WO2020156144A1 - 木制品及其制备方法 - Google Patents
木制品及其制备方法 Download PDFInfo
- Publication number
- WO2020156144A1 WO2020156144A1 PCT/CN2020/071956 CN2020071956W WO2020156144A1 WO 2020156144 A1 WO2020156144 A1 WO 2020156144A1 CN 2020071956 W CN2020071956 W CN 2020071956W WO 2020156144 A1 WO2020156144 A1 WO 2020156144A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amino
- alkyl
- wood
- silane
- wood product
- Prior art date
Links
- 239000002023 wood Substances 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000576 coating method Methods 0.000 claims abstract description 101
- 239000011248 coating agent Substances 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 89
- 229910000077 silane Inorganic materials 0.000 claims abstract description 76
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 71
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- 239000008199 coating composition Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 20
- 230000001737 promoting effect Effects 0.000 claims description 52
- -1 N-substituted amino Chemical group 0.000 claims description 39
- 238000001723 curing Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000011342 resin composition Substances 0.000 claims description 25
- 229920001864 tannin Polymers 0.000 claims description 23
- 239000001648 tannin Substances 0.000 claims description 23
- 235000018553 tannin Nutrition 0.000 claims description 23
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 239000003899 bactericide agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 125000005333 aroyloxy group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000005372 silanol group Chemical group 0.000 claims description 5
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 4
- 241000218691 Cupressaceae Species 0.000 claims description 4
- 241000219492 Quercus Species 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 4
- 241001070941 Castanea Species 0.000 claims description 3
- 235000014036 Castanea Nutrition 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 240000008670 Pinus densiflora Species 0.000 claims description 3
- 235000000405 Pinus densiflora Nutrition 0.000 claims description 3
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000011121 hardwood Substances 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- 241000208140 Acer Species 0.000 claims description 2
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 2
- 240000001548 Camellia japonica Species 0.000 claims description 2
- 241001655736 Catalpa bignonioides Species 0.000 claims description 2
- 241000218645 Cedrus Species 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 240000005109 Cryptomeria japonica Species 0.000 claims description 2
- 235000014466 Douglas bleu Nutrition 0.000 claims description 2
- 241000893932 Fagus japonica Species 0.000 claims description 2
- 241000758789 Juglans Species 0.000 claims description 2
- 244000184861 Juglans nigra Species 0.000 claims description 2
- 235000013740 Juglans nigra Nutrition 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 241000218378 Magnolia Species 0.000 claims description 2
- 240000002834 Paulownia tomentosa Species 0.000 claims description 2
- 240000001416 Pseudotsuga menziesii Species 0.000 claims description 2
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 claims description 2
- 229920002531 Rubberwood Polymers 0.000 claims description 2
- 240000002871 Tectona grandis Species 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 235000018597 common camellia Nutrition 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 150000004756 silanes Chemical class 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000001165 hydrophobic group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- 239000002966 varnish Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical group OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
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- 230000003796 beauty Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/001—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/02—Staining or dyeing wood; Bleaching wood
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
- B27M1/00—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching
- B27M1/003—Mechanical surface treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/06—Homopolymers or copolymers of esters of polycarboxylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D15/00—Woodstains
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/20—Wood or similar material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Definitions
- the present invention relates to a wood product containing a Michael addition cured coating. More specifically, the present invention relates to the use of a functionalized silane containing amino or imino groups to form an adhesion promoting layer to improve the resistance of the Michael addition cured coating to acidic substances. The adhesion of the wood substrate, and the wood products with Michael addition cured coating assisted by the adhesion promotion layer.
- Wood products include wood furniture, which is the most commonly used product in production and life, which is mainly made of wood substrates. It is well-known that wood substrates have special textures, natural color and other materials that are unmatched by other materials. However, the wooden substrate inevitably has the characteristics of complex structure, uneven material, porous, swelling and shrinking when exposed to water, and containing undesirable substances such as grease, tannins and other colored impurities. It is not an ideal industrial material. Therefore, the research on wood lacquers that can provide a protective layer for wooden substrates has attracted particular attention.
- the Michael addition curing coating system with low volatile organic compounds has received special attention in recent years, and it is expected to replace two-component polyurethane (PU) curing coatings in the fields of ships, aerospace, construction, and metal profiles.
