invention is the insulating products based on mineral fibers treated with said sizing composition.

Description

1 SIZING COMPOSITION FOR MINERAL FIBERS AND RESULTING PRODUCTS 5 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. 10 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. 15 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. On leaving the spinner, the filaments are attenuated and entrained by a high-velocity high 20 temperature gas stream to a receiving member in order to form a web of fibers. As for external centrifugation, 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 25 member are also provided. 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 0 C) so as to polycondense the 30 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. Generally, the 2 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 5 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. 10 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. In general, a resin is considered to be able to be used as a size when its dilutability at 200C is 1000% or higher. 15 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 180C and that its dilutability at the end of this period is, at 20 0 C, 1000% or 20 higher, preferably 2000% or higher (infinite dilutability). Furthermore, 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 25 environment. The 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 30 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 3 phenol and the formaldehyde and to reduce the residual phenol content in the resin. To reduce the amount of residual formaldehyde, it is known to add a sufficient amount of urea to the resin, the urea reacting with the free 5 formaldehyde, forming urea-formaldehyde condensates (see EP 0 148 050 Al). 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%. 10 Although the amount of residual phenol is acceptable, the amount of residual formaldehyde is however too high to meet the current regulatory constraints. Moreover, it has been found that the resin is not stable under the conditions of the heat treatment to which the sized fibers are subjected in order 15 for the resin to crosslink and effectively bond the fibers in the final insulating product. At the temperatures customarily used in the oven, generally above 100 0 C, 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 20 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 Al 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 25 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 30 reacting with the formaldehyde. According to the present invention, there is provided a sizing composition for mineral fibers, containing: a liquid phenolic resin having a free formaldehyde content, expressed 533O974_1 (GHMatters) P85352.AU 4 with respect to the total weight of liquid, of 0.1% or less said resin being mainly composed of phenol-formaldehyde and phenol-formaldehyde-amine condensates and having a pH of less than 7, and a compound capable of reacting with the free formaldehyde chosen 5 from compounds having active methylene(s), alcohols, phenolic compounds, amines, hydrazides, aromatic nitrogen-containing heterocyclic compounds, sulfites, sulfamates, imides, natural products and sulfur dioxide. The present invention also provides a resin composition containing: a liquid phenolic resin having a free formaldehyde content, expressed 10 with respect to the total weight of liquid, of 0.1% or less said resin being mainly composed of phenol-formaldehyde and phenol-formaldehyde-amine condensates having a pH of less than 7, and a compound capable of reacting with the free formaldehyde chosen from compounds having active methylene(s), alcohols, phenolic compounds, 15 amines, hydrazides, aromatic nitrogen-containing heterocyclic compounds, sulfites, sulfamates, imides, natural products and sulfur dioxide. The present application further provides an insulation product comprising mineral fibres sized with the sizing composition described herein, the use of the resin composition described herein for the fabrication of a sizing 20 composition intended for the fabrication of insulating products based on mineral fibres, and the use of the sizing composition described herein for the fabrication of insulating products based on mineral fibres. 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 25 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 30 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 53300741 (GHMauters) P85352.AU 4A 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 5 (P-F) and phenol-formaldehyde-amine (P-F-A) condensates. It is understood here that 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 10 compounds (i), (ii), (iii). According to some embodiments the resin has a dilutability, measured at 20 0 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) 15 condensates known for their aptitude to degrade under the effect of temperature. As for the 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 20 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 Mannich reaction. 25 As soon as the amine is introduced the cooling is interrupted and the reaction mixture is maintained at the introduction temperature for a time that 33074 1 IGHMatiens P8532.AU 5 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. Preferably, the phenol and the formaldehyde are made to react in a formaldehyde/phenol molar ratio of between 2 and 4, or advantageously less 5 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%). The expression "degree of phenol conversion" is understood to mean 10 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, 15 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. As examples, mention may be made of alkanolamines, in particular monoethanolamine and diethanolamine, and cyclic 20 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 0 C, preferably of about 60 0 C. The phase during which the temperature is maintained allows the amine 25 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. By maintaining the mixture at the abovementioned temperature, it is also possible to reduce the free phenol content in the resin, in particular when 30 the latter is obtained with a formaldehyde/phenol molar ratio of less than 3. The free phenol content in the resin is thus 0.5% 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 6 cooling phase. In the first phase, formaldehyde and phenol are made to react in the presence of a basic catalyst, while progressively heating to a temperature between 60 and 750C, preferably about 700C. The formaldehyde/phenol molar 5 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 10 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. In the second phase, the temperature of the reaction mixture, which is reached after heating the reaction mixture (end of the first phase), is maintained 15 until the degree of phenol conversion is at least equal to 93%. 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 20 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 amount of amine, in particular of alkanolamine, is added in an amount of 0.2 to 0.7 mol, preferably 0.25 to 0.5 mol, of amine per mole of 25 starting phenol. The duration of the amine addition may vary from 10 to 120 minutes, preferably 20 to 100 minutes and advantageously 25 to 50 minutes. Preferably, the addition of the amine is carried out at a temperature between 50 and 65*C and advantageously of about 60*C. 30 After the amine has been added, a temperature hold is effected by maintaining the temperature at the end of the introduction for 10 to 120 minutes, preferably at least 15 minutes, so as to continue the condensation reaction of the formaldehyde and the phenol with the amine until a more advanced stage 7 and further reduce the amount of free formaldehyde and free phenol, the dilutability of the resin, measured at 20*C, having to be maintained at least at 1000%. After the P-F-A condensates have been formed, the reaction mixture is 5 cooled so that its temperature reaches about 20 to 25*C and is neutralized so as to stop the condensation reactions. The reaction mixture is neutralized by adding an acid until a pH of less than 7, preferably less than 6 and advantageously above 4 and better still of around 5 is obtained. The acid is chosen from sulfuric acid, sulfamic acid, 10 phosphoric acid and boric acid. Sulfuric acid and sulfamic acid are preferred. The compound capable of reacting with the formaldehyde is chosen from: 1 - compounds having active methylene(s), preferably corresponding to the following formulae: 15 > FORMULA (1) 0 0 R1-(0)a (O)b-R2 R3 n (i) in which: - R, and R 2 , which are identical or different, represent a 20 hydrogen atom, a C1-C20, preferably C1-C6, alkyl radical, an amino radical or a radical of formula: -(CH2)p-O-C-R4 in which R 4 represents a

