Sizing composition for mineral fibers and resulting products

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, expressed with respect to the total weight of liquid, of 0.1% or less and a compound capable of reacting with the free formaldehyde. Preferably, the liquid phenolic resin is mainly composed of phenol-formaldehyde and phenol-formaldehyde-amine condensates and has a water dilutability, at 20° C., at least equal to 1000%. Another subject of the present invention is the insulating products based on mineral fibers treated by said sizing composition.

1 . A sizing composition comprising a liquid phenolic resin having a free formaldehyde content, expressed with respect to the total weight of liquid, of 0.1% or less and a compound capable of reacting with the free formaldehyde. 
     
     
         2 . The composition as claimed in  claim 1 , wherein the liquid phenolic resin consists essentially of phenol-formaldehyde and phenol-formaldehyde-amine condensates. 
     
     
         3 . The composition as claimed in  claim 1 , wherein said composition has a free phenol content, expressed with respect to the total weight of liquid, of 0.5% or less. 
     
     
         4 . The composition as claimed in  claim 1 , wherein the amine is an alkanolamine or a cyclic amine. 
     
     
         5 . The composition as claimed in  claim 4 , wherein the amine is monoethanolamine or diethanolamine. 
     
     
         6 . The composition as claimed in  claim 1 , wherein 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. 
     
     
         7 . The composition as claimed in  claim 1 , wherein the compound capable of reacting with the formaldehyde is selected from the group consisting of a compound having an active methylene, an alcohol, a phenolic compound, an amine, an amide, a hydrazide, an aromatic heterocyclic compound comprising nitrogen, a sulfite, a sulfamate, an imide, a natural product and sulfur dioxide. 
     
     
         8 . The composition as claimed in  claim 7 , wherein the compound having an active methylene is represented by one of the formulae (I) to (IV) below: 
       
         
           
           
               
               
           
         
         in which:
 R 1  and R 2 , which are identical or different, represent a hydrogen atom, a C 1 -C 20 , preferably C 1 -C 6 , alkyl radical, an amino radical or a radical of formula: 
 
       
       
         
           
           
               
               
           
         
         in which R 4  represents a 
       
       
         
           
           
               
               
           
         
         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 C 1 -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,
   R 6 —CHR 7 —C≡N  (II)
 
 
 
         in which:
 R 6  represents a cyano radical or a 
 
       
       
         
           
           
               
               
           
         
         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 
 
 R 7  represents a hydrogen atom, a C 1 -C 10  alkyl radical, a phenyl radical or a halogen atom, 
 
       
       
         
           
           
               
               
           
         
         in which:
 R 9  represents a —C≡N or —CO—CH 3  radical; and 
 q is an integer that varies from 1 to 4, 
 
       
       
         
           
           
               
               
           
         
         in which:
 A represents a —(CH 2 ) 3 — or —C(CH 3 ) 2 — radical; and 
 r is equal to 0 or 1. 
 
       
     
     
         9 . The composition as claimed in  claim 8 , wherein the compound of formula (I) is selected from the group consisting of 2,4-pentanedione, 2,4-hex anedione, 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 dimethyl acetonedicarboxylate. 
     
     
         10 . The composition as claimed in  claim 8 , wherein the compound of formula (II) is selected from the group consisting of 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-cyanoacetamide and propanedinitrile. 
     
     
         11 . The composition as claimed in  claim 8 , wherein the compound of formula (III) is trimethylolpropane triacetoacetate or trimethylolpropane tricyanoacetate. 
     
     
         12 . The composition as claimed in  claim 8 , wherein the compound of formula (IV) is 1,3-cyclohexanedione or Meldrum's acid. 
     
     
         13 . The composition as claimed in  claim 7 , wherein the compound capable of reacting with formaldehyde is at least one amine selected from the group consisting of an alkanolamine, a polyamine, an aromatic amine and a polyamidoamine. 
     
     
         14 . The composition as claimed in  claim 7 , wherein the compound capable of reacting with formaldehyde is at least one hydrazide selected from the group consisting of:
 a monohydrazide of formula R 1 CONHNH 2  in which R 1  represents an alkyl radical, or an aryl radical, wherein 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;   a dihydrazide 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, wherein 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, for example a methyl, ethyl or n-propyl radical;   a trihydrazide, a tetrahydrazide and a polyhydrazide formed from a hydrazide monomer comprising a polymerizable group, for example a poly(acrylic acid hydrazide) or a poly(methacrylic acid hydrazide).   
     
     
         15 . The composition as claimed in  claim 1 , wherein said composition also comprises 0 to 40 parts of urea per 100 parts by dry weight of the mixture comprising the resin and the urea. 
     
     
         16 . The composition as claimed in  claim 1 , wherein 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 optionally urea. 
     
     
         17 . The composition as claimed in  claim 1 , wherein said composition 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;   0 to 20 parts of oil; and   0 to 20 parts of aqueous ammonia (20 wt % solution).   
     
     
         18 . A resin composition comprising a liquid phenolic resin having a free formaldehyde content, expressed with respect to the total weight of liquid, of 0.1% or less and a compound capable of reacting with the free formaldehyde. 
     
     
         19 . An insulation product comprising mineral fibers sized with the sizing composition as claimed in  claim 1 . 
     
     
         20 . A product as claimed in  claim 19 , wherein the mineral fibers are glass fibers or rock fibers. 
     
     
         21 - 22 . (canceled) 
     
     
         23 . A method of fabricating an insulation product comprising sizing mineral fibers with the sizing composition as claimed in  claim 1 . 
     
     
         24 . A method of fabricating an insulation product comprising sizing mineral fibers with a sizing composition comprising the resin of  claim 18 .