- VOC volatile organic compounds
- PU polyurethane
- the coating industry needs wood products coated with this low-VOC Michael addition curing coating system.
- One aspect of the present invention discloses a wood product, which comprises: i) a wooden substrate containing an acidic substance, the wooden substrate having at least one main surface; ii) directly coated on the main surface of the wooden substrate And iii) a Michael addition-cured coating coated on the adhesion promoting layer, wherein the adhesion promoting layer is formed of a composition containing a functionalized silane, the The functionalized silane contains amino and/or imino functional groups; the Michael addition curable coating is formed from a two-component curable coating composition.
- the wood product has an adhesion of 5B or higher, and the adhesion is measured by the cross-hatch method according to ASTM D3359.
- a method for preparing the above-mentioned wood product includes the following steps: (a) providing a wood substrate containing an acidic substance, which has at least one major surface; (b) Directly coating a composition containing functionalized silane on the main surface of the wooden substrate to form an adhesion promoting layer; and (c) coating a two-component curing coating composition on the adhesion promoting layer, To form a Michael addition cured coating.
- Another aspect of the present invention discloses a method for improving the adhesion of a Michael addition cured coating to a wooden substrate containing an acidic substance, the method comprising directly coating an adhesion promoting layer on the wooden substrate On at least one major surface of the step, wherein the adhesion promoting layer is formed of a composition containing a functionalized silane, the functionalized silane containing amino and/or imino functional groups; and wherein the Michael addition
- the cured coating is formed by a two-component cured coating composition, the two-component cured coating composition comprising:
- the second reactive component, and optional additional additives are selected from one of solvents, fillers, surfactants, defoamers, dispersants, UV absorbers, crosslinking retardants, preservatives, and bactericides. Multiple; and
- Another aspect of the present invention discloses the use of an adhesion promoting layer for improving the adhesion of a Michael addition cured coating to a wood substrate containing acidic substances, wherein the adhesion promoting layer is composed of functionalized
- the functionalized silane contains amino and/or imino functional groups; and wherein the Michael addition curable coating is formed by a two-component curing coating composition, the two-component curing
- the coating composition contains:
- the second reactive component, and optional additional additives are selected from one of solvents, fillers, surfactants, defoamers, dispersants, UV absorbers, crosslinking retardants, preservatives, and bactericides. Multiple; and
- the functionalized silane has a structure represented by general formula I:
- R 1 , R 2 and R 3 each independently represent C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 6 -C 10 aryloxy, C 1 -C 6 alkanoyloxy, C 6 -C 10 aroyloxy, C 1 -C 6 alkane oxime or C 6 -C 10 aryl ketoxime, wherein R 1 , R 2 and R 3 may be the same or different;
- R 4 represents an unsubstituted or N-substituted amino C 1 -C 6 alkyl group, wherein the substituent is selected from amino C 1 -C 6 alkyl group, C 1 -C 6 alkyl group, C 6 -C 10 aryl group , One or more of C 7 -C 14 aralkyl and C 7 -C 14 alkaryl;
- R 5 and R 6 each independently represent a C 1 -C 6 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 14 aralkyl group, or a C 7 -C 14 alkaryl group;
- p is an integer from 0 to 4, preferably 0.
- the functionalized silane includes one or more silanol groups chemically bonded to the molecular backbone of the functionalized silane.
- this functionalized silane has the following structure (formula II):
- R independently represents optionally substituted C 1 -C 20 alkyl, C 6 -C 10 aryl, unsubstituted or N-substituted amino C 1 -C 6 alkyl;
- Each occurrence of X independently represents an unsubstituted or N-substituted amino C 1 -C 6 alkyl group
- n is an integer greater than or equal to 1 and less than 50
- the sum of m and n is greater than or equal to 2.
- the applicant pioneered the application of a composition containing amino and/or imino functionalized silanes directly onto the surface of a wood substrate containing acidic substances as an adhesion promoting layer, which is a Michael addition curing coating.
- an adhesion promoting layer which is a Michael addition curing coating.
- the application of layers on wood substrates containing acidic substances provides new ideas.