-CH

2

-C-CH

3 25 or 8

-C=CH

2 R5 radical where

R

5 = H or -CH 3 and p is an integer that varies from 1 to 6; - R 3 represents a hydrogen atom, a C1-C10 alkyl radical, a phenyl radical or a halogen atom; 5 - a is equal to 0 or 1; - b is equal to 0 or 1; and - n is equal to 1 or 2. The preferred compounds of formula (1) are: - 2,4-pentanedione: 10 R 1 = -CH 3 ; R 2 = -CH3; R3 = H; a 0; b = 0; n = 1; - 2,4-hexanedione: R1 = -CH 2

-CH

3 ; R 2 = -CH 3 ; R 3 = H; a = 0; b = 0; n = 1; - 3,5-heptanedione: R1 = -CH 2

-CH

3 ; R 2 = -CH 2

-CH

3 ; R 3 = H; a = 0; b = 0; n = 1; 15 - 2,4-octanedione: R1 = -CH 3 ; R 2 = -(CH 2

)

3

-CH

3 ; R 3 = H; a = 0; b = 0; n = 1; - acetoacetamide:

R

1 = -CH 3 ; R 2 = -NH 2 ; R 3 = H; a = 0; b = 0; n = 1; - acetoacetic acid: 20 R 1 = -CH 3 ; R 2 = H; R 3 = H; a = 0; b = 1; n = 1; - methyl acetoacetate: R1 = -CH 3 ; R 2 = -CH 3 ; R 3 = H; a = 0; b = 1; n = 1 - ethyl acetoacetate: R1 = -CH 3 ; R 2 = -CH 2

-CH

3 ; R 3 = H; a = 0; b = 1; n = 1; 25 - n-propyl acetoacetate: R1 = -CH 3 ; R 2 = -(CH 2

