WO2014001518A1 - Formaldehyde-free binder and use for mineral wool insulation products - Google Patents
Formaldehyde-free binder and use for mineral wool insulation products Download PDFInfo
- Publication number
- WO2014001518A1 WO2014001518A1 PCT/EP2013/063660 EP2013063660W WO2014001518A1 WO 2014001518 A1 WO2014001518 A1 WO 2014001518A1 EP 2013063660 W EP2013063660 W EP 2013063660W WO 2014001518 A1 WO2014001518 A1 WO 2014001518A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder composition
- formaldehyde
- starch
- acrylic
- weight
- Prior art date
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- 239000011230 binding agent Substances 0.000 title claims abstract description 155
- 239000011490 mineral wool Substances 0.000 title claims abstract description 30
- 238000009413 insulation Methods 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 97
- 229920002472 Starch Polymers 0.000 claims abstract description 92
- 235000019698 starch Nutrition 0.000 claims abstract description 92
- 239000008107 starch Substances 0.000 claims abstract description 87
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 57
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001253 acrylic acids Chemical class 0.000 claims description 6
- 239000008121 dextrose Substances 0.000 claims description 6
- 150000002689 maleic acids Chemical class 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 238000010410 dusting Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 description 23
- 239000004925 Acrylic resin Substances 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000002557 mineral fiber Substances 0.000 description 12
- 239000004971 Cross linker Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 235000000346 sugar Nutrition 0.000 description 8
- 229920002245 Dextrose equivalent Polymers 0.000 description 7
- 150000001720 carbohydrates Chemical class 0.000 description 7
- 235000014633 carbohydrates Nutrition 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 vinyl compound Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920001353 Dextrin Polymers 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 235000019425 dextrin Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000008163 sugars Chemical class 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229920005825 ACRODUR® DS 3530 Polymers 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000133063 Trixis Species 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0082—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability making use of a rise in temperature, e.g. caused by an exothermic reaction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1006—Absence of well-defined organic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/52—Sound-insulating materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to formaldehyde-free resins and their use in the manufacture of mineral wool insulation products of zero formaldehyde emissions .
- the mineral wool produc s have traditionally being manufactured by adhering mineral fibers by means of phenol- formaldehyde resins, profiting from relatively low costs and good mechanical properties,, stability and water resistance granted to the finished products.
- Most common phenol - formaldehyde resins for mineral wool production are resols manufactured by condensation of formaldehyde and phenol catalyzed by alkalis and using a large molar excess of the formaldehyde .
- polyester resins based on carboxylated polymers .
- Most common ones contain a combination of one acrylic (co) olymer and one low molecular weight poiyol .
- the resin cures at high temperatures under acidic conditions via the formation of ester-bonds.
- EP 583 086 US 5,763,524
- EP 0 990 729 Al US 6,331,350
- US 6,136,916 US 6,221,973
- Rohm&Haas describe the use of polyacrylic acid and either hydroxy1amines (such as triethanolamine) or glycerol as cross- linkers .
- US 5,318, 990 [Owens Corning] teaches the use of polycarboxylic polymer and glycerol or trimethylolpropane .
- US 6,331,350 [Johns Manvender] describes a binder consisting of polycarboxylic polymer and poiyol such as triethanolamine , at a K not greater than 3.5.
- Another group of binders contain resins based on co-polymers of acrylic acid.
- US 6,071,994 [BASF] describes the use of co-polymers based on acrylic and maieic acids , and poiyols as cross-linkers at a pH lower than 3,5.
- Another important group of formaldehyde- free resins found in the art refers o bio-resins based on carbohydrates and low molecular weight poly-acid, such as citric acid, as cross- linker .
- the resins cure at high temperatures under acidic conditions via, in most cases, the formation of ester-bonds.
- carbohydrates soluble in water it is preferred the use of carbohydrates soluble in water to facilitate the processing and the curing of the resins .
- One representative group is based on sugars . For instance WO 2009/19232 and US 2011/260094 [Knauf] describe a bindex" based on the MaiHard type reaction composed of a reducing sugar, acid precursor derivable from an inorganic salt and a source of nitrogen.
- WO 2012/028810 describes a binder composition consisting of non-reducing sugar such as glucose and one inorganic acid metal salt .
- WO 2010/139899 describes a binder compositxon consisting of saccharide such as glucose and polycarboxylic acid .
- a second representative group consists of a combination of dextrins derived upon chemical or enzymatic treatment of native starches.
- US 2005/0215153 Al [Ovens Corning] teaches the use of dextrin in combination with cross- linkers .
- WO 2011/044490 Al teaches the use of water soluble carbohydrates havxng a Dextrose Equivalent (DE) between 2 and 20 in combination with cross - linkers .
- DE Dextrose Equivalent
- WO 2011/002730 Al describes the use of modified starches with a degree of polymerization between 20 and 4000 units, in combination with cross- linkers .
- this group of patent applications it is claimed that the dextrination to obtain water soluble modified starches favors the processability of the binder, because of the lowering of the viscosity, and an increase of the curing rate in the presence of cross- linkers .
- US 2008/108741 and WO 2008/053332 [Dynea] describe mixtures of water-soluble starches containing more than 80 weight % of amylopectin and a polycarboxylic acid as cross -linker.
- bio- resins based on renewable polyols offer important advantages over the synthetic -resins, particularly their lower costs and better sustainability profile. Yet, these bio-resins shall be used in higher dosage on mineral fibers compared to the phenolic or acrylic resins because the mechanical properties, particularly upon aging, delivered to mineral wool are normally lower, and because of the greater mass losses due to thermal degradation during the process of curing. Indeed, the process of curing of these bio-resins requires a strict control of the temperature between narrow ranges. This is needed to achieve the suitable mechanical properties and to avoid unwanted thermal degradation.
- the obj ect is solved by a formaldehyde- free aqueous binder composition in the form of a dispersion, comprising starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and one or more acrylic component ⁇ s) , wherein the acrylic component ⁇ s ) is/are selected from the group consisting of polyacrylic acid, copolymers of acrylic and maleic acids, copolymers of ethylene -unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride; salts of any preceding (co) olymers , curable resins based on any preceding (co) olymers , and mixtures thereof.
- Another object of the present invention is to provide a mineral wool product comprising a cured formaldehyde -free binder obtainable by the following process steps;
- aqueous binder composition in the form of a dispersion comprising a) starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch; and b) one or more acrylic component (s) , selected from the group consisting of polyacrylic acid, copolymers of acrylic and maleic acids, copolymers of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride; salts of any preceding ⁇ co) olymers , curable resins based on any preceding (co) olymers , and mixtures thereof , wherein the mineral fibers are impregnated via spraying the aqueous binder composition with a solid content of 4 to 10 weight %, and
- the inventors have surprisingly found three synergic effects between native starch being water insoluble, and the acrylic component, such as acrylic resin or acrylic (co) olymers , which makes the new formaldehyde-free binder of the present invention most suitable as a binder for mineral wool ;
- the binding strength granted to mineral fibers by the mixture is maintained or even enhanced in comparison to acrylic binders .
- the later is particularly seen under stress 'wet' conditions, which are predictable of the behavior of the new binders upon aging .
- the mixture of these two components exceptionally improves the "cost per job' and the sustainability of the new binder.
- the viscosity and stability of the new binder is very suitable despite of the insolubility of the native starch component, due to the dispersing and stabilizing effect that the acrylic component exerts on the native s arch . This enables the production of binder dispersions of low viscosity very suitable for further application to mineral fibers by spray-on process ,
- the curing of the new binder can be done at reduced temperatures in comparison to other bio-resins based o high DE carbohydrates like dextrins o sugars, what results in a considerable energy saving.