- the presence of the adhesion promoting layer significantly reduces or eliminates the adverse effects of acidic substances such as tannin in the wood substrate on the Michael addition cured coating, which has never been recognized before the present invention.
- compositions are described as including or containing specific components, it is expected that the composition does not exclude optional components not involved in the present invention, and it is expected that the composition may be composed or composed of the involved components, or
- a method is described as including or containing specific process steps, it is expected that the method does not exclude optional process steps not involved in the present invention, and it is expected that the method can be constituted or composed of the involved process steps.
- any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
- every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit, combined with any other point or single numerical value, or combined with other lower or upper limits, to form an unclear range.
- major surface is the surface formed by the length and width dimensions of the wooden substrate for providing decoration.
- the term "adhesion promoting layer" is formed of a composition containing a functionalized silane, which may be continuous or discontinuous in the microscopic view, depending on the functionalized silane used. In embodiments where a smaller molecular weight amino and/or imino functionalized silane is used to form the adhesion promoting layer, the adhesion promoting layer is discontinuous. In embodiments where a higher molecular weight amino and/or imino-functionalized silane is used to form the adhesion promoting layer, the adhesion promoting layer is continuous.
- adheresion is a parameter used to measure whether a Michael addition cured coating can form an acceptable coating on a wood substrate. The higher the adhesion, the better the film-forming stability of the Michael addition cured coating on the wood substrate.
- the term “on” includes that the cured coating is applied directly or indirectly on the adhesion promoting layer.
- the Michael addition-cured coating is directly coated on the adhesion promoting layer and is in direct contact with the adhesion promoting layer.
- one or more colorant layers may be present between the Michael addition cured coating and the adhesion promoting layer to obtain the desired color.
- Figure 1 shows the cross-cut adhesion test results of a wooden substrate coated with a Michael addition cured coating prepared according to Example 1 of the present invention, where the upper column is the wooden substrate without a silane adhesion promoting layer , The bottom column is the wood substrate coated with a silane adhesion promoting layer.
- the thickness of the Michael addition cured coating is 30 microns; in Figure 1B, the thickness of the Michael addition cured coating is 100 microns; in Figure 1C, the thickness of the Michael addition cured coating is 200 microns .
- One aspect of the present invention provides a wood product comprising: i) a wooden substrate containing an acidic substance, the wooden substrate having at least one main surface; ii) directly coated on the main surface of the wooden substrate And iii) a Michael addition-cured coating coated on the adhesion promoting layer, wherein the adhesion promoting layer is formed of a composition containing a functionalized silane, the The functionalized silane contains amino and/or imino functional groups; the Michael addition curable coating is formed from a two-component curable coating composition.
- the wood product according to the present invention has an adhesion of 5B or higher, which is measured by the cross-hatch method according to ASTM D3359.
- the thickness of the Michael addition cured coating of the present invention is 30 micrometers or more, the wood product has an adhesion of 5B or higher.
- the thickness of the Michael addition cured coating of the present invention is 100 microns or more, the wood product has an adhesion of 5B or higher.
- the Michael addition cured coating of the present invention has a thickness of 200 microns or more, the wood product has an adhesion of 5B or higher.
- wood substrate used to manufacture the wood product of the present invention any suitable wood substrate known in the art can be used.
- woody substrate refers to any cellulose/lignin material derived from the hard, fibrous structural organization in the stems and roots of trees or other woody plants.
- Wood includes, for example, hardwood and softwood wood cut directly from trees, and engineered wood composite materials made of wood strips, wood chips, wood fibers or wood veneers. Examples of wood composite materials include, but are not limited to, plywood, oriented strand board (OSB), medium density fiberboard (MDF), particle board, and the like.
- OSB oriented strand board
- MDF medium density fiberboard
- the wood product of the present invention includes a wood substrate having an acidic substance.
- the acidic substance includes tannins, aldehydes and/or hemiacetals.
- the wood substrate has a tannin content of at least 0.1 wt%, preferably a tannin content of at least 1 wt%, more preferably a tannin content of at least 5 wt%, and even more preferably A tannin content of at least 10% by weight, and even more preferably a tannin content of at least 30% by weight, as determined by CNS4716-2005.