)

2

-CH

3 ; R 3 = H; a = 0; b = 1; n = 1, - isopropyl acetoacetate: R1 = -CH 3 ; R 2 = -CH(CH 3

)

2 ; R 3 = H; a = 0; b = 1; n = 1; - isobutyl acetoacetate: 30 R 1 = -CH 3 ; R 2 = -CH 2

-CH(CH

3

)

2 ; R 3 = H; a = 0; b = 1; n = 1; - t-butyl acetoacetate: R1 = -CH 3 ; R 2 = -C(CH 3

)

3 ; R 3 = H; a = 0; b = 1; n = 1; 9 - n-hexyl acetoacetate: R1 = -CH 3 ; R 2 = -(CH 2

)

5

-CH

3 ; R 3 = H; a = 0; b = 1; n = 1; - malonamide:

R

1 = -NH 2 ; R 2 = -NH 2 ; R 3 = H; a = 0; b = 0; n = 1; 5 - malonic acid: R1= H; R 2 = H; R 3 = H; a = 1; b = 1; n = 1; - dimethyl malonate: R, = -CH 3 ; R 2 = -CH 3 ; R 3 = H; a = 1; b = 1; n = 1; - diethyl malonate: 10 R1 = -CH 2

-CH

3 ; R 2 = -CH 2

-CH

3 ; R 3 = H; a = 1; b = 1; n = 1; - di-n-propyl malonate: R1 = -(CH 2

)

2

-CH

3 ; R 2 = -(CH 2

)

2

-CH

3 ; R 3 = H; a = 1; b = 1; n = 1; - diisopropyl malonate: R, = -CH(CH 3

)

2 ; R 2 = -CH(CH 3

)

2 ; R 3 = H; a = 1; b 1; n = 1; 15 - di-n-butyl malonate:

R

1 = -(CH 2

)

3

-CH

3 ; R 2 = -(CH 2

)

3

-CH

3 ; R 3 = H; a = 1; b = 1; n = 1; - acetonedicarboxylic acid: R1= H; R 2 = H; R 3 = H; a = 1; b = 1; n = 2; - dimethyl acetonedicarboxylate: 20 R 1 = -CH 3 ; R 2 = -CH 3 ; R 3 = H; a = 1; b = 1; n = 2; - 1,4-butanediol diacetate: R1 = -CH 3 ; R 2 = -(CH 2

)

4 -0-CO-CH 2

-CO-CH

3 ; R 3 = H; a = 0; b = 1; n = 1; - 1,6-hexanediol diacetate: R1 = -CH 3 ; R 2 = -(CH 2

)

6

-O-CO-CH

2

-CO-CH

3 ; R 3 = H; a = 0; b = 1; n = 1; 25 - methacryloxyethyl acetoacetate: R1 = -CH 3 ; R 2 = -(CH 2

)

2 -0-CO-C(CH 3

)=CH

2 ; R 3 = H; a = 0; b = 1; n = 1. > FORMULA (11)

R

6

-CHR

7 -C--N in which: 30 - R 6 represents a cyano radical or a -C-(0)c-Ra 0 radical 10 in which: - R 8 represents a hydrogen atom, a C 1

-C

20 , preferably C 1 C 6 , alkyl radical or an amino radical; - c is equal to 0 or 1; and 5 - R 7 represents a hydrogen atom, a C 1

-C

10 alkyl radical, a phenyl radical or a halogen atom. The preferred compounds of formula (II) are: - 2-methyl cyanoacetate: R6 = -CO-0-CH 3 ; R 7 = H; 10 - 2-ethyl cyanoacetate:

R

6 = -CO-0-CH 2

-CH

3 ; R 7 = H; - 2-n-propyl cyanoacetate: R6 = -CO-O-(CH 2

)

2

-CH

3 ; R 7 = H; - 2-isopropyl cyanoacetate: 15 R 6 = -CO-0-CH(CH 3

)

2 ; R 7 = H; - 2-n-butyl cyanoacetate: R6 = -CO-O-(CH 2

)

3

CH

3 ; R 7 = H; - 2-isobutyl cyanoacetate: R6 = -CO-0-CH 2

-CH(CH

3

)

