WO2024061769A1 - Adhesive - Google Patents
Adhesive Download PDFInfo
- Publication number
- WO2024061769A1 WO2024061769A1 PCT/EP2023/075462 EP2023075462W WO2024061769A1 WO 2024061769 A1 WO2024061769 A1 WO 2024061769A1 EP 2023075462 W EP2023075462 W EP 2023075462W WO 2024061769 A1 WO2024061769 A1 WO 2024061769A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive
- powder
- mass
- water
- water glass
- Prior art date
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 188
- 239000000853 adhesive Substances 0.000 title claims abstract description 186
- 239000000843 powder Substances 0.000 claims abstract description 78
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004971 Cross linker Substances 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 16
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 16
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 15
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 15
- 239000002023 wood Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 41
- 235000013312 flour Nutrition 0.000 claims description 36
- -1 cold tack improvers Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 239000011093 chipboard Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229920002522 Wood fibre Polymers 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 244000068988 Glycine max Species 0.000 claims description 8
- 240000004713 Pisum sativum Species 0.000 claims description 8
- 235000010582 Pisum sativum Nutrition 0.000 claims description 8
- 235000007238 Secale cereale Nutrition 0.000 claims description 8
- 235000014571 nuts Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 7
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 7
- 235000010749 Vicia faba Nutrition 0.000 claims description 7
- 240000006677 Vicia faba Species 0.000 claims description 7
- 235000002098 Vicia faba var. major Nutrition 0.000 claims description 7
- 239000011120 plywood Substances 0.000 claims description 7
- 239000002025 wood fiber Substances 0.000 claims description 7
- 244000025254 Cannabis sativa Species 0.000 claims description 6
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 6
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 235000009120 camo Nutrition 0.000 claims description 6
- 235000005607 chanvre indien Nutrition 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 239000011487 hemp Substances 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 244000082204 Phyllostachys viridis Species 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 241001133760 Acoelorraphe Species 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 4
- 235000007319 Avena orientalis Nutrition 0.000 claims description 4
- 244000075850 Avena orientalis Species 0.000 claims description 4
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 4
- 241000335053 Beta vulgaris Species 0.000 claims description 4
- 240000002791 Brassica napus Species 0.000 claims description 4
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 240000005979 Hordeum vulgare Species 0.000 claims description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 4
- 240000006240 Linum usitatissimum Species 0.000 claims description 4
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 4
- 240000003433 Miscanthus floridulus Species 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000014676 Phragmites communis Nutrition 0.000 claims description 4
- 241000209056 Secale Species 0.000 claims description 4
- 244000062793 Sorghum vulgare Species 0.000 claims description 4
- 239000002154 agricultural waste Substances 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 235000004426 flaxseed Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 235000021374 legumes Nutrition 0.000 claims description 4
- 235000019713 millet Nutrition 0.000 claims description 4
- 235000013379 molasses Nutrition 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000005871 repellent Substances 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 235000020238 sunflower seed Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 238000000855 fermentation Methods 0.000 claims description 3
- 230000004151 fermentation Effects 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 235000009973 maize Nutrition 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002393 azetidinyl group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 229920002472 Starch Polymers 0.000 description 21
- 235000019698 starch Nutrition 0.000 description 21
- 239000008107 starch Substances 0.000 description 21
- 239000012948 isocyanate Substances 0.000 description 18
- 150000002513 isocyanates Chemical class 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 239000007900 aqueous suspension Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 241000209140 Triticum Species 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- HONIICLYMWZJFZ-UHFFFAOYSA-O azetidin-1-ium Chemical compound C1C[NH2+]C1 HONIICLYMWZJFZ-UHFFFAOYSA-O 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 235000021251 pulses Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- HMJMQKOTEHYCRN-UHFFFAOYSA-N formaldehyde;phenol;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 HMJMQKOTEHYCRN-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000006225 natural substrate Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920006390 renewable thermoplastic Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J199/00—Adhesives based on natural macromolecular compounds or on derivatives thereof, not provided for in groups C09J101/00 -C09J107/00 or C09J189/00 - C09J197/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6446—Proteins and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
Definitions
- Adhesive _____ The invention relates to an adhesive for bonding particles, fibres, layers, strands or parts, for example to produce engineered wood products, and a method of preparing this adhesive.
- the invention further relates to products glued with this adhesive; and a method of bonding such products with this adhesive.
- an adhesive is used to connect wood particles, wood fibres, wood strands, wood layers and/or other wood parts or components. Examples of such engineered wood products are chip boards, wood fiber boards (such as MDF - Medium Density Fiberboard and HDF - High Density Fiberboard, OSB - Oriented Strand Board), and plywood boards. It is also possible to bond cellulose fibers or cellulose products into boards.
- Non-limiting examples are bamboo, straw, hemp fibers or hemp strands, kenaf.
- the most common adhesive used in the production of engineered wood products is an aminoplast polymer, produced via a polycondensation reaction from urea and formaldehyde to form a urea-formaldehyde resin (UF resin).
- UF resin urea-formaldehyde resin
- melamine is added and a melamine urea formaldehyde resin (MUF resin) is obtained, or melamine and phenol are added to form melamine urea phenol formaldehyde resins (MUPF resins).
- the major advantages of formaldehyde-based adhesives are their low cost – due to the use of cheap raw materials in their preparation – and their high reactivity.
- a disadvantage of such adhesives in engineered wood products is that they emit formaldehyde during and after polymerization. As a result, more and more people are looking to limit or even reduce formaldehyde emissions to zero. That is why formaldehyde-free adhesives for the production of engineered wood products are sought after.
- US2006/0163769 describes the use of water glass as an adhesive in the production of wood engineered products that are fire resistant.
- a known formaldehyde-free adhesive for use in the production of engineered wood products consists of polymeric methylene diphenyl diisocyanate (pMDI). These pMDI adhesives lead to wood products with high strength and good water resistance. However, these adhesives have a number of drawbacks.
- US4190459A describes a process for producing mineral fiber mats for use as insulation material.
- the mineral fibers are joined together by means of a glue that is applied as a so-called emulsion of water glass and an isocyanate. It is recommended in US4190459A to use water glass with a solid content between 40 and 55 % by mass.
- the so-called emulsions mentioned in US4190459A have an initial viscosity of 10 000 mPa.s. However, this so-called emulsion is not stable, as the viscosity increases rapidly over time.
- CA2019382A1 refers in its prior art section to US4190459A and states that the emulsions described in US4190459A have limited stability.
- CA2019382A1 describes a mixture of isocyanate and a sufficient amount of metal soap for use as an adhesive in engineered wood products.
- the metal soap is used as a blocking compound to prevent reaction between water and isocyanate, therefore a sufficient amount of metal soap is needed.
- CA2019382A1 describes that water glass can also be admixed to the mixture of isocyanate and the sufficient amount of metal soap to form an emulsion.
- WO2022/049513A1 describes an adhesive for engineered wood products.
- the glue is an emulsion of isocyanate in water.
- the isocyanate contains one or more of a diisocyanate, a multiisocyanate, a derivative of a diisocyanate or a derivative of a multiisocyanate.
- the emulsion further contains water glass.
- the ratio in the emulsion of the mass of the combination of water and water glass on the one hand to the mass of the isocyanate on the other is preferably between 1.2 and 6. It is a goal of the current invention to provide an adhesive which is free of formaldehyde, which is suited to bond natural substrates; and which can be easily used as adhesive in the production of engineered wood products, such as chip boards, wood fiber boards (such as MDF-boards and HDF-boards), OSB-boards, and plywood boards.
- the first aspect of the invention is an adhesive.
- the adhesive is characterized in that the adhesive contains at least a powder, water, water glass and a crosslinker; wherein the powder contains carbohydrates and proteins.
- the water glass is a combination of Na 2 O and SiO2 in water.
- the ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1, preferably between 30:1 and 3:1.
- the terms ’glue‘ and ‘adhesive‘ are synonymously used for a compound having some degree of adhesive properties, in essence the ability to provide bonding between two or more pieces of material.
- the terms ‘gluing’ and ‘bonding’ are synonymously used for the act of providing bonding between two or more pieces of material.
- This adhesive does not contain formaldehyde, is stable, is easy to produce and can be easily used as adhesive in the production of engineered wood products, such as chip boards, wood fiber boards (such as MDF-boards and HDF-boards), OSB-boards, and plywood boards.
- the ratio by mass of the powder to the mass of solids of the water glass of the adhesive of the first aspect of the invention provides a better stability of the adhesive, giving the adhesive a good workability.
- water glass is a combination of Na2O and SiO2 in water.
- the (molar) ratio between SiO 2 :Na 2 O and the mass of solids of the water glass (in water) can vary.
- water glass 2.0 has a SiO2:Na2O molar ratio of 2.0:1. Consequently, 1 gram of water glass 2.0, with a solid content of 40 % by mass, contains 0.13 gram of solid Na2O.
- Water glass 3.4 for example, has a SiO2:Na2O molar ratio of 3.4:1. Consequently, 1 gram of water glass 3.4, with a solid content of 37 % by mass, contains 0.084 grams of solid Na2O.
- Solid sodium silicate typically has a high Na2O content, which dissolved in water corresponds to water glass 1.0 to 1.5, or in other words a SiO2:Na2O molar ratio of 1.0:1 to 1.5:1.
- solid content refers to the percentage by mass of the solids, unless stated otherwise.