- An additional advantage over the bio-resins based on high DE carbohydrates like dextrins or sugars, is that the curing process of the new binder does not require a strict control of the temperature . This is because the mass loss by thermal degradation of the new resin during the curing is negligible. Indeed, the mineral wool product made with the new binder has a characteristic whitish color instead of brownish color of products made with above mentioned bio- resins .
- Figure 1 shows the bonding properties of binders A to D according to the present invention, native starch Meritena 120 and acrylic resin Aquaset BI700.
- Figure 2 shows the viscosity of binders A to D according to the present invention, and acrylic resin Aquaset BI700 alone . The viscosity has been measured on aqueous compositions containing a solid content of 50 weight % .
- Figure 3 shows the sedimentation time of binders A to D according to the present invention, and a dispersion of native starch Meritena 120. The sedimentation time has been measured on aqueous compositions containing a solid content of 45 weight %.
- Figure 4 shows the Young moduli under wet conditions for binders B and D according to the present invention, and bio- resin based on dextrose described in WO 2008/089851 Al at page 6.
- Figure 5 shows the mass loss (TGA, 10 °C/min, % solid losses at 200 °C) for binders B and D according to the present invention, acrylic resin Aquaset B1700, and for bio-resin based on dextrose described in WO 2008/089851 Al at page 6.
- the new formaldehyde- free binder is an aqueous composition containing at least one starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and one or more acrylic component (s) .
- the new formaldehyde-free binder of the present invention contains at least one starch wherein 95 to 100 weight % of the starch is water- insoluble native starch, and one or more acrylic component ( s ⁇ .
- the formaldehyde- free binder is an aqueous composition comprising at least one starch, wherein 99 or 100 weight % or an amount ranging between these two values of t e starch is water- insoluble native starch, and one or more acrylic component ( s ) .
- the binder composition of the present invention is ''formaldehyde- free' .
- the term 'formaldehyde-free' in the sense of the present application indicates that essentially no formaldehyde is contained in nor released from the binder composition of the present invention.
- the starch used as first component of the new binder of the present invention is a native starch with no chemical modification. It may be obtained from vegetable sources such as corn, potatoes , wheat, rice, cassava, soybean or other plants containing high starch conten .
- the native starches are usually available as white powders , which still contain small amounts of non- carbohydrate components such as proteins and salts . They also contain about 10 to 15 weight % humidity, which can be measured according to the method in ISO 1666.
- the native starch weight % values refer to the ldry f native starch excluding the humidity content .
- ⁇ insoluble i water' means a solubility of the starch lower than 0.15 g per 100 g of water at 20 °C, The solubility can be measured as follows ; prepare a homogeneous dispersion of starch in water at 20 °C, filter it through a standard laboratory filter paper to get a clear solution, and evaporate 100 g of said clear solution at 135 °C for 120 minutes to obtain a solid residue. The solubility is reported as per the weight of the solid residue in grams contained in the 100 g clear starch solution.
- the native starches contained in the binder according to the present invention have a Dextrose Equivalent ( DE) lower than 2, more pre erable lower than 1.
- DE Dextrose Equivalent
- Non- limiting examples of native starches useful for the binder of the present invention are Meritena 120 , Amyze 150, Meritena 400 or Amyzet 500 from Syrai , Maize Starch from Roquette or C*Gel series from Cargill.
- the one or more acrylic component (s) used as second component of the new formaldehyde-free binder in the present invention is a curable acrylic resin, an acrylic (co) olymer or a mixture thereof .
- the acrylic component used as a component of the formaldehyd -free binder according to the present invention is a curable acrylic resin described in the art.
- the curable acrylic resin comprises at least one acrylic (co) polymer and a. polyol , Optionally they can contain esterification catalysts and/or, pH modifiers.
- the acrylic (co) olymer is a copolymer of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride, and , mixtures thereof; preferably polyaerylie acid or copolymers of acrylic and maleic acids .
- the polyol is an alkane-polyol or a1kano1amines .of molecular weight lower than 1000 g/mol described in the art, like triethanolamine, glycerol, trimethylolpropane and the like.
- Hon- limiting examples of curable acrylic resin suitable for the new formaldehyde-free binder in the present invention are Aquaset BI700 from Dow Chemicals, Acrodur DS3530 from BASF, or Leaf Free series from Georgia Pacific,
- the acrylic component used as second component of the new formaldehyde- free binder in the present invention is an acrylic (co) olymer.
- the acrylic (co) polymer is a copolymer of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride, and mixtures thereof. More preferably the acrylic (co) olymer is polyacrylic acid or copolymers of acrylic and maleic acids.
- the acrylic (co) olymers are normally available as water solutions, dispersion or powders , which can be dissolved or dispersed in water by mechanical means at temperatures from about 10 to 50 °C .
- Non- limi ing examples of acrylic (co) olymers useful for the new binder in the present invention are Syn an 8220 from Interpolymer , Craymul 2154 from Cray Valley, or Acumer 1000 from Dow Chemicals.
- the acrylic component used as second component of the new formaldehyde-free binder in the present invention is an acrylic (co) polymer
- aqueous binder compos it ion as used in the pre sent application means a binder composition that is composed of a solid content and water. Due to the water- insolubility of the water- insoluble native starch, the formaldehyde-free aqueous binder composition of the invention is a dispersion.
- the solid content of the aqueous binder composi ions is not particularly limited, and depends on its intended application. So, for example, for application of the binder composition in the form of a dispersion to the mineral fibers via spraying it is preferred that the formaldehyde- free binder composition according to the present invention contains a solid content of 4 to 10 weight % . Particularly preferred in this case is a solid content of 5 to 8 weight %.
- Other application methods of the aqueous binder composition according to the present invention ar ⁇ e also possible, for example spreading or immersion. In those cases, other solid content ranges might be more appropriate. Thus, for example, a solid content of 15 to 30 weight % , e.g.
- 20 weight % may be more suitable if the binder composition is applied by immersion of the substrate in the aqueous binder composition according to the presen invention.
- a reference solid content of 50 weight % is selected.
- the amount of native starch and the amount of acrylic component to be used in the binder of the present invention are not specifically limited. However it is suitable that the amount of native starch is 10 to 35 weight % based on the total solid content of the binder composition, the amount of acrylic component is 5 to 90 weight % based on the total solid content of the binder composition, and the sum of the amount of native starch and the amount of acrylic component is at least 70 weight % based on the total solid content of the binder composition.
- very useful binder compositions in form of low viscosity dispersions are obtained when the amount of native starch is 25 to 80 weight % based on the total solid content, the amount of acrylic component is 75 to 20 weight % based on the total solid content, and and the sum of the amount of native starch and acrylic component of at least 80% with respect to the total solid content of the binder composition.
- the amount of native starch is from about 60 to about 90 weight % with respect o the total solid content of the binder composition
- the amount of acrylic component is from about 10 to about 40 weight % with respect to the total solid content of the binder composition
- the sum of the amount of native starch and acrylic component is at least 70 weight % with respect to the total solid content of the binder composition.
- This above embodiment covers binder compositions that are economically attractive (the acrylic component is normally more expensive than the native starch) and, at the same time, after they are applied and cured on the substrates show good binding strength in dry and wet conditions, and good ageing behavior .
- the binder composition in the form of a dispersion according o the present invention comprises an amount of native starch of 25 to 50 weight % based on the total solid content, an amount of acrylic component of 75 to 50 weight % based on the total solid content, and the native starch and the acrylic component amounts add at least 90 weight % with respect to the total solid content of the binder composition.
- Such binder compositions after being applied and cured on the substrates, result in improved binding strength in wet conditions and improved ageing behavior of the bonded products in humid conditions .