2 ; R 7 = H; 20 - 2-tert-butyl cyanoacetate:

R

6 = -CO-0-C(CH 3

)

3 ; R 7 = H; - 2-cyanoacetamide: R6 = -CO-NH 2 ; R 5 = H; - propanedinitrile: 25 R 6 = -C~ N; R 5 = H. > FORMULA (1ll)

CH

2

-O-CO-CH

2

-R

9

R

9

-CH

2 -C0C H 2

-C-(CH

2 )q-CH 3

CH

2 -0-CO-CH 2

-R

9 in which: - R 9 represents a -C-N or -CO-CH 3 radical; and 30 - q is an integer that varies from 1 to 4.

11 The preferred compounds of formula (Ill) are: - trimethylol propane triacetoacetate: R9 = -CO-CH 3 ; q = 1; - trimethylolpropane tricyanoacetate: 5 R 9 =-C-N;q=1. > FORMULA (IV) o 0 (0)r~ AO~ A. (IV) in which: - A represents a -(C H 2

)

3 or C(H 3

)

2 - radical; and 10 - r is equal to 0 or 1. The preferred compounds of formula (IV) are: - 1,3-cyclohexanedione: A = -(CH 2

)

3 ; r = 0; - Meldrum's acid: 15 A = -C(CH 3

)

2 -; r = 1; 2 - alcohols, for example monoalcohols such as benzyl alcohol and polyols such as diethylene glycol, pentaerythritol, inositol and sorbitol, in particular d-sorbitol; 3 - phenolic compounds, for example phenol, substituted phenols such 20 as o-cresol, m-cresol, p-cresol and substituted cresols, resorcinol and phloroglucinol; 4 - amines, for example: a) alkanolamines such as diethanolamine and triethanolamine; b) polyamines such as polyethylene amines, especially diethylene 25 triamine, triethylene tetramine, tetraethylene pentamine and derivatives thereof, for example in the form of salts, and amines derived from urea such as guanidine, melamine, ammeline, benzoguanamine, acetoguanamine, dicyandiamide and thiourea; c)-.aromatic amines such as para-aminobenzoic acid, aniline and 12 derivatives thereof, for example in the form of salts; d) amino acids, for example glycine, lysine and threonine; e) polyamidoamines; 5 - amides, for example urea, 1,3-dimethylurea, ethyleneurea and 5 derivatives thereof such as N-hydroxyethyleneurea, N-aminoethylethyleneurea, N-(3-allyloxy-2-hydroxypropyl)aminoethylethyleneurea, N-acryloxyethyl ethyleneurea, N-methacryloxyethylethyleneurea, N-acrylaminoethylethylene urea, N-methacrylaminoethylethyleneurea, N-methacryloxyacetoxyethylene urea, N-methacryloxyacetaminoethylethyleneurea and N-di(3-allyoxy-2 10 hydroxypropyl)aminoethylethyleneurea, biurea; biuret, triuret, acrylamide, methacrylamide, polyacrylamides and polymethacrylamides; 6 - hydrazides, for example: a) monohydrazides of formula R 1

CONHNH

2 in which R 1 represents an alkyl radical, for example a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl 15 or tert-butyl radical, or an aryl radical, for example a phenyl, biphenyl or naphthyl radical, it being. understood that a hydrogen atom from said alkyl or aryl radicals may be replaced by a hydroxy group or a halogen atom, and said aryl radical may be substituted by an alkyl radical, for example a methyl, ethyl or n-propyl radical; 20 b) dihydrazides of formula H 2