- a preferred embodiment of the first aspect of the invention is characterized in that the ratio by mass of the powder to the mass of solid Na 2 O of the water glass is between 140:1 and 6:1, preferably between 80:1 and 10:1, more preferably from 60:1 and 15:1.
- the ratio of the mass of the powder to the mass of solid Na2O of the water glass according to this embodiment of the invention also ensures good water resistance of engineered wood products bonded with this adhesive.
- the powder is preferably mainly composed of proteins and carbohydrates.
- the powder may still contain a certain amount of water, even if the powder itself feels dry.
- the powder has only limited solubility in water.
- suspensions can be obtained with a sufficiently low viscosity and a sufficiently high solid content.
- An adhesive with a low viscosity can be sufficiently distributed over the substrate, for example by spraying or nebulizing the adhesive.
- an adhesive could always have a sufficiently low viscosity by adding sufficient water, but an excess of water leads to too high a pressure build-up when pressing the glued substrates, which can cause cracks in the cured substrate.
- carbohydrates such as starch
- proteins such as gelatin were often used as glue.
- Starch is also often used as an adhesive in, for example, the paper industry, where different layers of paper are glued together. However, the starch is first boiled up so that the crystalline phase of the starch is broken and the adhesive power of the starch increases. In all these cases, adhesives with a low solid content and a high viscosity are obtained.
- the aim of the invention is precisely to make an adhesive of which the carbohydrates present have retained their crystalline structure. Furthermore, the proteins present in the powder ensure a further insolubility of the powder in water at temperatures below 50 °C. At higher temperatures, preferably above 60 °C, the crystalline structure of the carbohydrate can be broken and the affinity of the powder for water increases, with a significant increase in viscosity.
- the adhesive can be produced by initially placing the powder in an aqueous suspension, preferably by high shear or turbulence. Because the powder has a limited solubility in water due to its composition, a suspension with a high solid content can be obtained, while the viscosity remains limited.
- a low viscosity is important to be able to sufficiently distribute the resulting adhesive over the substrate, for example by spraying the adhesive.
- the water glass can be added to the aqueous suspension of the powder.
- the water glass interacts with the powder. This results in a moderate increase of viscosity and an activation of the powder. This activation also ensures that the dispersing capacity of the powder is increased and that the addition of a crosslinker at a later stage leads to a homogeneous and stable suspension.
- a crosslinker which is capable of reacting with both the substrate and the powder, can be added to the aqueous suspension of the powder and the waterglass.
- crosslinkers are used which contain isocyanate, epoxy, azetidinium and/or cyclic anhydride groups. It is an important advantage of the invention that a stable suspension of the crosslinker (e.g. isocyanate) in water is obtained.
- the combination of the powder and the water glass thereby acts as a dispersant for the crosslinker. Addition of the water glass provides for an increased adhesive strength of the powder. After applying the adhesive, pressure is applied at elevated temperature. At this elevated temperature, the proteins of the powder are denatured and the carbohydrates lose their crystallinity. Functional groups are also released at this elevated temperature, mainly on the proteins, as a result of which the water glass connected to the powder undergoes a hardening reaction.
- the amount of the expensive crosslinker can remain limited.
- the amount of water glass is therefore preferably chosen such that the water glass is not only active as a dispersant, but also to a significant extent as an adhesive component. This allows to use less crosslinker, and therefore to obtain a cheaper adhesive (and cheaper engineered wood products produced with this adhesive), that can be well dosed and uniformly distributed. It is an important advantage of the invention that the crosslinker does not merely act as a chain extender of the powder, but that it is also capable of reacting with the hydroxyl groups of the substrate (e.g. wood) to improve adhesive strength.
- the substrate e.g. wood
- the water glass can moreover lead to an improvement of the reactivity of hydroxyl groups of wood on the one hand, and the crosslinker (e.g. isocyanate) on the other hand.
- the water glass is thus not only active as an emulsifier for the crosslinker (e.g. isocyanate).
- the suspension is broken, and the water glass can act as a catalyst for the reaction of the crosslinker (e.g. isocyanate) with the hydroxyl groups of wood.
- a preferred embodiment of the first aspect of the invention is characterized in that the powder containing carbohydrates and proteins is obtained by grinding a vegetable raw material, such as cereals (for example, wheat, rye, barley, millet, rice or oats), maize, beets, nuts (for example, palm nuts or coconuts), seeds (for example, rapeseed, linseed or sunflower seeds) or legumes (for example, soybeans, peas, beans, faba beans); or is a combination of two or more of these.
- cereals for example, wheat, rye, barley, millet, rice or oats
- maize for example, palm nuts or coconuts
- seeds for example, rapeseed, linseed or sunflower seeds
- legumes for example, soybeans, peas, beans, faba beans
- a more preferred embodiment of the first aspect of the invention is characterized in that the powder is obtained by grinding pulse beans, such as soybeans, peas, beans, faba beans.
- a preferred embodiment of the first aspect of the invention is characterized in that the powder is starch and/or flour; such as cereal starch and/or flour (for example, wheat, rye, barley, millet, rice or oats), low-grade flour, maize starch and/or flour, beet starch and/or flour, nut starch and/or flour (for example, palm nuts or coconuts), seed starch and/or flour (for example, from rapeseed, linseed or sunflower seeds) or legume starch and/or flour (for example, from soybeans, peas, beans, faba beans); or is a combination of two or more of these.
- cereal starch and/or flour for example, wheat, rye, barley, millet, rice or oats
- low-grade flour for example, maize starch and
- starch and “flour” are interchangeably used for a powder obtained from grinding a vegetable raw material
- the powder is pulse bean starch and/or flour, such as soybean flour, pea starch, faba bean starch, or a combination of two or more of these.
- Flour and starch are readily available. It is also an important advantage that different types of flour and/or starch can be used. Production of the adhesive according to the invention is therefore not bound to one specific raw material or flour and/or starch type.
- a particularly interesting kind of flour for use in the invention is the so-called ‘low-grade flour’, which is a residual material of the wheat flour production.
- a preferred embodiment of the first aspect of the invention is characterized in that the powder in water is obtained by a process in which a fermentation is performed on a vegetable raw material. This allows to prepare the powder from residual flows from the agricultural industry and thus improves the valorisation of these residual flows. In such fermentation processes, microorganisms such as fungi or bacteria convert natural raw materials into powders in aqueous suspension.
- a preferred embodiment of the first aspect of the invention is characterized in that, in the powder, the ratio by mass of the proteins to the mass of the carbohydrates is between 2:1 and 1:30; preferably between 1.5:1 and 1:15, more preferably between 1:2 and 1:10.
- a preferred embodiment of the first aspect of the invention is characterized in that the viscosity of the adhesive at 25 °C is less than 1000 mPa.s, preferably less than 500 mPa.s. An adhesive with such viscosity values ensures a good distribution of the adhesive over the products to be bonded. Due to its low viscosity, the adhesive can also be applied by spraying.
- a preferred embodiment of the first aspect of the invention is characterized in that the powder, the water, the water glass and the crosslinker are homogeneously distributed in the adhesive. This embodiment has the advantage that the adhesive can be used as a one-component system. The adhesive can be stored and is easily usable without further limitation.
- a preferred embodiment of the first aspect of the invention is characterized in that the adhesive is a two-component adhesive; with a first component and a second component. Wherein the first component differs from the second component in the presence of the powder and the crosslinker, respectively.
- the first component can contain no waterglass, or a part of the water glass or the total amount of the water glass. If the first component contains a part of the water glass or the total amount of the water glass, this promotes dispersing the powder.
- the second component can contain no waterglass, or a part of the water glass or the total amount of the water glass. If the second component contains a part of the water glass or the total amount of the water glass, this promotes emulsification of the crosslinker in the second component.
- both components can be stored separately, and mixed when the adhesive is needed; or separately applied to the to-be-glued products. Separate storage of both components of the (two-component) adhesive provides for a prolonged shelf life of the adhesive.
- a preferred embodiment of the first aspect of the invention is characterized in that the solid content in the adhesive is between 10 and 40 % by mass, preferably between 15 and 35 % by mass.
- the adhesive according to this embodiment is easy to process, without too much water having to be transported when transporting the glue.
- a preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a product containing a least two isocyanate groups, preferably wherein the crosslinker contains one or more of a diisocyanate, a multiisocyanate, a derivative of a diisocyanate or a derivative of a multiisocyanate.
- Such crosslinkers are readily available. Moreover, a limited amount of such crosslinker is sufficient.
- a preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a derivative or a polymer of methylene diphenyl diisocyanate (MDI), preferably a polymeric methylene diphenyl diisocyanate (pMDI).
- MDI methylene diphenyl diisocyanate
- pMDI polymeric methylene diphenyl diisocyanate
- Such crosslinkers are also readily available, and again a limited amount of such crosslinker suffices.
- multiple types of isocyanates can be used in the invention.
- polymeric methylene diphenyl diisocyanate (pMDI) is preferred.
- polymeric methylene diphenyl diisocyanate (pMDI) has little to no compatibility with water.
- polymeric methylene diphenyl diisocyanate has a large number of reactive groups per molecule. This is advantageous for the adhesive strength since a dense network of crosslinking is obtained.
- Polymeric methylene diphenyl diisocyanate (pMDI) is moreover the cheapest option of the commercially available isocyanates. Because of these aspects, polymeric methylene diphenyl diisocyanate (pMDI) allows to obtain the advantages of the suspension according to the invention in the most optimal way, with a low cost of the adhesive and the products bonded with the adhesive.