- the binder composition of the present invention also comprises additives described in the art to enhance the performance for its use for mineral wool.
- additives are esterification catalysts such as sodium hypophosphite, pH control agent such as ammonium sulfate, hydropho ic ing agent such as silicones, de -dusting agent such as paraffin oils, adhesion promoter agent such as alkoxysilanes , fiber softeners, preservatives, dyes and corrosion inhibitors.
- the new binder additionally comprises at least one filler or chain extender such as, but not limited to, urea, sugars, molasses, iignosulfonates or tannins.
- the pH of the new binder composition there is no limitation about the pH of the new binder composition. Nevertheless it is preferred that the pH of the new binder is above 2.
- binder composition of the present invention has the following characteristic: when the binder composition has a solid content of 50 weight- %, the viscosity of the binder composition is less than 200 mPa.s at 20 °C, and preferably less than 50 m?a . s . at 20 °C.
- the process for manufacturing the formaldehyde- free binder composition according to the present invention comprises the steps of :
- step (b) contacting the dispersion obtained in step (a) with one or more acrylic component (s) and, optionally, further additives, at a temperature of 10 to 40 °C,
- the dispersion step (a) is done with mechanical stirring until obtaining a homogenous mixture. It is important to carry out this step at a temperature between 10 to 40 °C, and preferably from about 20 to 30 °C . This range of temperature is suitable to disperse the starch in water and low enough to avoiding % gelatinization' of the starch granules what otherwise would increase the viscosity and difficult the processing.
- the time of dispersing is not particularly limited because depends on the specific dispersion equipment.
- the contacting in step (b) is done with mechanical stirring until obtaining a homogenous mixture. It is important to carry out said contacting process at a temperature between 10 to 40 °C, and preferably from about 20 to 30 °C, for the reasons mentioned above. Additionally, this range of temperature is also suitable to avoid unwanted hydrolysis and solubilization of the native starch.
- the time of contacting step (b) is not particularly limited. Nevertheless it is preferred to carry out this step in less than 60 minutes . Dnder these conditions it is possible, for example, to obtain a binder composition having a viscosity below 50 mPa.s at a solid content of 50 weight % solids.
- the temperature during the preparation of the binder compositio according to the present invention should be kept below 65 °C, preferably below 50 °C, and most preferably below 40 °C. According to a particularly preferred embodiment of the present invention, the temperature during the process of preparing the binder composition of the present invention is not raised above room temperature. In other words, the un-modified insoluble native starch is applied as such to the fibers as part of the binder composition. The binder composition on the fibers is subsequently dried and cured at tempe atures above 100 °C.
- the process for manufacturing of the new formaldehyde-free binder composition according to the present invention may comprise the step of dispersing starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, in an aqueous mixture containing the acrylic component and, optionally, further additives, at a temperature of 10 to 40 °C .
- the new formaldehyde-free binders according to the present invention are to be used as binder for fibrous substrates, particularly mineral wool fibers.
- the new binder is applied to the mineral fibers so that they become impregnated.
- the application is via spraying .
- the total solid content of the new binder composition is not particularly limited. Nevertheless it is particularly suitable to use an aqueous binder composition wherein the solid content is from between 4 to 10 weight %.
- the amount of new binder to be applied onto the mineral fibers is not particularly limited and is suitably adjusted depending on the type of mineral wool product.
- a typical amount of dried, binder applied onto the fibers is in the range of 4 to 20 weight % of dried binder with respect to the weight of mineral wool fibers.
- the impregnated fibers are then collected in a forming chamber and then conveyed to a curing oven where the new binder cures to set.
- the binder composition of the present invention cures at temperatures of above 100 °C, preferably at a temperature of 140 °C to 180 °C, e.g. at 170 °C, which is lower than the curing temperatures required for sugar-based bio-binders described in the art.
- the bio-binder described in WO 2008/089851 Al at page 6 has a curing temperature of 190 °C, s seen in Figure 4.
- the new binder composition of he present invention looses a very low amount of mass during the process of curing, preferable less than 1 % at 200 °C .
- binder- efficiency defined as the amount of binder solids after curing compared to the amount of binder solids applied on mineral fibers.
- sugar-based bio-binders described in the art loose significantly more mass . This deteriorates the binder efficiency.
- the bio- binder described in WO 2008/089851 Al at page 6 looses about 25 % mass at 200 °C.
- the mineral wool mat is afterwards cut and shaped into its final dimensions and packaged.
- the mineral wool product manufactured with the new binder may comprise at least one additional facing made of paper, aluminum, glass veil or mixtures thereof .
- the mineral wool product obtained may be used for thermal or acoustic insulation purposes in buildings, conducts, particularly air-conditioning conducts, electrical appliances, ships, aircrafts and spaceships.
- One example of the first embodiment of the present invention is a binder composed by a mixture of native starch Meritena 120 supplied by Syral and acrylic resin Aquaset BI 700 supplied by Dow Chemicals, at 50 weight % each with respect to the total solid %.
- Meritena 120 is a native starch derived from corn, with DE close to zero, supplied as a whitish powder containing 12% humidity.
- Aquaset BI 700 is an acrylic resin based on polyacrylic acid and triethanolamine , supplied as a 55 weight % solids water solution.
- a 2.5 liter round-bottom flask is charged with 489 mL of water and a mechanical s irring bar . Then, 511 grams of Meritena 120 powder are added and the mixture vigorously stirred for 30 minutes at 20 °C, obtaining a homogenous white dispersion of approximately 45 weight % solids. Afterwards, 818 grams of Aquaset BI 700 were added and the mixture stirred for additional 10 minutes at 20 °C . The resulting binder C is a milky dispersion of approximately 50 weight 3 ⁇ 4 solids . , consisting of a 50:50 solids mixture of starch and acrylic component .
- a series of new binders based on mixtures of Meritena 120 and Aguaset Bl 700 are provided in Table 1. All of them can be similarly prepared following the method above, by varying the mixing ratio between both components .
- the bonding strength on mineral fibers of the new binders A to D was measured in a strain-strength test, as per the Young modulus of a glass paper treated with the binder.
- the treatment of the glass paper consists of impregnating the glass paper with 20 weight % solids of the new binder, and curing for 3 min at 170 °C .
- the modulus measured under these conditions is referred as under 'dry' conditions.
- the effect of ageing on the bonding properties of the new binders was also evaluated in a consecutive experiment, consisting of immersing the cured treated glass paper specimens in water at 85 °C for 10 minutes , drying and measuring again the Young modulus value in a strain-strength test.
- the Young modulus measured under these conditions is referred as under 'wet' conditions .
- the Fig. 1 shows the Young moduli measured under 'dry' and 'wet' conditions for binders A to D, composed of mixtures of native starch Meritena 120 and acrylic resin Aquaset BI 700.
- the Young modulus values for native starch Meritena 120 and acrylic resin Aquaset BI 700 on their own measured under the same conditions are also provided.
- the bonding strength of the new binders under wet conditions is improved in comparison to that of the acrylic resin alone or the native starch alone.
- the best performing under wet conditions is binder B; i.e. a composition of about 35 weight % of native starch and 65% of acrylic component.
- the bonding properties under 'dry' conditions for binders A to D are very suitable.
- Young modulus is measured on 25x75mm strips of glass paper type Borosilicate GF/A from Whatman International, impregnated with ' binder and cured as described above, by using a tensile strength tester set at a constant extension rate of 6 mm/rain.
- the viscosity of the new binders was measured with a Brookfield viscometer with spindle 1 at 20 C C at a solid content of 50 weight %.