NHN-X-NHNH

2 in which X represents a -CO- or -CO-Y-CO radical, and Y is an alkylene radical, for example a methylene, ethylene or trimethylene radical, or an arylene radical, for example a phenylene, biphenylene or naphthylene radical, it being understood that a hydrogen atom from said alkylene or arylene radicals may be replaced by a 25 hydroxy group or a halogen atom, and said aryl radical may be substituted by an alkyl radical, for example a methyl, ethyl or n-propyl radical. As examples, mention may be made of oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, 30 tartaric acid dihydrazide, malic aicd dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide and carbohydrazide; c) polyhydrazides such as trihydrazides, in particular citric acid trihydrazide, pyromellitic acid trihydrazide, 1,2,4-benzenetrihydrazide, 13 nitriloacetic acid trihydrazide and cyclohexanetricarboxylic acid trihydrazide, tetrahydrazides, in particular ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, and polyhydrazides formed from a hydrazide monomer containing a polymerizable group, for example a 5 poly(acrylic acid hydrazide) or a poly(methacrylic acid hydrazide); 7 - aromatic nitrogen-containing heterocyclic compounds, for example pyrrole, indole, triazoles, especially 1,2,3-triazole and 1,2,4-triazole, diazines, especially pyrazine, pyrimidine and pyrazidine, and derivatives thereof, and triazines, especially 1,2,3-triazine, 1,2,4-triazine and 1,3,5-triazine, and 10 derivatives thereof; 8 - sulfites, for example ammonium, potassium or sodium bisulfites, and metabisulfites of alkali metals, especially sodium, or of alkaline-earth metals; 9 - sulfamates, for example sodium or ammonium sulfamate; 15 10 - imides, for example succinimide and phthalimide; 11 - natural products, for example soft wheat flour, wheat flour, charcoal, animal or plant proteins, such as soybean proteins, and hydrolyzates of these proteins, tannins especially condensed tannins, such as tannins from mimosa, quebracho, pine, pecan nut, hemlock wood and sumac, and 20 polysaccharides that may or may not be chemically modified, such as hydrolyzed or unhydrolyzed starches and heteropolysaccharides, especially chitosan; 12 - sulfur dioxide. The sizing composition may also comprise 0 to 40 parts of urea per 25 100 parts by dry weight of the mixture constituted by the resin and the urea. In the sizing composition, the content of the compound capable of reacting with the formaldehyde represents 1 to 35 parts per 100 parts by dry weight of liquid resin and where appropriate of urea, preferably 1 to 30 parts, advantageously is 20 parts or less, for example from 3 to 20 parts and in 30 particular is 15 parts or less. Generally, the sizing composition also comprises the following additives, per 100 parts by dry weight of resin and where appropriate of urea: - 0 to 10 parts of a polycondensation catalyst, for example ammonium 14 sulfate, preferably less than 7 parts; - 0 to 2 parts of silane, in particular an aminosilane; - 0 to 20 parts of oil, preferably 6 to 15 parts; and - 0 to 20 parts of aqueous ammonia (20 wt% solution), preferably less 5 than 12 parts. The role of the additives is known and is briefly recalled: 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 10 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 be prepared extemporaneously, for an 15 immediate application to the mineral fibers, by mixing the various constituents. 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 20 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 examples that follow allow the invention to be illustrated without however limiting it. 25 In the examples, the following analytical methods are used: - the amount of free phenol is measured by gas chromatography using a filled column (stationary phase: Carbowax 20 M) and a flame ionization detector (FID); - the amount of free formaldehyde is measured by high-performance 30 liquid chromatography (HPLC) and post-column reaction under the conditions of the ASTM D 5910-96 standard modified in that the mobile phase is water buffered to pH 6.8, the oven temperature is equal to 90*C and the detection is carried out at 420 nm; and 15 - the formaldehyde emissions coming from an insulation product based on glass wool are measured under the conditions of the ISO 16000 and EN 13419 standards. The measurement of the formaldehyde released is carried out after 3 days of testing at a temperature of 230C and under a relative humidity of 5 50%. EXAMPLE I Introduced into a 2-liter reactor topped with a condenser and equipped with a stirring system were 378 g of phenol (4 mol) and 809 g of formaldehyde (10 mol) as a 37% aqueous solution (formaldehyde/phenol molar ratio equal to 10 2.5) and the mixture was heated at 450C with stirring. 52.7 g of sodium hydroxide as a 50% aqueous solution (i.e. 7% by weight relative to the phenol) were regularly added over 30 minutes, the 'temperature was then progressively raised to 700C over 30 minutes, and this temperature was maintained for 80 minutes so as to reach a degree of phenol 15 conversion equal to 93%. Next, the temperature was reduced to 600C 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 600C for 15 minutes, the mixture was cooled down to about 250C over 30 minutes, and 20 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) 25 and a dilutability greater than 2000%. The solids content of the liquid resin, by weight, 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 120C for 7 days. This mixture was called reference resin composition 1. 30 APPLICATION TO THE PREPARATION OF A SIZE a) Preparation and use of the size 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 16 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. Conventionally, the sizing composition was sprayed 5 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 0 C in the middle of the product. 10 The final insulating product had a nominal thickness of 200 mm and a nominal density of 11 kg/m 3 . a') Preparation of a comparative product The comparative product was fabricated with a sizing composition that was identical in every respect but that did not contain acetoacetamide, all the 15 other parameters for fabrication of the product also being the same. b) Measurement of the formaldehyde emissions The formaldehyde emissions generated by the product obtained with the sizing composition according to the invention were three times lower compared to the formaldehyde emissions released by the comparative product. 20 c) Measurement of the stability of the size A simplified sizing composition was prepared by mixing the reference resin composition 1 with acetoacetamide in an amount of 100 parts by dry weight of resin and urea per 10 parts by weight of acetoacetamide. Table 1 collates the dilutability measurements of the sizing composition 25 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 80C and 120C.