- a preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a product containing at least two epoxy groups, or at least two cyclic anhydride groups, or at least two azetidine functional groups; or mixtures of two or more of these products.
- These crosslinkers are products containing functional groups that are highly reactive with hydroxyl and/or carboxyl groups.
- Examples of crosslinkers that contain at least two epoxy groups, and that can therefore be used in the invention, are bisphenol A (BPA) diepoxide, glycidyl cyclohexene oxide, epoxidized soybean or linseed oil, multi-functional glycidyl ethers or esters.
- BPA bisphenol A
- azetidinium-containing crosslinkers are those used in the paper industry to make the paper stronger, mainly under wet conditions, for example Kymene 557H.
- cyclic anhydride-containing crosslinkers are maleinized oils such as those from soybean or linseed oil. It is an advantage that different types of crosslinkers can be used.
- the invention is not limited to the use of one type of crosslinker.
- a preferred embodiment of the first aspect of the invention is characterized in that the ratio by mass of the crosslinker to the mass of the powder is between 1:15 and 2:1, preferably between 1:10 and 1:1, more preferably between 1:8 and 1:1.25, even more preferably between 1:2.5 and 1:1.5.
- the amount of crosslinker used in the adhesive can therefore be limited.
- a preferred embodiment of the first aspect of the invention is characterized in that the adhesive contains a thermoplastic adhesive component, preferably a biorenewable thermoplastic adhesive component, such as an aqueous dispersion of polylactic acid or a natural latex.
- the adhesive can be tailored for specific applications.
- the use of a thermoplastic adhesive component allows to reduce the amount of crosslinker.
- the use of a biologically renewable thermoplastic adhesive component ensures the "natural" character of the adhesive.
- a preferred embodiment of the first aspect of the invention is characterized in that the molar ratio of SiO2 to Na2O in the waterglass is between 4 and 1.5, preferably between 3.8 and 2.0, more preferably between 3.5 and 2.5, even more preferably between 3.5 and 2.8. It appeared that use of the adhesive according to this embodiment results in a higher water fastness of the bonded product. A relatively small amount of Na2O, relative to the amount of SiO 2 , in the water glass, seems to accomplish this feature.
- a preferred embodiment of the first aspect of the invention is characterized in that the adhesive contains one or more of water repellent additives, catalysts, dyes, pigments, flame retardants, cold tack improvers, or blowing agents.
- the adhesive may contain such additives to give the glued products specific properties and/or to improve the processability of the glue.
- water repellents that can be used are wax emulsions (e.g. based on paraffin or hydrogenated vegetable oils), alkene-ketene dimers, and alkyl succinic anhydride.
- these water-repellent agents are added as an emulsion.
- catalysts to accelerate and improve the reaction between the hydroxyl groups of wood and an isocyanate crosslinker e.g. pMDI
- catalysts to accelerate and improve the reaction between the hydroxyl groups of wood and an isocyanate crosslinker e.g. pMDI
- pMDI tertiary amines and derivatives of tin; these products are well known in the polyurethane industry.
- a preferred embodiment of the first aspect of the invention is characterized in that the D 50 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction (Beckman Coulter laser diffraction device LS 13320), is less than 200 micrometer, preferably less than 100 micrometer, more preferably less than 50 micrometer, even more preferably less than 30 micrometer.
- the D50 value is the particle size – expressed in microns – wherein 50 % of the particles are smaller than this value.
- a preferred embodiment of the first aspect of the invention is characterized in that the D90 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction, is less than 200 micrometer, preferably less than 100 micrometer.
- the D90 value is the particle size – expressed in microns – wherein 90 % of the particles are smaller than this value.
- the invention provides a method of preparing the adhesive as described herein, the method comprising the steps of: - mixing a powder and water to obtain a first aqueous suspension; - adding water glass and a crosslinker to the first aqueous suspension; and - further mixing the resulting suspension to obtain the adhesive; wherein the powder contains carbohydrates and proteins; wherein the water glass contains a combination of Na 2 O and SiO 2 ; and wherein the ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1, preferably between 30:1 and 3:1.
- a preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the powder and water are mixed by high shear or turbulence.
- a preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the water glass is added first to, and mixed with, the first aqueous suspension, before the crosslinker is added.
- the affinity of the powder may increase at elevated temperatures, such as at 60 °C or more, resulting in an increase of viscosity.
- the temperature may be maintained by any suitable means known in the art, such as cooling devices.
- a preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the temperature during preparation of the first aqueous suspension and/or the adhesive is maintained below 60 °C, preferably below 50 °C, more preferably below 40 °C, even more preferably below 30 °C. It may be beneficial for the adhesive strength of the adhesive, if the adhesive is applied on or mixed with the substrate shortly after the crosslinker has been added to the powder, the water glass, and the water, such as within 1 hour, within 50 min, within 40 min, within 30 min, even within 10 min after adding the crosslinker to the other components of the adhesive.
- the invention provides an adhesive prepared according to the method as defined herein. In a yet a further aspect, the invention provides a product.
- the product contains particles, fibres, layers, strands or parts; wherein the particles, fibres, layers, strands or parts are glued together with an adhesive according to any one of embodiments of the first aspect of the invention, in a pressing process at elevated temperature in which water is evaporated from the adhesive and the adhesive provides bonding of the particles, fibres, layers, strands or parts.
- the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive is between 99:1 and 92:8, preferably between 98:2 and 95:5.
- a preferred embodiment of the product of the invention is characterized in that the ratio by mass of solids of the crosslinker in the adhesive to the total amount of particles, fibres, layers, strands of the product is between 0.5 and 2 % by mass, preferably between 0.75 and 1.75 % by mass, more preferably between 1 and 1.5 % by mass.
- the cheap water glass contributes to the adhesive strength, which allows using a smaller amount of the expensive crosslinker in the adhesive, relative to the total amount of particles, fibres, layers, strands in the product.
- the adhesive does not contain formaldehyde. The bonding can be achieved with a small quantity of the adhesive.
- the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board.
- the product may also be a pressed molded part wherein the glued wood parts are pressed in a mold into the desired shape, for example for making pallet blocks.
- the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams. It appeared that the adhesive is particularly suited for gluing together wood components, such as wood chips, wood strands or wood fibres.
- the final aspect of the invention relates to a method of preparing a product.
- the method contains the steps: - providing a quantity of particles, fibres, layers, strands or parts; - applying an adhesive according to any one of the embodiments of the first aspect of the invention to the particles, fibres, layers, strands or parts; - putting the mixture of the particles, fibres, layers, strands or parts and the adhesive into a shape, for example in the form of a board; - curing the adhesive at elevated temperature and under pressure, wherein water evaporates from the adhesive, and wherein the curing of the adhesive results in a product in which the particles, fibres, layers, strands or parts are bound together by the adhesive.
- the products are obtained by pressing the glued wood parts with heated press plates, but for thicker products or molded parts, additional heating can be used via the injection of steam.
- the glue does not contain formaldehyde and can be easily used in the method.
- the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams. It appeared that the adhesive is particularly suited for gluing together wood components, such as wood chips, wood strands or wood fibres.
- a preferred embodiment of the method of preparing the product of the invention is characterized in that, in the product, the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive, is between 99:1 and 92:8, preferably between 98:2 and 95:5. It is therefore possible to work with a limited amount of adhesive, relative to the mass of the components to be glued together.
- a preferred embodiment of the method of preparing the product of the invention is characterized in that the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board.
- the adhesive is particularly suitable for such products.
- the obtained boards have good mechanical properties; and are also resistant to water.
- a preferred embodiment of the method of preparing the product of the invention is characterized in that the adhesive is applied to the particles, fibres, layers, strands or parts within 1 hour after the crosslinker has been added to the powder, the water glass, and the water, preferably within 50 min, more preferably within 40 min, even more preferably within 30 min.
- Example 1 In a first example according to the invention, a suspension is obtained by mixing under high shear 10 grams of rye flour (with a solid content of 90 % by mass) with 60 grams of water. Then 2.5 grams of water glass 2.0 (with a solid content of 40 % by mass), which corresponds to 0.33 grams of Na2O solids, and 5.5 grams of pMDI are added to the suspension and mixed. The resulting adhesive (suspension) has good physical stability, and the viscosity is 150 mPa.s (measured at 25°C). 7.5 grams of Vivastar 9061 is first added to 450 grams of wood chips and mixed, and subsequently the suspension as described above is added and mixed.
- the glued chips are placed in a molded part and the resulting mat is pressed at 200 °C for 2 minutes to form a board with a thickness of 13 mm and a density of 680 kg/m 3 .
- the internal tensile strength of the sheet was 0.50 N/mm 2 and the degree of swelling after immersion in water for 2 hours was 10 %.
- Example 2 In a second example according to the invention, the glued chips as described in example 1 are first stored at 25 °C for 30 min and then pressed according to the same conditions as example 1. The measured tensile strength was 0.48 N/mm 2 and the degree of swelling after immersion in water for 2 hours was 11 %.
- Example 3 In a third example according to the invention, the procedure of example 1 is repeated, but with 10 grams of pea starch E1370D instead of rye flour.
- the resulting adhesive (suspension) has good physical stability, and the viscosity is 130 mPa.s (measured at 25°C).