- the Fig. 2 shows the viscosity for binder A to D, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700, at 50 weight % solids. As a reference, the viscosity of acrylic resin Aquaset BI700 is also provided also at 50 weight % solids. It can be seen that all the binders A to D have a viscosity below 50 mPa.s at 20 °C which is very favorable for their use in mineral wool manufacturing.
- the starch component lias a significant viscosity reduction effect on the high viscous acrylic component .
- Fig. 3 shows the sedimentation time for binders A to D according to the present invention, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700 at 45% weight % solids .
- the sedimentation time of a homogeneous dispersion of native starch Meritena 120 alone in water is provided. It can be seen that ail binder dispersions A to D according to the present invention have an increased stability, with sedimentation time above 5 minutes, in comparison to the low stability of the dispersion of insoluble native starch in water. This is also very suitable for the use of the new binders in mineral wool manufacturing.
- the curing temperature of the new binders was compared to other bio-resins using the respective values of the Young modulus under wet conditions .
- the Figure 4 shows the Young modulus under wet conditions for the binders B and D according to the present invention, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700, cured for 3 minutes at 170 °C .
- As a reference it has been also measured the Young modulus under wet conditions of a bio-resin composed of dextrose (82%) , citric acid (15%) and ammonia (3.1%) (see WO 2008/089851 Al; page 6 ) .
- the bio-resin was cured at 170 °C and 190 °C, in both cases for 3 minutes. It can be seen that the binders B and D according to the present invention already achieve mechanical strength curing at 170 °C, whereas the bio-resin needs curing at 190 °C to provide sufficient mechanical strength.
- the mass loss % upon curing for the new binders was measured by TGA (Thermal Gravimetric Analysis) , as the relative solids content weight diminution at 200 °C using a ramp of 10 °C/min in a nitrogen atmosphere. This is representative of the maximum temperatures at -which resins are normally exposed during the curing process.
- the Figure 5 shows the mass loss of binders B and D according to the present invention. As a comparison, it also shows the mass loss % for the acrylic resin Aguaset BI700 and a bio-resin composed of dextrose (82%), citric acid (15%) and ammonia (3.1%) (described in patent application WO 2008/089851 Al at page 8) .
- the mass loss, referred as relative solids content weight diminution, for the new binders B and D is less 0.3%, similar to the acrylic resin but significantly lower tha the bio-resin based on dextrose, which loses up to 25% mass.
- Table 2 New binders based on mixtures of native starch and acrylic component. Composition i given in weight % with respect to the total solid %.
Abstract
The present invention relates to a new formaldehyde - free binder composition for mineral wool products., wherein the binder composition is an aqueous composition containing starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and an acrylic component. The present invention also relates to the use of this formaldehyde-free binder composition in the manufacturing of mineral wool insulation products. Finally, the present invention relates to a process for manufacturing the formaldehyde-free binder composition wherein a dispersion of starch, wherein an amount of 95 weight % or more of the starch is water-insoluble native starch, is brought in contact with the acrylic component at a temperature of not higher than 40 °C.
Description
Formaldehyde-free binder and use for mineral wool insulation products
Field of the Invention
The present invention relates to formaldehyde-free resins and their use in the manufacture of mineral wool insulation products of zero formaldehyde emissions .
State of rhe A."
The mineral wool produc s have traditionally being manufactured by adhering mineral fibers by means of phenol- formaldehyde resins, profiting from relatively low costs and good mechanical properties,, stability and water resistance granted to the finished products. Most common phenol - formaldehyde resins for mineral wool production are resols manufactured by condensation of formaldehyde and phenol catalyzed by alkalis and using a large molar excess of the formaldehyde .
The main drawback of the used phenol- formaldehyde resins is the slo release of formaldehyde in finished products to the environment, contributing to worsen the indoor air quality; hence the interest of formaldehyde-free resins for mineral wool products. Different alternative resins have been described in. the art,
One alternative to the use of phenol-formaldehyde resins in mineral wool production are the polyester resins based on carboxylated polymers . Most common ones contain a combination
of one acrylic (co) olymer and one low molecular weight poiyol . The resin cures at high temperatures under acidic conditions via the formation of ester-bonds. For instance EP 583 086 (US 5,763,524), EP 0 990 729 Al (US 6,331,350), US 6,136,916 and US 6,221,973 [Rohm&Haas] describe the use of polyacrylic acid and either hydroxy1amines (such as triethanolamine) or glycerol as cross- linkers . US 5,318, 990 [Owens Corning] teaches the use of polycarboxylic polymer and glycerol or trimethylolpropane . US 6,331,350 [Johns Manviile] describes a binder consisting of polycarboxylic polymer and poiyol such as triethanolamine , at a K not greater than 3.5. Another group of binders contain resins based on co-polymers of acrylic acid. For instance, US 6,071,994 [BASF] describes the use of co-polymers based on acrylic and maieic acids , and poiyols as cross-linkers at a pH lower than 3,5. US 2010/0029160 [Georgia Pacific] teaches the use of hydrolyzed copolymer of maieic anhydride and a vinyl compound such as styrene and a monomeric poiyol as cross - linker , at a. pH of more than 7. The acrylic resins above confer excellent mechanical properties to the mineral wool products . Unfortunately, the costs of these resins are about two to three -fold higher than the conventional phenolic -based resins, this being a significant dra -back for their use in indus ry . Additionally, acrylic resins normally have the processing disadvantage of a relatively high viscosity which limits the use for manufacturing high density, mineral wool products .
Another important group of formaldehyde- free resins found in the art refers o bio-resins based on carbohydrates and low molecular weight poly-acid, such as citric acid, as cross- linker . The resins cure at high temperatures under acidic conditions via, in most cases, the formation of ester-bonds. In general, it is preferred the use of carbohydrates soluble in water to facilitate the processing and the curing of the
resins . One representative group is based on sugars . For instance WO 2009/19232 and US 2011/260094 [Knauf] describe a bindex" based on the MaiHard type reaction composed of a reducing sugar, acid precursor derivable from an inorganic salt and a source of nitrogen. WO 2012/028810 [Isover] describes a binder composition consisting of non-reducing sugar such as glucose and one inorganic acid metal salt . WO 2010/139899 [Isover] describes a binder compositxon consisting of saccharide such as glucose and polycarboxylic acid . A second representative group consists of a combination of dextrins derived upon chemical or enzymatic treatment of native starches. For instance, US 2005/0215153 Al [Ovens Corning] teaches the use of dextrin in combination with cross- linkers . WO 2011/044490 Al teaches the use of water soluble carbohydrates havxng a Dextrose Equivalent (DE) between 2 and 20 in combination with cross - linkers . WO 2011/002730 Al describes the use of modified starches with a degree of polymerization between 20 and 4000 units, in combination with cross- linkers . In this group of patent applications, it is claimed that the dextrination to obtain water soluble modified starches favors the processability of the binder, because of the lowering of the viscosity, and an increase of the curing rate in the presence of cross- linkers . US 2008/108741 and WO 2008/053332 [Dynea] describe mixtures of water-soluble starches containing more than 80 weight % of amylopectin and a polycarboxylic acid as cross -linker. The bio- resins based on renewable polyols offer important advantages over the synthetic -resins, particularly their lower costs and better sustainability profile. Yet, these bio-resins shall be used in higher dosage on mineral fibers compared to the phenolic or acrylic resins because the mechanical properties, particularly upon aging, delivered to mineral wool are normally lower, and because of the greater mass losses due to thermal degradation during the process of curing. Indeed, the process of curing of
these bio-resins requires a strict control of the temperature between narrow ranges. This is needed to achieve the suitable mechanical properties and to avoid unwanted thermal degradation.
It is an object of the present invention to provide a formaldehyde -free binder which is particularly valuable for the use in mineral wool production due to excellent binding strength, easy manufacture and low costs.