17 Table 1 Sizing composition Reference resin according to the invention composition 80C 0 day 2000% 2000% 3 days 2000% 1800% 6 days 2000% 1600% 9 days 2000% 1300% 12 days 1700% 1200% 120C 0 day 2000% 2000% 3 days 2000% 1600% 6 days 2000% 1200% 9 days 1400% 800% 12 days 1100% 600% EXAMPLES, 2 TO 8 A liquid resin was prepared under the conditions from example 1, 5 modified in that the solids content of the resin was adjusted to 43.6%. 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 10 dilutability. Sizing compositions were then prepared containing 100 parts by dry weight of the mixture of resin and urea and a variable amount (10 or 20 parts by weight) of a compound below capable of reacting with the formaldehyde: - Acetoacetamide: example 2 15 - Ethyl acetoacetate: example 3 - Malonic acid: example 4 - Dimethyl malonate: example 5 - Malonamide: example 6 - Acetonedicarboxylic acid: example 7 18 - Dimethyl acetonedicarboxylate: example 8. 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 5 after the preparation of the sizes, all the compositions (size and reference) having been kept at 230C. Table 2 Number of parts Dilutability Ex. 2 10 1000% 20 1200% Ex. 3 10 1000% 20 ,1200% Ex. 4 10 1900% 20 1800% Ex. 5 10 1000% 20 1200% Ex. 6 10 1000% 20 1200% Ex. 7 10 1900% 20 1900% Ex. 8 10 1000% 20 1400% Reference - 900% The addition of a compound capable of reacting with the formaldehyde 10 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%). 15 EXAMPLES 9 TO 14 A liquid resin was prepared under the conditions from example 1. 20 parts by weight of urea were added to 80 parts by dry weight of the 19 resin in order to obtain a resin composition. 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 5 reacting with the formaldehyde: - Acetoacetamide: example 9 - Ethyl acetoacetate: example 10 - Dimethyl acetonedicarboxylate: example 11 - Adipic acid dihydrazide: example 12 10 - Ethyleneurea: example 13 - Sodium bisulfite: example 14 The sizing compositions from series a and from series b had a solids content equal to 35.8% and 27.5% respectively. For each series, a resin composition was prepared that did not contain 15 an agent capable of reacting with the formaldehyde, which had an identical solids content (References a and b). The sizing compositions and the resin compositions were stored at 120C and their water dilutability was measured at various intervals. 20 Series a: Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 14 Ref. a Number of parts 11.1 11.1 11.1 11.1 11.1 Dilutability 2 days 2000% 2000% 2000% 2000% 2 2000% 2000% 28 days 800% 2000% 1000% 2000% 1400% 500% Series b: Ex. 9 Ex. 10 Ex. 11 Ex. 12 Number of parts 31.6 31.6 31.6 31.6 Dilutability 8 days -22000% 2000% 2000% 2000% 34 days 1000% 2000% 1000% 2 2000% 20 Ex. 13 Ex. 14 Ref. b Number of parts 31.6 31.6 Dilutability 8 days 2000% 2000% 2000% 34 days 900% 2000% 200% It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other 5 country. In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the 10 stated features but not to preclude the presence or addition of further features in various embodiments of the invention. 53309741 (GHMalters) P85352.AU