- the measured tensile strength and the degree of swelling were 0.52 N/mm 2 and 6 %, respectively, for a board with a density of 700 kg/m 3 and a thickness of 12 mm.
- the D50 value of the particle size distribution by volume measured in aqueous dispersion by laser diffraction, of the powder used in the third example is 29.8 micrometers.
- the D 90 value of the particle size distribution by volume, measured in aqueous dispersion by laser diffraction, of the powder used in the third example is 67.4 micrometers.
- Example 4 In a fourth example according to the invention, the procedure of example 1 is repeated, but with 10 grams of pea starch F70D instead of rye flour; and 80 grams of water instead of 60 grams. The resulting adhesive (suspension) has good physical stability, and the viscosity is 400 mPa.s (measured at 25°C). The measured tensile strength and the degree of swelling were 0.58 N/mm 2 and 6 %, respectively, for a board with a density of 680 kg/m 3 and a thickness of 13 mm.
- Comparative example 5 In comparative example 5, the procedure of example 1 is repeated, but without adding water glass. The resulting suspension has poor physical stability. After a few minutes, pMDI drops become visible in the suspension, indicating phase separation. The measured tensile strength and the degree of swelling were 0.15 N/mm 2 and 20 %, respectively, for a board with a density of 680 kg/m 3 and a thickness of 13 mm.
- Example 6 In a sixth example according to the invention, the procedure of example 1 is repeated, but a first component of the adhesive is obtained by mixing under high shear 10 grams of rye flour (with a solid content of 90 %) with 35 grams of water.
- a second component of the adhesive is separately obtained by mixing 25 grams of water, 2.5 grams of water glass 2.0 and 5.5 grams pMDI under high shear to provide an emulsion.
- the first component and the second component are dosed separately onto the wood chips and mixed well for 2 minutes.
- the measured tensile strength and degree of swelling of the chipboard obtained were 0.45 N/mm 2 and 14 %, respectively, for a board with a density of 710 kg/m 3 and a thickness of 12 mm.
- Example 7 In a seventh example according to the invention, the procedure of example 1 is repeated, but a suspension is obtained by mixing under high shear 10 grams of faba bean starch with 60 grams of water.
- Example 8 In an eighth example according to the invention, the procedure of example 1 is repeated, but with 6 grams of water glass 2.0 (with a solid content of 40 %), which corresponds to 0.79 grams of Na 2 O solids, and 4.5 grams of pMDI. The resulting adhesive (suspension) has good physical stability, and the viscosity is 140 mPa.s (measured at 25°C).
- Example 9-10 In a ninth and tenth example according to the invention, the procedure of example 1 is repeated, but with low-grade flour having a different particle size as powder. For this purpose, 10 grams of low-grade flour (1 or 2) are suspended in 60 grams of water and then 4.0 grams of water glass 3.4 and 4.5 grams of pMDI are added. Both mixtures have good physical stability. 10 grams of Vivastar 9061 is first added to 450 grams of wood chips and mixed, and subsequently the suspension as described above is added and mixed. The glued chips are pressed at 200 °C for 2 minutes.
- the obtained chip boards with a thickness of 13 mm both show a degree of swelling of 6 % after immersion in water for 2 hours.
- the tensile strength of the chip board with Low-grade flour 1 is 0.38 N/mm 2
- the tensile strength of the chip board with Low-grade flour 2 is 0.58 N/mm 2 .
- Both boards have a density of 615 kg/m 3 .
- the tables below give an overview of the adhesives according to the different examples, a number of parameters of the composition and the viscosity of the adhesives, as well as the tensile strength and swelling of the products made with the adhesives. Overview Examples Mass Mass ratio Ratio P M li M 1C Tensile Powder/ Mass ratio Visco Swelling E h
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to an adhesive, its method of preparation and products obtained with the aid of the adhesive. The glue contains at least a powder, water, water glass and a crosslinker. The powder contains carbohydrates and proteins. The ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1.
Description
Adhesive ____ The invention relates to an adhesive for bonding particles, fibres, layers, strands or parts, for example to produce engineered wood products, and a method of preparing this adhesive. The invention further relates to products glued with this adhesive; and a method of bonding such products with this adhesive. In engineered wood products, an adhesive is used to connect wood particles, wood fibres, wood strands, wood layers and/or other wood parts or components. Examples of such engineered wood products are chip boards, wood fiber boards (such as MDF - Medium Density Fiberboard and HDF - High Density Fiberboard, OSB - Oriented Strand Board), and plywood boards. It is also possible to bond cellulose fibers or cellulose products into boards. Non-limiting examples are bamboo, straw, hemp fibers or hemp strands, kenaf. The most common adhesive used in the production of engineered wood products is an aminoplast polymer, produced via a polycondensation reaction from urea and formaldehyde to form a urea-formaldehyde resin (UF resin). Optionally, melamine is added and a melamine urea formaldehyde resin (MUF resin) is obtained, or melamine and phenol are added to form melamine urea phenol formaldehyde resins (MUPF resins). The major advantages of formaldehyde-based adhesives are their low cost – due to the use of cheap raw materials in their preparation – and their high reactivity. A disadvantage of such adhesives in engineered wood products is that they emit formaldehyde during and after polymerization. As a result, more and more people are looking to limit or even reduce formaldehyde emissions to zero. That is why formaldehyde-free adhesives for the production of engineered wood products are sought after. US2006/0163769 describes the use of water glass as an adhesive in the production of wood engineered products that are fire resistant.
A known formaldehyde-free adhesive for use in the production of engineered wood products consists of polymeric methylene diphenyl diisocyanate (pMDI). These pMDI adhesives lead to wood products with high strength and good water resistance. However, these adhesives have a number of drawbacks. First, they are much more expensive than the aminoplasts traditionally used; this leads to a significant increase in the cost of engineered wood products. On the other hand, such adhesives have a lower stability than the classic aminoplasts, have a strong tendency to stick to process equipment – which leads, among other things, to the need for frequent cleaning of process equipment – and can lead to the release of isocyanate monomers upon application. This has a detrimental effect on the efficiency of the production process of the engineered wood products. The pMDI adhesives have a better adhesive strength than the traditionally used aminoplasts, so that less adhesive is needed. However, this can be disadvantageous, because the smaller amount of adhesive can lead to insufficient distribution of the adhesive over the substrate. US4190459A describes a process for producing mineral fiber mats for use as insulation material. The mineral fibers are joined together by means of a glue that is applied as a so-called emulsion of water glass and an isocyanate. It is recommended in US4190459A to use water glass with a solid content between 40 and 55 % by mass. The so-called emulsions mentioned in US4190459A have an initial viscosity of 10 000 mPa.s. However, this so-called emulsion is not stable, as the viscosity increases rapidly over time. CA2019382A1 refers in its prior art section to US4190459A and states that the emulsions described in US4190459A have limited stability. CA2019382A1 describes a mixture of isocyanate and a sufficient amount of metal soap for use as an adhesive in engineered wood products. The metal soap is used as a blocking compound to prevent reaction between water and isocyanate, therefore a sufficient amount of metal soap is needed. Furthermore, CA2019382A1 describes that water glass can also be admixed to the mixture of isocyanate and the sufficient amount of metal soap to form an emulsion.
WO2022/049513A1 describes an adhesive for engineered wood products. The glue is an emulsion of isocyanate in water. The isocyanate contains one or more of a diisocyanate, a multiisocyanate, a derivative of a diisocyanate or a derivative of a multiisocyanate. The emulsion further contains water glass. The ratio in the emulsion of the mass of the combination of water and water glass on the one hand to the mass of the isocyanate on the other is preferably between 1.2 and 6. It is a goal of the current invention to provide an adhesive which is free of formaldehyde, which is suited to bond natural substrates; and which can be easily used as adhesive in the production of engineered wood products, such as chip boards, wood fiber boards (such as MDF-boards and HDF-boards), OSB-boards, and plywood boards. To accomplish this goal, the invention contains different aspects. The first aspect of the invention is an adhesive. The adhesive is characterized in that the adhesive contains at least a powder, water, water glass and a crosslinker; wherein the powder contains carbohydrates and proteins. The water glass is a combination of Na2O and SiO2 in water. The ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1, preferably between 30:1 and 3:1. In the context of the current invention, the terms ’glue‘ and ‘adhesive‘ are synonymously used for a compound having some degree of adhesive properties, in essence the ability to provide bonding between two or more pieces of material. Likewise, the terms ‘gluing’ and ‘bonding’ are synonymously used for the act of providing bonding between two or more pieces of material. This adhesive does not contain formaldehyde, is stable, is easy to produce and can be easily used as adhesive in the production of engineered wood products, such as chip boards, wood fiber boards (such as MDF-boards and HDF-boards), OSB-boards, and plywood boards.