It is a further object of the present invention to provide a process for the preparation of the new formaldehyde- free binder.
Summary of the invention
The above object is solved by a formaldehyde - free aqueous binder composition comprising
- starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and
- one or more acrylic component <s) .
According to a preferred embodiment, the obj ect is solved by a formaldehyde- free aqueous binder composition in the form of a dispersion, comprising starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and one or more acrylic component { s) , wherein the acrylic component { s ) is/are selected from the group consisting of polyacrylic acid, copolymers of acrylic and maleic acids, copolymers of ethylene -unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride; salts of any preceding (co) olymers , curable resins based on any preceding (co) olymers , and mixtures thereof.
Another object of the present invention is to provide a mineral wool product comprising a cured formaldehyde -free binder obtainable by the following process steps;
- impregnating mineral fibers of a binder- free mineral wool product with an aqueous binder composition in the form of a dispersion comprising a) starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch; and b) one or more acrylic component (s) , selected from the group consisting of polyacrylic acid, copolymers of acrylic and maleic acids, copolymers of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride; salts of any preceding {co) olymers , curable resins based on any preceding (co) olymers , and mixtures thereof , wherein the mineral fibers are impregnated via spraying the aqueous binder composition with a solid content of 4 to 10 weight %, and
- curing the aqueous binder composition at a temperature above 100°C.
The inventors have surprisingly found three synergic effects between native starch being water insoluble, and the acrylic component, such as acrylic resin or acrylic (co) olymers , which makes the new formaldehyde-free binder of the present invention most suitable as a binder for mineral wool ;
- Firstly, the binding strength granted to mineral fibers by the mixture is maintained or even enhanced in comparison to acrylic binders . The later is particularly seen under stress 'wet' conditions, which are predictable of the behavior of the new binders upon aging . Hence the mixture of these two components exceptionally improves the "cost per job' and the sustainability of the new binder.
- Secondly, the viscosity and stability of the new binder is very suitable despite of the insolubility of the native starch component, due to the dispersing and stabilizing effect that the acrylic component exerts on the native s arch . This enables the production of binder dispersions of low viscosity very suitable for further application to mineral fibers by spray-on process ,
- Thirdly, the curing of the new binder can be done at reduced temperatures in comparison to other bio-resins based o high DE carbohydrates like dextrins o sugars, what results in a considerable energy saving. An additional advantage over the bio-resins based on high DE carbohydrates like dextrins or sugars, is that the curing process of the new binder does not require a strict control of the temperature . This is because the mass loss by thermal degradation of the new resin during the curing is negligible. Indeed, the mineral wool product made with the new binder has a characteristic whitish color instead of brownish color of products made with above mentioned bio- resins .
Brief Description of the Drawings
Figure 1 shows the bonding properties of binders A to D according to the present invention, native starch Meritena 120 and acrylic resin Aquaset BI700.
Figure 2 shows the viscosity of binders A to D according to the present invention, and acrylic resin Aquaset BI700 alone . The viscosity has been measured on aqueous compositions containing a solid content of 50 weight % .
Figure 3 shows the sedimentation time of binders A to D according to the present invention, and a dispersion of native starch Meritena 120. The sedimentation time has been measured on aqueous compositions containing a solid content of 45 weight %.
Figure 4 shows the Young moduli under wet conditions for binders B and D according to the present invention, and bio- resin based on dextrose described in WO 2008/089851 Al at page 6.
Figure 5 shows the mass loss (TGA, 10 °C/min, % solid losses at 200 °C) for binders B and D according to the present invention, acrylic resin Aquaset B1700, and for bio-resin based on dextrose described in WO 2008/089851 Al at page 6.
Composition of the new binder
According to the present invention, the new formaldehyde- free binder is an aqueous composition containing at least one starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and one or more acrylic component (s) . This means that the new formaldehyde-free binder of the present invention contains at least one starch wherein 95 to 100 weight % of the starch is water- insoluble native starch, and one or more acrylic component ( s} . Preferentially the formaldehyde- free binder is an aqueous composition comprising at least one starch, wherein 99 or 100 weight % or an amount ranging between these two values of t e starch is water- insoluble native starch, and one or more acrylic component ( s ) .
The binder composition of the present invention is ''formaldehyde- free' . The term 'formaldehyde-free' in the sense
of the present application indicates that essentially no formaldehyde is contained in nor released from the binder composition of the present invention.
95 weight % or more of the starch used as first component of the new binder of the present invention is a native starch with no chemical modification. It may be obtained from vegetable sources such as corn, potatoes , wheat, rice, cassava, soybean or other plants containing high starch conten . The native starches are usually available as white powders , which still contain small amounts of non- carbohydrate components such as proteins and salts . They also contain about 10 to 15 weight % humidity, which can be measured according to the method in ISO 1666. In the present application, the native starch weight % values refer to the ldryf native starch excluding the humidity content .
95 to 100 weight % of the starch used in the binder of the present invention is insoluble in water. It is particularly preferred that all of the starch used in the binder composition of the present invention is water- insoluble . The term λ insoluble i water' as used herein means a solubility of the starch lower than 0.15 g per 100 g of water at 20 °C, The solubility can be measured as follows ; prepare a homogeneous dispersion of starch in water at 20 °C, filter it through a standard laboratory filter paper to get a clear solution, and evaporate 100 g of said clear solution at 135 °C for 120 minutes to obtain a solid residue. The solubility is reported as per the weight of the solid residue in grams contained in the 100 g clear starch solution.
It is preferred that the native starches contained in the binder according to the present invention have a Dextrose Equivalent ( DE) lower than 2, more pre erable lower than 1.
Non- limiting examples of native starches useful for the binder of the present invention are Meritena 120 , Amyze 150, Meritena 400 or Amyzet 500 from Syrai , Maize Starch from Roquette or C*Gel series from Cargill.
The one or more acrylic component (s) used as second component of the new formaldehyde-free binder in the present invention is a curable acrylic resin, an acrylic (co) olymer or a mixture thereof .
In one embodiment of the present invention, the acrylic component used as a component of the formaldehyd -free binder according to the present invention is a curable acrylic resin described in the art. Preferably, the curable acrylic resin comprises at least one acrylic (co) polymer and a. polyol , Optionally they can contain esterification catalysts and/or, pH modifiers. The acrylic (co) olymer is a copolymer of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride, and, mixtures thereof; preferably polyaerylie acid or copolymers of acrylic and maleic acids . The polyol is an alkane-polyol or a1kano1amines .of molecular weight lower than 1000 g/mol described in the art, like triethanolamine, glycerol, trimethylolpropane and the like. Hon- limiting examples of curable acrylic resin suitable for the new formaldehyde-free binder in the present invention are Aquaset BI700 from Dow Chemicals, Acrodur DS3530 from BASF, or Leaf Free series from Georgia Pacific,
I another embodiment of the present invention, the acrylic component used as second component of the new formaldehyde- free binder in the present invention is an acrylic (co) olymer. Preferably, the acrylic (co) polymer is a
copolymer of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maleic acid or maleic anhydride, and mixtures thereof. More preferably the acrylic (co) olymer is polyacrylic acid or copolymers of acrylic and maleic acids. The acrylic (co) olymers are normally available as water solutions, dispersion or powders , which can be dissolved or dispersed in water by mechanical means at temperatures from about 10 to 50 °C . Non- limi ing examples of acrylic (co) olymers useful for the new binder in the present invention are Syn an 8220 from Interpolymer , Craymul 2154 from Cray Valley, or Acumer 1000 from Dow Chemicals.