Claims

1. A sizing composition for mineral fibers, containing: 5 a liquid phenolic resin having a free formaldehyde content, expressed with respect to the total weight of liquid, of 0.1% or less said resin being mainly composed of phenol-formaldehyde and phenol-formaldehyde-amine condensates and having a pH of less than 7, and a compound capable of reacting with the free formaldehyde chosen 10 from compounds having active methylene(s), alcohols, phenolic compounds, amines, hydrazides, aromatic nitrogen-containing heterocyclic compounds, sulfites, sulfamates, imides, natural products and sulfur dioxide.

2. The composition as claimed in claim 1, characterized in that it has a free phenol content, expressed with respect to the total weight of liquid, of 0.5% 15 or less, preferably 0.4% or less.

3. The composition as claimed in claim 1 or claim 2, characterized in that the amine is an alkanolamine or a cyclic amine.

4. The composition as claimed in claim 3, characterized in that the amine is monoethanolamine or diethanolamine. 20

5. The composition as claimed in one of claims 1 to 3, characterized in that the resin has a free formaldehyde content of 0.1% or less, a free phenol content of less than 0.4% and a water dilutability, at 20*C, of 1000% or higher.

6. The composition as claimed in any one of claims 1 to 5, characterized in that the compound having active methylene(s) corresponds to 25 one of the formulae (1) to (IV) below: > FORMULA (I) O 0 R1-(0)a (O)b-R2 R3 n(I) in which: $33074) {OHMalters) PBS352.At 22 - R 1 and R 2 , which are identical or different, represent a hydrogen atom, a C-C 20 , preferably C 1 -C 6 , alkyl radical, an amino radical or a radical of formula: -(CH 2 )p-O-C -R 4 5 in which R 4 represents a -CH 2 -C-CH 3 II or -- -CH2 R5 radical where R 5 = H or -CH 3 and p is an integer that varies from 1 to 6; 10 - R 3 represents a hydrogen atom, a C-C 10 alkyl radical, a phenyl radical or a halogen atom; - a is equal to 0 or 1; - b is equal to 0 or 1; and - n is equal to 1 or 2, Is > FORMULA (11) R 6 -CHR 7 -C -N in which: 20 - R 6 represents a cyano radical or a -C - (O) R 8 0 radical in which: - R 8 represents a hydrogen atom, a C 1 -C 2 0 , preferably C C 6 , alkyl radical or an amino radical; 25 - c is equal to 0 or 1; and - R 7 represents a hydrogen atom, a C 1 -C 10 alkyl radical, a phenyl radical or a halogen atom, 33S0741 (GHMatters) P5352.AL? 23 > FORMULA (111) CH 2 -0-CO-CH 2 -R 9 R 9 -CH 2 -CO-0-CH2--C - (CH2)q-CH3 CH 2 -0-CO-CH 2 -R l in which: 5 - RC represents a -- CN or -CO-CH 3 radical; and - q is an integer that varies from 1 to 4, > FORMULA (IV) O 0 (O)r x( 0 )r A (IV) 10 in which: -A represents a -(CH 2 ) 3 - or C(CH3)2 radical; and - r is equal to 0 or 1.

7. The composition as claimed in claim 6, characterized in that the compound of formula (1) is chosen from: 2,4-pentanedione, 2,4-hexanedione, 15 3,5-heptanedione, 2,4-octanedione, acetoacetamide, acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, n-hexyl acetoacetate, malonamide, malonic acid, dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, acetonedicarboxylic acid and 20 dimethyl acetonedicarboxylate.