The ratio by mass of the powder to the mass of solids of the water glass of the adhesive of the first aspect of the invention provides a better stability of the adhesive, giving the adhesive a good workability. As mentioned above, water glass is a combination of Na2O and SiO2 in water. The (molar) ratio between SiO2:Na2O and the mass of solids of the water glass (in water) can vary. For example, water glass 2.0 has a SiO2:Na2O molar ratio of 2.0:1. Consequently, 1 gram of water glass 2.0, with a solid content of 40 % by mass, contains 0.13 gram of solid Na2O. Water glass 3.4, for example, has a SiO2:Na2O molar ratio of 3.4:1. Consequently, 1 gram of water glass 3.4, with a solid content of 37 % by mass, contains 0.084 grams of solid Na2O. Solid sodium silicate typically has a high Na2O content, which dissolved in water corresponds to water glass 1.0 to 1.5, or in other words a SiO2:Na2O molar ratio of 1.0:1 to 1.5:1. In the context of the present invention, “solid content” refers to the percentage by mass of the solids, unless stated otherwise. A preferred embodiment of the first aspect of the invention is characterized in that the ratio by mass of the powder to the mass of solid Na2O of the water glass is between 140:1 and 6:1, preferably between 80:1 and 10:1, more preferably from 60:1 and 15:1. The ratio of the mass of the powder to the mass of solid Na2O of the water glass according to this embodiment of the invention also ensures good water resistance of engineered wood products bonded with this adhesive. In the first aspect of the invention, the powder is preferably mainly composed of proteins and carbohydrates. The powder may still contain a certain amount of water, even if the powder itself feels dry. Typically, the powder has only limited solubility in water. As a result, suspensions can be obtained with a sufficiently low viscosity and a sufficiently high solid content. An adhesive with a low viscosity can be sufficiently distributed over the substrate, for
example by spraying or nebulizing the adhesive. In principle, an adhesive could always have a sufficiently low viscosity by adding sufficient water, but an excess of water leads to too high a pressure build-up when pressing the glued substrates, which can cause cracks in the cured substrate. The use of carbohydrates (such as starch) and proteins as an adhesive are each known separately. Before the development of formaldehyde-based adhesives, proteins such as gelatin were often used as glue. Starch is also often used as an adhesive in, for example, the paper industry, where different layers of paper are glued together. However, the starch is first boiled up so that the crystalline phase of the starch is broken and the adhesive power of the starch increases. In all these cases, adhesives with a low solid content and a high viscosity are obtained. The aim of the invention is precisely to make an adhesive of which the carbohydrates present have retained their crystalline structure. Furthermore, the proteins present in the powder ensure a further insolubility of the powder in water at temperatures below 50 °C. At higher temperatures, preferably above 60 °C, the crystalline structure of the carbohydrate can be broken and the affinity of the powder for water increases, with a significant increase in viscosity. The adhesive can be produced by initially placing the powder in an aqueous suspension, preferably by high shear or turbulence. Because the powder has a limited solubility in water due to its composition, a suspension with a high solid content can be obtained, while the viscosity remains limited. As mentioned earlier, a low viscosity is important to be able to sufficiently distribute the resulting adhesive over the substrate, for example by spraying the adhesive. In a next phase of producing the adhesive according to the invention, the water glass can be added to the aqueous suspension of the powder. The water glass interacts with the powder. This results in a moderate increase of viscosity and an activation of the powder. This activation also ensures that the dispersing capacity of the powder is increased and
that the addition of a crosslinker at a later stage leads to a homogeneous and stable suspension. In a next process step, a crosslinker, which is capable of reacting with both the substrate and the powder, can be added to the aqueous suspension of the powder and the waterglass. Preferably, crosslinkers are used which contain isocyanate, epoxy, azetidinium and/or cyclic anhydride groups. It is an important advantage of the invention that a stable suspension of the crosslinker (e.g. isocyanate) in water is obtained. The combination of the powder and the water glass thereby acts as a dispersant for the crosslinker. Addition of the water glass provides for an increased adhesive strength of the powder. After applying the adhesive, pressure is applied at elevated temperature. At this elevated temperature, the proteins of the powder are denatured and the carbohydrates lose their crystallinity. Functional groups are also released at this elevated temperature, mainly on the proteins, as a result of which the water glass connected to the powder undergoes a hardening reaction. These functional groups are therefore latent at low temperatures and are only expressed when the adhesive is heated to temperatures above 50 °C. Since the cheap water glass will also contribute to the adhesive strength, the amount of the expensive crosslinker can remain limited. The amount of water glass is therefore preferably chosen such that the water glass is not only active as a dispersant, but also to a significant extent as an adhesive component. This allows to use less crosslinker, and therefore to obtain a cheaper adhesive (and cheaper engineered wood products produced with this adhesive), that can be well dosed and uniformly distributed. It is an important advantage of the invention that the crosslinker does not merely act as a chain extender of the powder, but that it is also capable of reacting with the hydroxyl groups of the substrate (e.g. wood) to improve adhesive strength.
The water glass can moreover lead to an improvement of the reactivity of hydroxyl groups of wood on the one hand, and the crosslinker (e.g. isocyanate) on the other hand. The water glass is thus not only active as an emulsifier for the crosslinker (e.g. isocyanate). When using the adhesive and while elevating the temperature and after evaporation of the water, the suspension is broken, and the water glass can act as a catalyst for the reaction of the crosslinker (e.g. isocyanate) with the hydroxyl groups of wood. A preferred embodiment of the first aspect of the invention is characterized in that the powder containing carbohydrates and proteins is obtained by grinding a vegetable raw material, such as cereals (for example, wheat, rye, barley, millet, rice or oats), maize, beets, nuts (for example, palm nuts or coconuts), seeds (for example, rapeseed, linseed or sunflower seeds) or legumes (for example, soybeans, peas, beans, faba beans); or is a combination of two or more of these. These are readily available raw materials from which the powder can be extracted. It is also an important advantage that different raw materials can be used. Production of the adhesive according to the invention is therefore not bound to one specific raw material. A more preferred embodiment of the first aspect of the invention is characterized in that the powder is obtained by grinding pulse beans, such as soybeans, peas, beans, faba beans. A preferred embodiment of the first aspect of the invention is characterized in that the powder is starch and/or flour; such as cereal starch and/or flour (for example, wheat, rye, barley, millet, rice or oats), low-grade flour, maize starch and/or flour, beet starch and/or flour, nut starch and/or flour (for example, palm nuts or coconuts), seed starch and/or flour (for example, from rapeseed, linseed or sunflower seeds) or legume starch and/or flour (for example, from soybeans, peas, beans, faba beans); or is a combination of two or more of these.
As generally known, the terms “starch” and “flour” are interchangeably used for a powder obtained from grinding a vegetable raw material A more preferred embodiment of the first aspect of the invention is characterized in that the powder is pulse bean starch and/or flour, such as soybean flour, pea starch, faba bean starch, or a combination of two or more of these. Flour and starch are readily available. It is also an important advantage that different types of flour and/or starch can be used. Production of the adhesive according to the invention is therefore not bound to one specific raw material or flour and/or starch type. A particularly interesting kind of flour for use in the invention is the so-called ‘low-grade flour’, which is a residual material of the wheat flour production. Due to the browner color of the low-grade flour, this product is declared unsuitable for the production of wheat bread and is processed as animal feed. Low-grade flour has a higher ratio of proteins to carbohydrates compared to the grain from which it is obtained. Without willing to be bound to any theory, the inventors suspect that the higher ratio of proteins to carbohydrates may lead to better adhesive properties. A preferred embodiment of the first aspect of the invention is characterized in that the powder in water is obtained by a process in which a fermentation is performed on a vegetable raw material. This allows to prepare the powder from residual flows from the agricultural industry and thus improves the valorisation of these residual flows. In such fermentation processes, microorganisms such as fungi or bacteria convert natural raw materials into powders in aqueous suspension. These powders have a homogeneous combination of carbohydrates and proteins. A preferred embodiment of the first aspect of the invention is characterized in that, in the powder, the ratio by mass of the proteins to the mass of the carbohydrates is between 2:1 and 1:30; preferably between 1.5:1 and 1:15, more preferably between 1:2 and 1:10.
A preferred embodiment of the first aspect of the invention is characterized in that the viscosity of the adhesive at 25 °C is less than 1000 mPa.s, preferably less than 500 mPa.s. An adhesive with such viscosity values ensures a good distribution of the adhesive over the products to be bonded. Due to its low viscosity, the adhesive can also be applied by spraying. These viscosity values also ensure good penetration of the adhesive into the pores of the products to be bonded. Due to the low viscosity, the workability of the adhesive is therefore better. A preferred embodiment of the first aspect of the invention is characterized in that the powder, the water, the water glass and the crosslinker are homogeneously distributed in the adhesive. This embodiment has the advantage that the adhesive can be used as a one-component system. The adhesive can be stored and is easily usable without further limitation. A preferred embodiment of the first aspect of the invention is characterized in that the adhesive is a two-component adhesive; with a first component and a second component. Wherein the first component differs from the second component in the presence of the powder and the crosslinker, respectively. The first component can contain no waterglass, or a part of the water glass or the total amount of the water glass. If the first component contains a part of the water glass or the total amount of the water glass, this promotes dispersing the powder. The second component can contain no waterglass, or a part of the water glass or the total amount of the water glass. If the second component contains a part of the water glass or the total amount of the water glass, this promotes emulsification of the crosslinker in the second component.