In the case that the acrylic component used as second component of the new formaldehyde-free binder in the present invention is an acrylic (co) polymer, it is a more preferred embodiment to combine said acrylic (co) polymer with at least one cross - linker, such as alkane-polyol or alkanolamines of molecular weight lower than 1000 g/mol described in the art, like triethanolamine , glycerol, trime hy1 oIpropane and the like.
The term "aqueous binder compos it ion" as used in the pre sent application means a binder composition that is composed of a solid content and water. Due to the water- insolubility of the water- insoluble native starch, the formaldehyde-free aqueous binder composition of the invention is a dispersion.
The solid content of the aqueous binder composi ions is not particularly limited, and depends on its intended application. So, for example, for application of the binder composition in the form of a dispersion to the mineral fibers via spraying it is preferred that the formaldehyde- free binder composition according to the present invention contains a solid content of 4 to 10 weight % . Particularly preferred in this case is a
solid content of 5 to 8 weight %. Other application methods of the aqueous binder composition according to the present invention ar~e also possible, for example spreading or immersion. In those cases, other solid content ranges might be more appropriate. Thus, for example, a solid content of 15 to 30 weight % , e.g. 20 weight % , may be more suitable if the binder composition is applied by immersion of the substrate in the aqueous binder composition according to the presen invention. Merely for comparison purposes of the properties of the binder compositions through this description and in the examples, a reference solid content of 50 weight % is selected.
The amount of native starch and the amount of acrylic component to be used in the binder of the present invention are not specifically limited. However it is suitable that the amount of native starch is 10 to 35 weight % based on the total solid content of the binder composition, the amount of acrylic component is 5 to 90 weight % based on the total solid content of the binder composition, and the sum of the amount of native starch and the amount of acrylic component is at least 70 weight % based on the total solid content of the binder composition.
According to a another preferred embodiment, very useful binder compositions in form of low viscosity dispersions are obtained when the amount of native starch is 25 to 80 weight % based on the total solid content, the amount of acrylic component is 75 to 20 weight % based on the total solid content, and and the sum of the amount of native starch and acrylic component of at least 80% with respect to the total solid content of the binder composition.
According to a more preferred embodiment, the amount of native starch is from about 60 to about 90 weight % with respect o the total solid content of the binder composition, the amount of acrylic component is from about 10 to about 40 weight % with respect to the total solid content of the binder composition, and the sum of the amount of native starch and acrylic component is at least 70 weight % with respect to the total solid content of the binder composition.
This above embodiment covers binder compositions that are economically attractive (the acrylic component is normally more expensive than the native starch) and, at the same time, after they are applied and cured on the substrates show good binding strength in dry and wet conditions, and good ageing behavior .
According to another preferred embodiment, the binder composition in the form of a dispersion according o the present invention comprises an amount of native starch of 25 to 50 weight % based on the total solid content, an amount of acrylic component of 75 to 50 weight % based on the total solid content, and the native starch and the acrylic component amounts add at least 90 weight % with respect to the total solid content of the binder composition. Such binder compositions, after being applied and cured on the substrates, result in improved binding strength in wet conditions and improved ageing behavior of the bonded products in humid conditions .
According to a yet more preferred embodiment, the binder composition of the present invention also comprises additives described in the art to enhance the performance for its use for mineral wool. Non- limiting examples of additives are esterification catalysts such as sodium hypophosphite, pH
control agent such as ammonium sulfate, hydropho ic ing agent such as silicones, de -dusting agent such as paraffin oils, adhesion promoter agent such as alkoxysilanes , fiber softeners, preservatives, dyes and corrosion inhibitors. It is also preferred that the new binder additionally comprises at least one filler or chain extender such as, but not limited to, urea, sugars, molasses, iignosulfonates or tannins.
There is no limitation about the pH of the new binder composition. Nevertheless it is preferred that the pH of the new binder is above 2.
In view of its suitability as a binder composition for mineral fibers, it is particularly preferred that binder composition of the present invention has the following characteristic: when the binder composition has a solid content of 50 weight- %, the viscosity of the binder composition is less than 200 mPa.s at 20 °C, and preferably less than 50 m?a . s . at 20 °C.
Manufacturing of the new binder
The process for manufacturing the formaldehyde- free binder composition according to the present invention comprises the steps of :
(a) preparation of a dispersion of starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, in water at a temperature of 10 to 40 °C;
(b) contacting the dispersion obtained in step (a) with one or more acrylic component (s) and, optionally, further additives, at a temperature of 10 to 40 °C,
Preferably, the dispersion step (a) is done with mechanical stirring until obtaining a homogenous mixture. It is important to carry out this step at a temperature between 10 to 40 °C, and preferably from about 20 to 30 °C . This range of temperature is suitable to disperse the starch in water and low enough to avoiding %gelatinization' of the starch granules what otherwise would increase the viscosity and difficult the processing. The time of dispersing is not particularly limited because depends on the specific dispersion equipment.
Preferably, the contacting in step (b) is done with mechanical stirring until obtaining a homogenous mixture. It is important to carry out said contacting process at a temperature between 10 to 40 °C, and preferably from about 20 to 30 °C, for the reasons mentioned above. Additionally, this range of temperature is also suitable to avoid unwanted hydrolysis and solubilization of the native starch. The time of contacting step (b) is not particularly limited. Nevertheless it is preferred to carry out this step in less than 60 minutes . Dnder these conditions it is possible, for example, to obtain a binder composition having a viscosity below 50 mPa.s at a solid content of 50 weight % solids.
In order to avoid premature reaction and/or gelatinization of the starch and to maintain the binder composition in the form of a dispersion with low viscosity, the temperature during the preparation of the binder compositio according to the present invention should be kept below 65 °C, preferably below 50 °C, and most preferably below 40 °C. According to a particularly preferred embodiment of the present invention, the temperature during the process of preparing the binder composition of the present invention is not raised above room temperature. In other words, the un-modified insoluble native starch is applied as such to the fibers as part of the binder
composition. The binder composition on the fibers is subsequently dried and cured at tempe atures above 100 °C.
Alternatively, the process for manufacturing of the new formaldehyde-free binder composition according to the present invention may comprise the step of dispersing starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, in an aqueous mixture containing the acrylic component and, optionally, further additives, at a temperature of 10 to 40 °C .
Use of the new binders for mineral wool
The new formaldehyde-free binders according to the present invention are to be used as binder for fibrous substrates, particularly mineral wool fibers. The new binder is applied to the mineral fibers so that they become impregnated. Preferably, the application is via spraying . Fo the application, the total solid content of the new binder composition is not particularly limited. Nevertheless it is particularly suitable to use an aqueous binder composition wherein the solid content is from between 4 to 10 weight %, The amount of new binder to be applied onto the mineral fibers is not particularly limited and is suitably adjusted depending on the type of mineral wool product. A typical amount of dried, binder applied onto the fibers is in the range of 4 to 20 weight % of dried binder with respect to the weight of mineral wool fibers.
The impregnated fibers are then collected in a forming chamber and then conveyed to a curing oven where the new binder cures to set. The binder composition of the present invention cures at temperatures of above 100 °C, preferably at a temperature
of 140 °C to 180 °C, e.g. at 170 °C, which is lower than the curing temperatures required for sugar-based bio-binders described in the art. For instance, the bio-binder described in WO 2008/089851 Al at page 6 has a curing temperature of 190 °C, s seen in Figure 4. Additionally, the new binder composition of he present invention looses a very low amount of mass during the process of curing, preferable less than 1 % at 200 °C . This is very suitable to increase the binder- efficiency, defined as the amount of binder solids after curing compared to the amount of binder solids applied on mineral fibers. In contrast, sugar-based bio-binders described in the art loose significantly more mass . This deteriorates the binder efficiency. For instance, the bio- binder described in WO 2008/089851 Al at page 6 looses about 25 % mass at 200 °C.