8. The composition as claimed in claim 6, characterized in that the compound of formula (11) is chosen from: 2-methyl cyanoacetate, 2-ethyl cyanoacetate, 2-n-propyl cyanoacetate, 2-isopropyl cyanoacetate, 2-n-butyl cyanoacetate, 2-isobutyl cyanoacetate, 2-tert-butyl cyanoacetate, 2 25 cyanoacetamide and propanedinitrile.

9. The composition as claimed in claim 6, characterized in that the 6330741 (GHMaiiers) P863S2.AU 24 compound of formula (Ill) is chosen from: trimethylolpropane triacetoacetate and trimethylolpropane tricyanoacetate.

10. The composition as claimed in claim 6, characterized in that the compound of formula (IV) is chosen from 1,3-cyclohexanedione and Meldrum's 5 acid.

11. The composition as claimed in any one of claims 1 to 10, characterized in that the amine is chosen from alkanolamines, polyamines, aromatic amines and polyamidoamines.

12. The composition as claimed in any one of claims 1 to 10, 10 characterized in that the hydrazide is chosen from: - monohydrazides of formula R1CONHNH 2 in which R 1 represents an alkyl radical, or an aryl radical, it being understood that a hydrogen atom from said alkyl or aryl radicals may be replaced by a hydroxy group or a halogen atom, and said aryl radical may be substituted by an alkyl radical; 15 - dihydrazides of formula H 2 NHN-X-NHNH 2 in which X represents a -CO- or -CO-Y-CO radical, and Y is an alkylene radical, or an arylene radical, it being understood that a hydrogen atom from said alkylene or arylene radicals may be replaced by a hydroxy group or a halogen atom, and said aryl radical may be substituted by an alkyl radical; 20 - trihydrazides, tetrahydrazides and polyhydrazides formed from a hydrazide monomer containing a polymerizable group.

13. The composition as claimed in any one of claims 1 to 12, characterized in that it also comprises 0 to 40 parts of urea per 100 parts by dry weight of the mixture constituted by the resin and the urea. 25

14. The composition as claimed in any one of claims 1 to 13, characterized in that the content of the compound capable of reacting with the formaldehyde represents 1 to 35 parts per 100 parts by dry weight of liquid resin and where appropriate of urea.

15. The composition as claimed in claim 14, characterized in that the 30 content of the compound capable of reacting with the formaldehyde represents 15 parts or less per 100 parts by dry weight of liquid resin and where appropriate of urea.

16. The composition as claimed in one of claims 1 to 15, characterized 5330974_1 (GHMatoers) P85352.AUI 25 in that it also comprises the following additives, per 100 parts by dry weight of liquid resin and where appropriate of urea: - 0 to 10 parts of a catalyst; - 0 to 2 parts of silane; 5 - to 20 parts of oil; and - 0 to 20 parts of aqueous ammonia (20 wt% solution).

17. A resin composition containing: a liquid phenolic resin having a free formaldehyde content, expressed with respect to the total weight of liquid, of 0.1% or less said resin being mainly 10 composed of phenol-formaldehyde and phenol-formaldehyde-amine condensates having a pH of less than 7, and a compound capable of reacting with the free formaldehyde chosen from compounds having active methylene(s), alcohols, phenolic compounds, amines, hydrazides, aromatic nitrogen-containing heterocyclic compounds, 15 sulfites, sulfamates, imides, natural products and sulfur dioxide.

18. An insulation product comprising mineral fibers sized with the sizing composition as claimed in one of claims 1 to 16.

19. A product as claimed in claim 18, characterized in that the fibers are glass fibers or rock fibers.

20 20. The use of a resin composition as claimed in claim 17 for the fabrication of a sizing composition intended for the fabrication of insulating products based on mineral fibers.

21. The use of a sizing composition as claimed in one of claims I to 16 for the fabrication of insulating products based on mineral fibers. 25

22. A sizing composition for mineral fibers, an insulation product comprising the sizing composition or use of the sizing composition for the fabrication of insulating products based on mineral fibers, or a resin composition or use thereof for the fabrication of a sizing composition intended for the fabrication of insulating products, substantially as herein described with 30 reference to the Examples, excluding reference examples. 53309741 (GHMailers) PB$362.AU