- wood substrates hardwood, chestnut, oak, red chrysanthemum, camellia, press wood, Douglas fir, Japanese cedar, American cypress, Japanese pine, Japanese cypress, water walnut, black walnut, maple One or more of wood, Japanese beech, Japanese paulownia, birch, Sal, magnolia, ash, teak, oak, catalpa, mountain camphor, cedar, oak, and rubber wood.
- the wood substrate has at least one, preferably two major surfaces facing each other.
- the "major surface” is the surface for decoration formed by the length and width dimensions of the wooden substrate.
- the main surface of the wood substrate may have polar groups such as hydroxyl, amino, mercapto, etc.
- the hydroxyl groups on the surface of the wooden substrate are derived from the cellulose in the wooden substrate, or the surface treatment method is used to make the wooden substrate obtain a main surface with hydroxyl groups, such as oxidation by corona treatment, thereby introducing hydroxyl groups on the surface of the wooden substrate .
- the adhesion promoting layer is formed directly on the main surface of the wood substrate and is formed of a composition containing amino and/or imino functionalized silane.
- the amino and/or imino functionalized silane may have a structure represented by Formula 1:
- R 1 , R 2 and R 3 each independently represent C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 6 -C 10 aryloxy, C 1 -C 6 alkanoyloxy, C 6 -C 10 aroyloxy group, C 1 -C 6 alkane oxime group or C 6 -C 10 aryl ketoxime group, wherein R 1 , R 2 and R 3 may be the same or different;
- R 4 represents Unsubstituted or N-substituted amino C 1 -C 6 alkyl, wherein the substituent is selected from amino C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 6 -C 10 aryl, C 7 -C 14 aralkyl group and C 7 -C 14 alkyl aryl group;
- R 5 and R 6 each independently represent C 1 -C 6 alkyl, C 6 -C 10 aryl, C 7 -C 14 aralkyl
- the functionalized silane having the above structure is selected from the group consisting of amino C 1 -C 6 alkyl trimethoxysilane, amino C 1 -C 6 alkyl triethoxy silane, amino C 1 -C 6 alkyl tripropoxy silane Base silane, amino C 1 -C 6 alkyl tributoxy silane, amino C 1 -C 6 alkyl triisopropoxysilane, amino C 1 -C 6 alkyl tributyl ketoxime silane, N-(amino C 1 -C 6 alkyl)-amino C 1 -C 6 alkyl trimethoxysilane, N-(amino C 1 -C 6 alkyl)-amino C 1 -C 6 alkyl triethoxy silane, N -(Amino C 1 -C 6 alkyl)-amino C 1 -C 6 alkyl tripropoxysilane, N-(amino C 1 -C 6 alkyl trip
- the functionalized silane having the above structure is selected from aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-aminoethyl-aminopropyltrimethoxysilane, N-aminoethyl- One or more of aminopropyltriethoxysilane, anilinomethyltriethoxysilane, and anilinomethyltrimethoxysilane.
- the above-mentioned functionalized silane and the hydroxyl group on the surface of the wooden substrate are connected through the following: the condensable functional groups in the functionalized silane, such as alkoxy, alkenyloxy, aryloxy, alkanoyloxy, aroyloxy, and alkane
- the oxime group or aryl ketone oxime group forms a complementary reactive linking group pair with the hydroxyl groups on the surface of the wood substrate; such complementary reactive linking groups undergo a coupling reaction through a condensation reaction and release small molecular substances, such as Alcohols, esters, ketoximes, etc., to form an adhesion promoting layer on the surface of the wood substrate.
- the inventors of the present invention surprisingly discovered that the amino groups (-NH 2 ) and/or imino groups (-NH-) in the above-mentioned functionalized silanes can react with the acidic substances contained in the wood substrate to reduce The acidity of the wood surface is eliminated or eliminated, thereby realizing the Michael addition curing reaction that is beneficial to alkali catalysis, and improving the adhesion of the Michael addition curing coating to the wood substrate.
- the adhesion promotion layer formed therefrom may be discontinuous under microscopic conditions. Even so, the adhesion promotion layer according to the present invention still has a very beneficial adhesion promotion effect, which can significantly improve the adhesion of the Michael addition cured coating to the wood substrate containing acidic substances.