In the case of the two-component adhesive, both components can be stored separately, and mixed when the adhesive is needed; or separately applied to the to-be-glued products. Separate storage of both components of the (two-component) adhesive provides for a prolonged shelf life of the adhesive. A preferred embodiment of the first aspect of the invention is characterized in that the solid content in the adhesive is between 10 and 40 % by mass, preferably between 15 and 35 % by mass. The adhesive according to this embodiment is easy to process, without too much water having to be transported when transporting the glue. A preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a product containing a least two isocyanate groups, preferably wherein the crosslinker contains one or more of a diisocyanate, a multiisocyanate, a derivative of a diisocyanate or a derivative of a multiisocyanate. Such crosslinkers are readily available. Moreover, a limited amount of such crosslinker is sufficient. A preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a derivative or a polymer of methylene diphenyl diisocyanate (MDI), preferably a polymeric methylene diphenyl diisocyanate (pMDI). Such crosslinkers are also readily available, and again a limited amount of such crosslinker suffices. In principle, multiple types of isocyanates can be used in the invention. However, polymeric methylene diphenyl diisocyanate (pMDI) is preferred. Unlike many other isocyanates, polymeric methylene diphenyl diisocyanate (pMDI) has little to no compatibility with water. In many types of isocyanates, water reacts with the isocyanate groups, resulting in the release of carbon dioxide. Since polymeric
methylene diphenyl diisocyanate (pMDI) and water show little or no compatibility, there is only a limited reaction when water and polymeric methylene diphenyl diisocyanate (pMDI) come into contact. This is a result from the fact that when water and polymeric methylene diphenyl diisocyanate (pMDI) are mixed and the mixing is stopped, the water and the polymeric methylene diphenyl diisocyanate (pMDI) separate from each other. The use of the water glass and the powder according to the invention however stabilizes the suspension. Moreover, the polymeric methylene diphenyl diisocyanate (pMDI) has a large number of reactive groups per molecule. This is advantageous for the adhesive strength since a dense network of crosslinking is obtained. Polymeric methylene diphenyl diisocyanate (pMDI) is moreover the cheapest option of the commercially available isocyanates. Because of these aspects, polymeric methylene diphenyl diisocyanate (pMDI) allows to obtain the advantages of the suspension according to the invention in the most optimal way, with a low cost of the adhesive and the products bonded with the adhesive. A preferred embodiment of the first aspect of the invention is characterized in that the crosslinker is a product containing at least two epoxy groups, or at least two cyclic anhydride groups, or at least two azetidine functional groups; or mixtures of two or more of these products. These crosslinkers are products containing functional groups that are highly reactive with hydroxyl and/or carboxyl groups. Examples of crosslinkers that contain at least two epoxy groups, and that can therefore be used in the invention, are bisphenol A (BPA) diepoxide, glycidyl cyclohexene oxide, epoxidized soybean or linseed oil, multi-functional glycidyl ethers or esters. Examples of azetidinium-containing crosslinkers are those used in the paper industry to make the paper stronger, mainly under wet conditions, for example Kymene 557H. Examples of cyclic anhydride-containing crosslinkers are maleinized oils such as those from soybean or linseed oil.
It is an advantage that different types of crosslinkers can be used. The invention is not limited to the use of one type of crosslinker. A preferred embodiment of the first aspect of the invention is characterized in that the ratio by mass of the crosslinker to the mass of the powder is between 1:15 and 2:1, preferably between 1:10 and 1:1, more preferably between 1:8 and 1:1.25, even more preferably between 1:2.5 and 1:1.5. The amount of crosslinker used in the adhesive can therefore be limited. This lowers the price of the adhesive, since the crosslinker represents the most expensive in the adhesive. A preferred embodiment of the first aspect of the invention is characterized in that the adhesive contains a thermoplastic adhesive component, preferably a biorenewable thermoplastic adhesive component, such as an aqueous dispersion of polylactic acid or a natural latex. The adhesive can be tailored for specific applications. The use of a thermoplastic adhesive component allows to reduce the amount of crosslinker. Furthermore, the use of a biologically renewable thermoplastic adhesive component ensures the "natural" character of the adhesive. A preferred embodiment of the first aspect of the invention is characterized in that the molar ratio of SiO2 to Na2O in the waterglass is between 4 and 1.5, preferably between 3.8 and 2.0, more preferably between 3.5 and 2.5, even more preferably between 3.5 and 2.8. It appeared that use of the adhesive according to this embodiment results in a higher water fastness of the bonded product. A relatively small amount of Na2O, relative to the amount of SiO2, in the water glass, seems to accomplish this feature.
A preferred embodiment of the first aspect of the invention is characterized in that the adhesive contains one or more of water repellent additives, catalysts, dyes, pigments, flame retardants, cold tack improvers, or blowing agents. The adhesive may contain such additives to give the glued products specific properties and/or to improve the processability of the glue. Examples of water repellents that can be used are wax emulsions (e.g. based on paraffin or hydrogenated vegetable oils), alkene-ketene dimers, and alkyl succinic anhydride. Preferably, these water-repellent agents are added as an emulsion. Examples of catalysts to accelerate and improve the reaction between the hydroxyl groups of wood and an isocyanate crosslinker (e.g. pMDI) are tertiary amines and derivatives of tin; these products are well known in the polyurethane industry. A preferred embodiment of the first aspect of the invention is characterized in that the D50 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction (Beckman Coulter laser diffraction device LS 13320), is less than 200 micrometer, preferably less than 100 micrometer, more preferably less than 50 micrometer, even more preferably less than 30 micrometer. The D50 value is the particle size – expressed in microns – wherein 50 % of the particles are smaller than this value. These embodiments provide better adhesive stability and good adhesive efficiency. A preferred embodiment of the first aspect of the invention is characterized in that the D90 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction, is less than 200 micrometer, preferably less than 100 micrometer. The D90 value is the particle size – expressed in microns – wherein 90 % of the particles are smaller than this value. In a further aspect, the invention provides a method of preparing the adhesive as described herein, the method comprising the steps of: - mixing a powder and water to obtain a first aqueous suspension;
- adding water glass and a crosslinker to the first aqueous suspension; and - further mixing the resulting suspension to obtain the adhesive; wherein the powder contains carbohydrates and proteins; wherein the water glass contains a combination of Na2O and SiO2; and wherein the ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1, preferably between 30:1 and 3:1. A preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the powder and water are mixed by high shear or turbulence. A preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the water glass is added first to, and mixed with, the first aqueous suspension, before the crosslinker is added. As mentioned hereinbefore, the affinity of the powder may increase at elevated temperatures, such as at 60 °C or more, resulting in an increase of viscosity. To avoid or minimize the increase of viscosity, it may be preferred to maintain the temperature during the steps of the method below 60 °C, such as below 50 °C, below 40 °C, and even below 30 °C. The temperature may be maintained by any suitable means known in the art, such as cooling devices. A preferred embodiment of the method of preparing the adhesive of the invention is characterized in that the temperature during preparation of the first aqueous suspension and/or the adhesive is maintained below 60 °C, preferably below 50 °C, more preferably below 40 °C, even more preferably below 30 °C. It may be beneficial for the adhesive strength of the adhesive, if the adhesive is applied on or mixed with the substrate shortly after the crosslinker has been added to the powder, the water glass, and the water, such as within 1 hour, within 50 min, within 40 min, within 30 min, even within 10 min after adding the crosslinker to the other components of the adhesive. By using the adhesive shortly after the crosslinker has been added to the powder, the water glass, and the water, less of the crosslinker may have reacted with the
powder, and consequently more of the crosslinker may still be available to react with the hydroxyl groups of the substrate (e.g. wood). In yet a further aspect, the invention provides an adhesive prepared according to the method as defined herein. In a yet a further aspect, the invention provides a product. The product contains particles, fibres, layers, strands or parts; wherein the particles, fibres, layers, strands or parts are glued together with an adhesive according to any one of embodiments of the first aspect of the invention, in a pressing process at elevated temperature in which water is evaporated from the adhesive and the adhesive provides bonding of the particles, fibres, layers, strands or parts. In the product, the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive, is between 99:1 and 92:8, preferably between 98:2 and 95:5. A preferred embodiment of the product of the invention is characterized in that the ratio by mass of solids of the crosslinker in the adhesive to the total amount of particles, fibres, layers, strands of the product is between 0.5 and 2 % by mass, preferably between 0.75 and 1.75 % by mass, more preferably between 1 and 1.5 % by mass. As mentioned previously, the cheap water glass contributes to the adhesive strength, which allows using a smaller amount of the expensive crosslinker in the adhesive, relative to the total amount of particles, fibres, layers, strands in the product. The adhesive does not contain formaldehyde. The bonding can be achieved with a small quantity of the adhesive. Preferably, the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board. The product may also be a pressed molded part wherein the glued wood parts are pressed in a mold into the desired shape, for example for making pallet blocks.
In a preferred embodiment of the invention, the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams. It appeared that the adhesive is particularly suited for gluing together wood components, such as wood chips, wood strands or wood fibres. The final aspect of the invention relates to a method of preparing a product. The method contains the steps: - providing a quantity of particles, fibres, layers, strands or parts; - applying an adhesive according to any one of the embodiments of the first aspect of the invention to the particles, fibres, layers, strands or parts; - putting the mixture of the particles, fibres, layers, strands or parts and the adhesive into a shape, for example in the form of a board; - curing the adhesive at elevated temperature and under pressure, wherein water evaporates from the adhesive, and wherein the curing of the adhesive results in a product in which the particles, fibres, layers, strands or parts are bound together by the adhesive. In principle, the products are obtained by pressing the glued wood parts with heated press plates, but for thicker products or molded parts, additional heating can be used via the injection of steam. The glue does not contain formaldehyde and can be easily used in the method. Preferably, the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams. It appeared that the adhesive is particularly suited for gluing together wood components, such as wood chips, wood strands or wood fibres.