The mineral wool mat is afterwards cut and shaped into its final dimensions and packaged. The mineral wool product manufactured with the new binder may comprise at least one additional facing made of paper, aluminum, glass veil or mixtures thereof . The mineral wool product obtained may be used for thermal or acoustic insulation purposes in buildings, conducts, particularly air-conditioning conducts, electrical appliances, ships, aircrafts and spaceships.
E amples
One example of the first embodiment of the present invention is a binder composed by a mixture of native starch Meritena 120 supplied by Syral and acrylic resin Aquaset BI 700 supplied by Dow Chemicals, at 50 weight % each with respect to the total solid %. Meritena 120 is a native starch derived from corn, with DE close to zero, supplied as a whitish powder containing 12% humidity. Aquaset BI 700 is an acrylic resin
based on polyacrylic acid and triethanolamine , supplied as a 55 weight % solids water solution.
A 2.5 liter round-bottom flask is charged with 489 mL of water and a mechanical s irring bar . Then, 511 grams of Meritena 120 powder are added and the mixture vigorously stirred for 30 minutes at 20 °C, obtaining a homogenous white dispersion of approximately 45 weight % solids. Afterwards, 818 grams of Aquaset BI 700 were added and the mixture stirred for additional 10 minutes at 20 °C . The resulting binder C is a milky dispersion of approximately 50 weight ¾ solids., consisting of a 50:50 solids mixture of starch and acrylic component .
A series of new binders based on mixtures of Meritena 120 and Aguaset Bl 700 are provided in Table 1. All of them can be similarly prepared following the method above, by varying the mixing ratio between both components .
Table 1 - New binders based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700. Composition is given in weight % with respect to the total solid % .
The bonding strength on mineral fibers of the new binders A to D was measured in a strain-strength test, as per the Young modulus of a glass paper treated with the binder. The treatment of the glass paper consists of impregnating the glass paper with 20 weight % solids of the new binder, and curing for 3 min at 170 °C . The modulus measured under these
conditions is referred as under 'dry' conditions. The effect of ageing on the bonding properties of the new binders was also evaluated in a consecutive experiment, consisting of immersing the cured treated glass paper specimens in water at 85 °C for 10 minutes , drying and measuring again the Young modulus value in a strain-strength test. The Young modulus measured under these conditions is referred as under 'wet' conditions . The Fig. 1 shows the Young moduli measured under 'dry' and 'wet' conditions for binders A to D, composed of mixtures of native starch Meritena 120 and acrylic resin Aquaset BI 700. As a reference the Young modulus values for native starch Meritena 120 and acrylic resin Aquaset BI 700 on their own measured under the same conditions are also provided. Remarkably, the bonding strength of the new binders under wet conditions is improved in comparison to that of the acrylic resin alone or the native starch alone. The best performing under wet conditions is binder B; i.e. a composition of about 35 weight % of native starch and 65% of acrylic component. The bonding properties under 'dry' conditions for binders A to D are very suitable.
Young modulus is measured on 25x75mm strips of glass paper type Borosilicate GF/A from Whatman International, impregnated with 'binder and cured as described above, by using a tensile strength tester set at a constant extension rate of 6 mm/rain.
The viscosity of the new binders was measured with a Brookfield viscometer with spindle 1 at 20 CC at a solid content of 50 weight %. The Fig. 2 shows the viscosity for binder A to D, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700, at 50 weight % solids. As a reference, the viscosity of acrylic resin Aquaset BI700 is also provided also at 50 weight % solids. It can be seen that all the binders A to D have a viscosity below 50 mPa.s at 20
°C which is very favorable for their use in mineral wool manufacturing. The starch component lias a significant viscosity reduction effect on the high viscous acrylic component .
The stability of the new binder dispersions was measured visually via sedimentation tests, as the time for a homogeneous mixture to start phase splitting at 20 °C . Fig. 3 shows the sedimentation time for binders A to D according to the present invention, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700 at 45% weight % solids . As a reference, the sedimentation time of a homogeneous dispersion of native starch Meritena 120 alone in water is provided. It can be seen that ail binder dispersions A to D according to the present invention have an increased stability, with sedimentation time above 5 minutes, in comparison to the low stability of the dispersion of insoluble native starch in water. This is also very suitable for the use of the new binders in mineral wool manufacturing.
The curing temperature of the new binders was compared to other bio-resins using the respective values of the Young modulus under wet conditions . The Figure 4 shows the Young modulus under wet conditions for the binders B and D according to the present invention, based on mixtures of native starch Meritena 120 and acrylic resin Aquaset BI700, cured for 3 minutes at 170 °C . As a reference it has been also measured the Young modulus under wet conditions of a bio-resin composed of dextrose (82%) , citric acid (15%) and ammonia (3.1%) (see WO 2008/089851 Al; page 6 ) . I this later case, the bio-resin was cured at 170 °C and 190 °C, in both cases for 3 minutes. It can be seen that the binders B and D according to the present invention already achieve mechanical strength curing
at 170 °C, whereas the bio-resin needs curing at 190 °C to provide sufficient mechanical strength.
The mass loss % upon curing for the new binders was measured by TGA (Thermal Gravimetric Analysis) , as the relative solids content weight diminution at 200 °C using a ramp of 10 °C/min in a nitrogen atmosphere. This is representative of the maximum temperatures at -which resins are normally exposed during the curing process. The Figure 5 shows the mass loss of binders B and D according to the present invention. As a comparison, it also shows the mass loss % for the acrylic resin Aguaset BI700 and a bio-resin composed of dextrose (82%), citric acid (15%) and ammonia (3.1%) (described in patent application WO 2008/089851 Al at page 8) . It can be seen that the mass loss, referred as relative solids content weight diminution, for the new binders B and D is less 0.3%, similar to the acrylic resin but significantly lower tha the bio-resin based on dextrose, which loses up to 25% mass.
Other new binders according to the present invention are provided in the Table 2, along with the main characteristics. All of them can be produced according to a similar method to the one described above for the Binder C.
Table 2 - New binders based on mixtures of native starch and acrylic component. Composition i given in weight % with respect to the total solid %.
(1) Supplied by Syral
(2) Supplied by Roquet te
(3) Supplied by Dow Chemicals
(4) Supplied by Sigma Aldrich . molecular weight 8000 g/mol, at pH 2.5
(5) Supplied by Sasol
(6) Glass paper impregnated with 20 weight % solids of binder .. and cured for 3 ι
(7) Glass paper impregnated with 20 weight % solids of binder, and cured for then submerged in water at 85 °C for 10 minutes, and dried.
(8 ) Brookfield spindle 1 at 20 °C . At 50 weight % solid.
(9) TGA, 10 °C/min. Weight loss % at 200 °C vs. initial solids weight % content.
Claims
1. A formaldehyde- free aqueous binder composition comprising
- starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, and
- one or more acrylic component (s) .
2. The formaldehyde -free binder composition according to claim 1, wherein the native starch has a DE (Dextrose. Equivalent) lower than 2.
3. The fornialdehyde-free binder composition according to claims 1 or 2 , wherein the amount of native starch is 10 to 95 weight % based on the total solid content of the binder composition, the amount of acrylic component is 5 to 90 weight % based on the total solid content of the binder composition, and the sum of the amount of native starch and the amount of acrylic component is at least 70 weight % based on the total solid content of the binder composition.
4. The formaldehyde- free binder composition according to any preceding claim, wherein the acrylic component is selected from the group consisting of polyacrylic acid, copolymers of acrylic and aieic acids, copolymers of ethylene-unsaturated moieties containing at least 10 mol % of acrylic acid, maieic acid or maieic anhydride; salts of any preceding (co) olymers , curable resins based on any preceding ( co) polymers , and mixtures thereof.