- the composition containing this functionalized silane is in the form of an organic solvent system.
- the organic solvent system of the functionalized silane refers to the functionalized silane dissolved in organic solvents including alcohols, ketones, ester solvents or a combination thereof, preferably dissolved in acetone.
- any suitable commercially available products can be used, such as amino silanes from Momentive, such as A-1100, A-1102, A-1106, A-1110, A-1120, A-1128, A-1130, A-1170/Y-9627, A-1387, A-1637, A-2120, A-2639, Y-9669, A-15.
- the composition comprising amino and/or imino functionalized silane is in the form of an aqueous dispersion.
- the aqueous dispersion of functionalized silane refers to a functionalized silane dispersed in an aqueous solvent including water, a solvent miscible with water, or a combination thereof, preferably a functionalized silane dispersed in water, which does not contain volatile organic components.
- the functionalized silane in the aqueous dispersion refers to a polymer containing -Si-O- structural units in the molecular backbone, namely siloxane, which contains molecules chemically bonded to the siloxane One or more amino and/or imino functional groups and one or more hydrophobic groups on the backbone.
- the siloxane may also contain one or more silanol groups.
- Hydrophobic group refers to an atom or group of atoms that has no affinity for water, is insoluble in water, or has very little solubility.
- Common hydrophobic groups include but are not limited to C 1 -C 20 hydrocarbon groups, including alkyl or aryl groups.
- the hydrophobic group includes a C 1 -C 20 alkyl group or a C 6 -C 10 aryl group.
- the hydrophobic group it can be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane
- one or more of the hydrophobic groups may also be one or more groups selected from unsubstituted or N-substituted amino C1-C6 alkyl groups.
- silanol group refers to a functional group having a -Si-OH structure.
- the presence of this group allows the silane to crosslink itself or react with reactive functional groups such as hydroxyl groups on other substances.
- the silanol group on the silane can also react with the hydroxyl functional group on the wood substrate to form an adhesion promoting layer.
- the aqueous dispersion suitable for the present invention has a lower viscosity.
- the aqueous dispersion has a viscosity of 50 mPa.s or less at 20°C, preferably has a viscosity of 30 mPa.s or less at 20°C, and more preferably has a viscosity at 20°C.
- the aqueous dispersion suitable for the present invention has a relatively high pH.
- the aqueous dispersion has a pH of 10 or higher at 20°C, preferably a pH of 10.5 or higher at 20°C, and more preferably a pH of 11 or higher at 20°C. ⁇ pH. It has been observed that an aqueous dispersion containing a functionalized silane with a pH in the above range will not adversely affect the formation of the Michael addition cured coating on it after forming the adhesion promoting layer.
- the functionalized silane having an amino group and/or an imino group may have the following structure (general formula II):
- Each occurrence of R independently represents an optionally substituted C 1 -C 20 alkyl group, a C 6 -C 10 aryl group, or an unsubstituted or N-substituted amino C 1 -C 6 alkyl group;
- Each occurrence of X independently represents an unsubstituted or N-substituted amino C 1 -C 6 alkyl group
- n is an integer greater than or equal to 1 and less than 50
- the sum of m and n is greater than or equal to 2.
- each occurrence of said R independently represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, ten Two-carbon alkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, amino C 1 -C 6 alkyl or N-(amino C 1 -C 6 alkyl)-amino C 1 -C 6 alkyl.
- each occurrence of the X independently represents an amino C 1 -C 6 alkyl group or an N-(amino C 1 -C 6 alkyl)-amino C 1 -C 6 alkyl group.
- the silane comprises a mixture of siloxane molecules having the structure of the general formula II, the mixture having a ratio of m to n in the range of 0.8:1 to 1.2:1, preferably having a ratio of m to n in the range of 0.9:1 to 1.1
- the ratio of m to n in the range of :1 is still more preferably a ratio of m to n in the range of 0.95:1 to 1.05:1, and even more preferably it is in the range of 0.98:1 to 1.02:1
- the ratio of m to n It has been observed that siloxanes having the above-mentioned ratio of m to n have beneficial dispersion stability, and aqueous dispersions containing such silanes can achieve particularly beneficial film-forming effects when coated on wooden substrates.