A preferred embodiment of the method of preparing the product of the invention is characterized in that, in the product, the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive, is between 99:1 and 92:8, preferably between 98:2 and 95:5. It is therefore possible to work with a limited amount of adhesive, relative to the mass of the components to be glued together. A preferred embodiment of the method of preparing the product of the invention is characterized in that the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board. The adhesive is particularly suitable for such products. The obtained boards have good mechanical properties; and are also resistant to water. As mentioned hereinbefore, it may be beneficial for the adhesive strength of the adhesive, and consequently of the tensile strength of the glued product, if the adhesive is applied on or mixed with the substrate shortly after the crosslinker has been added to the powder, the water glass, and the water. A preferred embodiment of the method of preparing the product of the invention is characterized in that the adhesive is applied to the particles, fibres, layers, strands or parts within 1 hour after the crosslinker has been added to the powder, the water glass, and the water, preferably within 50 min, more preferably within 40 min, even more preferably within 30 min. Materials used Mass ratio Powder Type Source D50 D90 i h
Low-grade flour 2 - 15:85 28 92
Water glass 2.0 with a solid content of 40 % by mass was obtained from PQ Chemicals and has a SiO2:Na2O molar ratio of 2.0:1. Water glass 3.4 with a solid content of 37 % by mass was also obtained from PQ Chemicals and has a SiO2:Na2O molar ratio of 3.4:1. I-Bond PB PM 4350 (pMDI) was obtained from Huntsman. A 40 % wax emulsion Vivastar 9061 was obtained from H&R, the Netherlands. Examples Example 1 In a first example according to the invention, a suspension is obtained by mixing under high shear 10 grams of rye flour (with a solid content of 90 % by mass) with 60 grams of water. Then 2.5 grams of water glass 2.0 (with a solid content of 40 % by mass), which corresponds to 0.33 grams of Na2O solids, and 5.5 grams of pMDI are added to the suspension and mixed. The resulting adhesive (suspension) has good physical stability, and the viscosity is 150 mPa.s (measured at 25°C). 7.5 grams of Vivastar 9061 is first added to 450 grams of wood chips and mixed, and subsequently the suspension as described above is added and mixed. After the entire mixture has been mixed for 2 minutes, the glued chips are placed in a molded part and the resulting mat is pressed at 200 °C for 2 minutes to form a board with a thickness of 13 mm and a density of 680 kg/m3. The internal tensile strength of the sheet was 0.50 N/mm2 and the degree of swelling after immersion in water for 2 hours was 10 %. Example 2 In a second example according to the invention, the glued chips as described in example 1 are first stored at 25 °C for 30 min and then pressed according to the same conditions
as example 1. The measured tensile strength was 0.48 N/mm2 and the degree of swelling after immersion in water for 2 hours was 11 %. Example 3 In a third example according to the invention, the procedure of example 1 is repeated, but with 10 grams of pea starch E1370D instead of rye flour. The resulting adhesive (suspension) has good physical stability, and the viscosity is 130 mPa.s (measured at 25°C). The measured tensile strength and the degree of swelling were 0.52 N/mm2 and 6 %, respectively, for a board with a density of 700 kg/m3 and a thickness of 12 mm. The D50 value of the particle size distribution by volume measured in aqueous dispersion by laser diffraction, of the powder used in the third example is 29.8 micrometers. The D90 value of the particle size distribution by volume, measured in aqueous dispersion by laser diffraction, of the powder used in the third example is 67.4 micrometers. Example 4 In a fourth example according to the invention, the procedure of example 1 is repeated, but with 10 grams of pea starch F70D instead of rye flour; and 80 grams of water instead of 60 grams. The resulting adhesive (suspension) has good physical stability, and the viscosity is 400 mPa.s (measured at 25°C). The measured tensile strength and the degree of swelling were 0.58 N/mm2 and 6 %, respectively, for a board with a density of 680 kg/m3 and a thickness of 13 mm. Comparative example 5 In comparative example 5, the procedure of example 1 is repeated, but without adding water glass. The resulting suspension has poor physical stability. After a few minutes, pMDI drops become visible in the suspension, indicating phase separation. The measured tensile strength and the degree of swelling were 0.15 N/mm2 and 20 %, respectively, for a board with a density of 680 kg/m3 and a thickness of 13 mm.
Example 6 In a sixth example according to the invention, the procedure of example 1 is repeated, but a first component of the adhesive is obtained by mixing under high shear 10 grams of rye flour (with a solid content of 90 %) with 35 grams of water. A second component of the adhesive is separately obtained by mixing 25 grams of water, 2.5 grams of water glass 2.0 and 5.5 grams pMDI under high shear to provide an emulsion. After adding the wax emulsion to the wood chips in accordance with example 1, the first component and the second component are dosed separately onto the wood chips and mixed well for 2 minutes. The measured tensile strength and degree of swelling of the chipboard obtained were 0.45 N/mm2 and 14 %, respectively, for a board with a density of 710 kg/m3 and a thickness of 12 mm. Example 7 In a seventh example according to the invention, the procedure of example 1 is repeated, but a suspension is obtained by mixing under high shear 10 grams of faba bean starch with 60 grams of water. Then 4.0 grams of water glass 3.4 (with a solid content of 37 % by mass), which corresponds to 0.34 grams of Na2O solids, and 4.5 grams of pMDI are added to the suspension and mixed. The resulting adhesive (suspension) has good physical stability, and the viscosity is 160 mPa.s (measured at 25°C). The measured tensile strength and degree of swelling of the chipboard obtained were 0.46 N/mm2 and 7 %, respectively, for a board with a density of 610 kg/m3 and a thickness of 12 mm. The D50 value of the particle size distribution by volume, measured in aqueous dispersion by laser diffraction, of the powder used in the seventh example is 28.4 micrometers. The D90 value of the particle size distribution by volume, measured in aqueous dispersion by laser diffraction, of the powder used in the seventh example is 87.9 micrometers.
Example 8 In an eighth example according to the invention, the procedure of example 1 is repeated, but with 6 grams of water glass 2.0 (with a solid content of 40 %), which corresponds to 0.79 grams of Na2O solids, and 4.5 grams of pMDI. The resulting adhesive (suspension) has good physical stability, and the viscosity is 140 mPa.s (measured at 25°C). The measured tensile strength and the degree of swelling were 0.45 N/mm2 and 15 %, respectively, for a board with a density of 680 kg/m3 and a thickness of 12 mm. Example 9-10 In a ninth and tenth example according to the invention, the procedure of example 1 is repeated, but with low-grade flour having a different particle size as powder. For this purpose, 10 grams of low-grade flour (1 or 2) are suspended in 60 grams of water and then 4.0 grams of water glass 3.4 and 4.5 grams of pMDI are added. Both mixtures have good physical stability. 10 grams of Vivastar 9061 is first added to 450 grams of wood chips and mixed, and subsequently the suspension as described above is added and mixed. The glued chips are pressed at 200 °C for 2 minutes. The obtained chip boards with a thickness of 13 mm both show a degree of swelling of 6 % after immersion in water for 2 hours. The tensile strength of the chip board with Low-grade flour 1 is 0.38 N/mm2, while the tensile strength of the chip board with Low-grade flour 2 is 0.58 N/mm2. Both boards have a density of 615 kg/m3. The tables below give an overview of the adhesives according to the different examples, a number of parameters of the composition and the viscosity of the adhesives, as well as the tensile strength and swelling of the products made with the adhesives.
Overview Examples Mass Mass ratio Ratio P M li M
1C Tensile Powder/ Mass ratio Visco Swelling E h
Claims
Claims _________ 1.- Adhesive, characterized in that the adhesive contains at least a powder, water, water glass and a crosslinker; wherein the powder contains carbohydrates and proteins; wherein the water glass contains a combination of Na2O and SiO2; wherein the ratio by mass of the powder to the mass of solids of the water glass is between 50:1 and 2:1, preferably between 30:1 and 3:1.
2.- Adhesive according to claim 1, characterized in that the ratio by mass of the powder to the mass of solid Na2O of the water glass is between 140:1 and 6:1, preferably between 80:1 and 10:1, more preferably from 60:1 and 15:1.
3.- Adhesive according to any one of the preceding claims, characterized in that the powder is obtained by grinding a vegetable raw material, such as cereals (for example, wheat, rye, barley, millet, rice or oats), maize, beets, nuts (for example, palm nuts or coconuts), seeds (for example, rapeseed, linseed or sunflower seeds) or legumes (for example, soybeans, peas, beans, faba beans); or is a combination of two or more of these.
4.- Adhesive according to any one of the preceding claims, characterized in that the powder is flour; such as cereal flour (for example, wheat, rye, barley, millet, rice or oats), low-grade flour, maize flour, beet flour, nut flour (for example, palm nuts or coconuts), seed flour (for example, from rapeseed, linseed or sunflower seeds) or legume flour (for example, from soybeans, peas, beans, faba beans); or is a combination of two or more of these.
5.- Adhesive according to any one of the preceding claims, characterized in that the powder in water is obtained by a process in which a fermentation is performed on a vegetable raw material.
6.- Adhesive according to any one of the preceding claims, characterized in that, in the powder, the ratio by mass of the proteins to the mass of the carbohydrates is between 2:1 and 1:30; preferably between 1.5:1 and 1:15, more preferably between 1:2 and 1:10.
7.- Adhesive according to any one of the preceding claims, characterized in that the viscosity of the adhesive at 25 °C is less than 1000 mPa.s, preferably less than 500 mPa.s.