5. The formaldehyde-free binder composition according to claim 4, wherein the acrylic component is a curable aqueous resin comprising at least one acrylic (co) olymer and one polyol , wherein the acrylic {co) olymer is polyacrylic acid or a copolymer of acrylic and maleic acids, and
- the polyol is a polyalkanols or alkanolamines of M.W. lower than 1O00 g/mol .
6. The formaldehyde-free binder composition according to claim 4, wherein the acrylic component is polyacrylic acid or copolymers of acrylic and maleic acids .
7. The formaldehyde- free binder composition according to claim 6, further comprising a cros -linker such as polyols of M.W. lower than 1000 g/mol.
8. The formaldehyde-free binder composition according to any preceding claim, further comprising additives such as esterification catalysts, pH control agents, hydrophobizing agents, de-dusting agents, adhesion promoters, fiber softeners, preservatives, dyes, corrosion inhibitors, fillers or chain extenders.
9. Use of the formaldehyde-free binder composition according to any one of claims 1-8 in the manufacturing of mineral wool insulation products.
10. A mineral wool product comprising a formaldehyde-- free binder composition according to any of the preceding claims .
11. The use of mineral wool product of claim 10 for thermal or acoustic insulation purposes in buildings, conducts, electrical appliances, ships , aircrafts and spaceships.
12. Process for manufacturing the formaldehyde-free binder composition according to any one of claims 1-8 comprising the steps of :
(a) preparation of a dispersion of starch, wherein an amount of 95 weight % or more of the starch is water- insoluble native starch, in water at a temperature of 10 to 40 °C;
(b) contacting the dispersion obtained in step (a) with the acrylic component and, optionally, further additives at a temperature of 10 to 40 °C.
13. Process for manufacturing the formaldehyde-free binder composition according to any one of claims 1-8 comprising dispersing starch, wherein an amount of 95 weight % or more of the starch is water-insoluble native starch, in an. aqueous mixture containing the acrylic component and, optionally, further additives, at a temperature of 10 to 40 °C.
Priority Applications (7)
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|---|---|---|---|
| US14/410,712 US9242899B2 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and use for mineral wool insulation products |
| JP2015519136A JP5945631B2 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and mineral wool insulation |
| EA201492086A EA028787B1 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder aqueous composition and use thereof for mineral wool insulation products |
| UAA201413548A UA112010C2 (en) | 2012-06-29 | 2013-06-28 | CONNECTIONS NOT CONTAINING FORMALDEHYDE AND ITS APPLICATION FOR MINERAL WOOL INSULATION PRODUCTS |
| CA2877593A CA2877593C (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and use for mineral wool insulation products |
| EP13735238.1A EP2867292B1 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and use for mineral wool insulation products |
| ES13735238.1T ES2596442T3 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and use for mineral wool insulation products |
Applications Claiming Priority (2)
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|---|---|---|---|
| EP12174362.9 | 2012-06-29 | ||
| EP20120174362 EP2679624A1 (en) | 2012-06-29 | 2012-06-29 | Formaldehyde-free binder and use for mineral wool insulation products |
Publications (1)
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|---|---|
| WO2014001518A1 true WO2014001518A1 (en) | 2014-01-03 |
Family
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| PCT/EP2013/063660 WO2014001518A1 (en) | 2012-06-29 | 2013-06-28 | Formaldehyde-free binder and use for mineral wool insulation products |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US9242899B2 (en) |
| EP (2) | EP2679624A1 (en) |
| JP (1) | JP5945631B2 (en) |
| CA (1) | CA2877593C (en) |
| EA (1) | EA028787B1 (en) |
| ES (1) | ES2596442T3 (en) |
| PL (1) | PL2867292T3 (en) |
| UA (1) | UA112010C2 (en) |
| WO (1) | WO2014001518A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385380A (en) * | 2014-08-21 | 2016-03-09 | 约翰斯曼维尔欧洲有限公司 | Binder-consolidated textile fabric, method for producing it, and use thereof |
| EP3034555A1 (en) | 2014-12-15 | 2016-06-22 | URSA Insulation, S.A. | Curable formaldehyde-free resin dispersion and improved mineral wool products produced therewith |
| US10400093B2 (en) | 2014-03-28 | 2019-09-03 | Ursa Insulation, S.A. | Curable formaldehyde-free resin dispersion with reduced viscosity and mineral wool products produced therewith |
| EP3169741B1 (en) | 2014-07-17 | 2022-11-02 | Knauf Insulation SPRL | Improved binder compositions and uses thereof |
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| DE102016011586A1 (en) * | 2016-09-24 | 2018-03-29 | Johns Manville Europe Gmbh | Binder-solidified textile fabric, process for its production and its use |
| ES2794079T3 (en) | 2016-10-27 | 2020-11-17 | Ursa Insulation Sa | Method for the manufacture of stone wool products with a binder based on phenol-formaldehyde resole |
| US11813833B2 (en) | 2019-12-09 | 2023-11-14 | Owens Corning Intellectual Capital, Llc | Fiberglass insulation product |
| EP3896045A1 (en) * | 2020-04-16 | 2021-10-20 | URSA Insulation, S.A. | Binders and curable resins for mineral wool |
| EP4019479A1 (en) | 2020-12-23 | 2022-06-29 | Prefere Resins Holding GmbH | Water-dilutable binders |
| CN117529393A (en) | 2021-06-07 | 2024-02-06 | 巴斯夫欧洲公司 | Method for producing a lignocellulosic composite, corresponding lignocellulosic composite and use thereof |
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- 2013-06-28 EP EP13735238.1A patent/EP2867292B1/en active Active
- 2013-06-28 WO PCT/EP2013/063660 patent/WO2014001518A1/en active Application Filing
- 2013-06-28 JP JP2015519136A patent/JP5945631B2/en active Active
- 2013-06-28 ES ES13735238.1T patent/ES2596442T3/en active Active
- 2013-06-28 US US14/410,712 patent/US9242899B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10400093B2 (en) | 2014-03-28 | 2019-09-03 | Ursa Insulation, S.A. | Curable formaldehyde-free resin dispersion with reduced viscosity and mineral wool products produced therewith |
| EP3169741B1 (en) | 2014-07-17 | 2022-11-02 | Knauf Insulation SPRL | Improved binder compositions and uses thereof |
| CN105385380A (en) * | 2014-08-21 | 2016-03-09 | 约翰斯曼维尔欧洲有限公司 | Binder-consolidated textile fabric, method for producing it, and use thereof |
| US10119213B2 (en) * | 2014-08-21 | 2018-11-06 | Johns Manville | Binder-consolidated textile fabric, method for producing it, and use thereof |
| EP3034555A1 (en) | 2014-12-15 | 2016-06-22 | URSA Insulation, S.A. | Curable formaldehyde-free resin dispersion and improved mineral wool products produced therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| US9242899B2 (en) | 2016-01-26 |
| JP5945631B2 (en) | 2016-07-05 |
| EP2867292B1 (en) | 2016-07-27 |
| PL2867292T3 (en) | 2017-08-31 |
| EP2679624A1 (en) | 2014-01-01 |
| ES2596442T3 (en) | 2017-01-09 |
| US20150321958A1 (en) | 2015-11-12 |
| JP2015527431A (en) | 2015-09-17 |
| CA2877593A1 (en) | 2014-01-03 |
| EP2867292A1 (en) | 2015-05-06 |
| EA201492086A1 (en) | 2015-09-30 |
| CA2877593C (en) | 2016-06-14 |
| EA028787B1 (en) | 2017-12-29 |
| UA112010C2 (en) | 2016-07-11 |
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