8.- Adhesive according to any one of the preceding claims, characterized in that the powder, the water, the water glass and the crosslinker are homogeneously distributed in the adhesive.
9.- Adhesive according to any one of the preceding claims 1-7, characterized in that the adhesive is a two-component adhesive; with a first component and a second component; wherein the first component contains the powder, a part of the water, and the total amount of the water glass or a part of the water glass or none of the water glass; wherein the second component contains the crosslinker, a part of the water, and the total amount of the water glass or a part of the water glass or none of the water glass.
10.- Adhesive according to any one of the preceding claims, characterized in that the solid content in the adhesive is between 10 and 40 % by mass, preferably between 15 and 35 % by mass.
11.- Adhesive according to any one of the preceding claims, characterized in that the crosslinker is a product containing a least two isocyanate groups, preferably wherein the crosslinker contains one or more of a diisocyanate, a multiisocyanate, a derivative of a diisocyanate or a derivative of a multiisocyanate.
12.- Adhesive according to any one of the preceding claims, characterized in that the crosslinker is a derivative or a polymer of methylene diphenyl diisocyanate (MDI), preferably a polymeric methylene diphenyl diisocyanate (pMDI).
13.- Adhesive according to any one of the preceding claims, characterized in that the crosslinker is a product containing at least two epoxy groups, or at least two cyclic anhydride groups, or at least two azetidine functional groups; or mixtures of two or more of these products.
14.- Adhesive according to any one of the preceding claims, characterized in that the ratio by mass of the crosslinker to the mass of the powder is between 1:15 and 2:1, preferably between 1:10 and 1:1, more preferably between 1:8 and 1:1.25, even more preferably between 1:2.5 and 1:1.5.
15.- Adhesive according to any one of the preceding claims, characterized in that the adhesive contains a thermoplastic adhesive component, preferably a biorenewable thermoplastic adhesive component, such as an aqueous dispersion of polylactic acid or a natural latex.
16.- Adhesive according to any one of the preceding claims, characterized in that the molar ratio of SiO2 to Na2O in the waterglass is between 4 and 1.5, preferably between 3.8 and 2.0, more preferably between 3.5 and 2.5, even more preferably between 3.5 and 2.8.
17.- Adhesive according to any one of the preceding claims, characterized in that the adhesive contains one or more of water repellent additives, catalysts, dyes, pigments, flame retardants, cold tack improvers, or blowing agents.
18.- Adhesive according to any one of the preceding claims, characterized in that the adhesive is liquid and the powder is in suspension in the adhesive.
19.- Adhesive according to any one of the preceding claims, characterized in that the D50 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction, is less than 200 micrometer, preferably less than 100 micrometer, more preferably less than 50 micrometer, even more preferably less than 30 micrometer.
20.- Adhesive according to any one of the preceding claims, characterized in that the D90 value of the particle size distribution by volume of the powder, measured in aqueous dispersion by laser diffraction, is less than 200 micrometer, preferably less than 100 micrometer.
21.- Product, wherein the product contains particles, fibres, layers, strands or parts; wherein the particles, fibres, layers, strands or parts are glued together with an adhesive according to any one of the preceding claims, in a pressing process at elevated temperature in which water is evaporated from the adhesive and the adhesive provides bonding of the particles, fibres, layers, strands or parts; wherein, in the product, the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive, is between 99:1 and 92:8, preferably between 98:2 and 95:5.
22.- Product according to claim 21, wherein the ratio by mass of solids of the crosslinker in the adhesive to the total amount of particles, fibres, layers, strands of the product is between 0.5 and 2 % by mass, preferably between 0.75 and 1.75 % by mass, more preferably between 1 and 1.5 % by mass.
23.- Product according to any one of the preceding claims 21-22, characterized in that the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board.
24.- Product according to any one of the preceding claims 21-22, characterized in that the products is a pressed molded part, for example a pallet block.
25.- Product according to any one of the preceding claims 21-24, characterized in that the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams.
26.- Method for preparing a product, wherein the method comprises the steps of - providing a quantity of particles, fibres, layers, strands or parts; - applying an adhesive, according to any one of the preceding claims 1-20, to the particles, fibres, layers, strands or parts; - putting the mixture of the particles, fibres, layers, strands or parts and the adhesive into a shape, for example in the form of a board; - curing the adhesive at elevated temperature and under pressure, wherein water evaporates from the adhesive, and wherein the curing of the adhesive results in a product in which the particles, fibres, layers, strands or parts are bound together by the adhesive.
27.- Method according to claim 26, characterized in that the particles, fibres, layers, strands or parts are wood based or cellulose based, such as bamboo, straw, reed, hemp, palm, miscanthus, bagasse, molasses or agricultural waste streams.
28.- Method according to any one of the preceding claims 26-27, characterized in that, in the product, the ratio by mass of the total amount of particles, fibres, layers, strands or parts to the solid content of the adhesive, is between 99:1 and 92:8, preferably between 98:2 and 95:5.
29.- Method according to any one of the preceding claims 26-28, characterized in that the product is a board, for example a wood fiber board (for example an MDF board or an HDF board), a chipboard, an OSB (Oriented Strand Board) board or a plywood board, or a pressed molded part, such as a pallet block.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE20225742A BE1030889B9 (en) | 2022-09-19 | 2022-09-19 | Glue |
BE2022/5742 | 2022-09-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024061769A1 true WO2024061769A1 (en) | 2024-03-28 |
Family
ID=83447842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2023/075462 WO2024061769A1 (en) | 2022-09-19 | 2023-09-15 | Adhesive |
Country Status (2)
Country | Link |
---|---|
BE (1) | BE1030889B9 (en) |
WO (1) | WO2024061769A1 (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3336246A (en) * | 1966-02-11 | 1967-08-15 | Westix Corp | Paper laminating adhesive compositions containing resorcinol |
US4190459A (en) | 1977-06-22 | 1980-02-26 | Bayer Aktiengesellschaft | Process for the production of mineral fiber mats |
CA2019382A1 (en) | 1989-06-21 | 1990-12-21 | Gerd A. Thone | Binder composition for chip like and/or fibrous material |
JPH02311582A (en) * | 1989-05-26 | 1990-12-27 | Kazuhiko Takagi | Water glass-isocyanate adhesive |
US20060163769A1 (en) | 2002-09-06 | 2006-07-27 | Volker Thole | Method for the production of fire-resistant moulded wood fibre pieces |
GB2524462A (en) * | 2014-01-08 | 2015-09-30 | Xiaobin Zhao | Algal Bio-adhesives: Compositions, Process for Manufacturing, Formulations and Uses |
US10428254B2 (en) * | 2014-01-08 | 2019-10-01 | Cambond Limited | Bio-adhesives |
WO2022049513A1 (en) | 2020-09-07 | 2022-03-10 | Flooring Industries Limited, Sarl | Adhesive for derived wood products |
-
2022
- 2022-09-19 BE BE20225742A patent/BE1030889B9/en active IP Right Grant
-
2023
- 2023-09-15 WO PCT/EP2023/075462 patent/WO2024061769A1/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3336246A (en) * | 1966-02-11 | 1967-08-15 | Westix Corp | Paper laminating adhesive compositions containing resorcinol |
US4190459A (en) | 1977-06-22 | 1980-02-26 | Bayer Aktiengesellschaft | Process for the production of mineral fiber mats |
JPH02311582A (en) * | 1989-05-26 | 1990-12-27 | Kazuhiko Takagi | Water glass-isocyanate adhesive |
CA2019382A1 (en) | 1989-06-21 | 1990-12-21 | Gerd A. Thone | Binder composition for chip like and/or fibrous material |
US20060163769A1 (en) | 2002-09-06 | 2006-07-27 | Volker Thole | Method for the production of fire-resistant moulded wood fibre pieces |
GB2524462A (en) * | 2014-01-08 | 2015-09-30 | Xiaobin Zhao | Algal Bio-adhesives: Compositions, Process for Manufacturing, Formulations and Uses |
US10428254B2 (en) * | 2014-01-08 | 2019-10-01 | Cambond Limited | Bio-adhesives |
WO2022049513A1 (en) | 2020-09-07 | 2022-03-10 | Flooring Industries Limited, Sarl | Adhesive for derived wood products |
Also Published As
Publication number | Publication date |
---|---|
BE1030889B1 (en) | 2024-04-15 |
BE1030889B9 (en) | 2024-04-22 |
BE1030889A1 (en) | 2024-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101640633B1 (en) | Stable acid denatured soy/urea adhesives and methods of making same | |
AU2011258190B2 (en) | Protein adhesive formulations with amine-epichlorohydrin and isocyanate additives | |
KR101398870B1 (en) | Stable adhesives from urea-denatured soy flour | |
US7722712B2 (en) | Formaldehyde-free adhesives and lignocellulosic composites made from the adhesives | |
US10087350B2 (en) | Formaldehyde-free protein-containing binder compositions | |
KR101941717B1 (en) | Low ph soy flour-non urea diluent and methods of making same | |
AU2012275228B2 (en) | Adhesive additive | |
WO2013112445A1 (en) | Method for the preparation of wood composite from soy flour | |
AU2012217689A1 (en) | Low pH soy flour-non urea diluent and methods of making same | |
WO2024061769A1 (en) | Adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23772237 Country of ref document: EP Kind code of ref document: A1 |