- the aqueous dispersion containing the functionalized silane can be prepared by a suitable method well known to those of ordinary skill in the art, for example, by performing the condensation of the silane compound by the gel-sol method.
- any suitable commercially available product can be used, such as the siloxane dispersion of Evonik, such as Hydrosil 2627, Hydrosil 2776, Hydrosil 1151.
- the functionalized silane having amino groups and/or imino groups can be coated by conventional coating methods known to those of ordinary skill in the art.
- the coating method includes dip coating, spin coating, spray coating, curtain coating, brush coating, roll coating and other coating methods known in the art.
- coating is performed using a spraying process.
- a Michael addition cured coating may be formed on the surface of the wood substrate having the adhesion promoting layer.
- the Michael addition cured coating can be directly applied to the adhesion promoting layer and directly contacting the adhesion promoting layer.
- the wood product according to the present invention has an adhesion of 5B or higher, which is measured by the cross-hatch method according to ASTM D3359.
- the wood product has an adhesion of 5B or higher.
- the thickness of the Michael addition cured coating according to the present invention is 100 micrometers or more
- the wood product has an adhesion of 5B or higher.
- the thickness of the Michael addition cured coating according to the present invention is 200 micrometers or more
- the wood product has an adhesion of 5B or higher.
- the Michael addition curing coating is formed from a two-component curing coating composition.
- the two-component curing coating composition comprises:
- the second reactive component, and optional additional additives are selected from one or more of solvents, surfactants, UV absorbers, crosslinking retardants, preservatives, and bactericides; and
- the first reactive component has a malonate or acetoacetate functional group as the first reactive functional group, and preferably mainly has a malonate functional group.
- the first reactive component mainly contains one type of first reactive functional group, preferably greater than 50, 75, 90 and most preferably 100% of the first reactive functional group comes from one type of first reactive functional group, It is preferably derived from malonate or acetoacetate, most preferably from malonate.
- the second reactive component has an acryl group as the second reactive functional group.
- the first reactive functional group and the second reactive functional group in the first reactive component and the second reactive component are preferably constructed in the polymer main chain or suspended on the side chain or terminal of the polymer main chain.
- the first reactive component and the second reactive component are polyesters and alkyd resins having a first reactive functional group and a second reactive functional group in its main chain, side chain, terminal or a combination thereof, respectively , Polyurethane, polyacrylate, epoxy resin, polyamide and polyvinyl resin group.
- the first reactive component and the second reactive component may be monomeric, but at least one, preferably at least two reactive components are polymers with a weight average molecular weight (Mw) of at least 250 g/mol, preferably Mw To be a polymer between 250, 300 and 5000, more preferably between 400 and 4000 or 500 and 3000 g/mol, the weight average molecular weight is measured by GPC.
- Mw weight average molecular weight
- the molar ratio of the reactive group CH is between 0.5 and 2, and preferably between 0.75 and 1.5, more preferably, between 0.8 and 1.2.
- the first reactive component and the second reactive component are both commercially available, such as Acure 510-170 commercially available from Allnex resin, with a solid content of 85% as the first reactive component, which is commercially available Acure 550-100 of Allnex resin, with a solid content of 85% as the second reactive component.
- the film-forming resin composition of the present invention may optionally include one or more fillers.
- filler refers to any volume extender suitable for coatings, which may be organic or inorganic, such as in particulate form. There is no particular limitation on the shape of the particles, and they can have any appropriate shape. The average particle size of the filler can vary within a wide range, for example within a range of about 10 nanometers to about 50 microns.
- Some fillers, in addition to functioning as volume extenders for coatings also impart one or more desired properties to the composition and/or coating formed from the composition. For example, some fillers can impart the desired color to the composition and the coating resulting from the composition. In this case, this filler is also called “pigment”.
- Some fillers can improve the chemical and/or physical properties, especially the mechanical properties of the coating obtained from the composition. In this case, this filler is also called “reinforcing filler”.
- the film-forming resin composition of the present invention may optionally further contain other additional additives commonly used in coating compositions, and these additives do not adversely affect the coating composition or the cured coating obtained therefrom.
- Suitable additives include, for example, those that can improve the processing or manufacturing properties of the composition, enhance the beauty of the composition, or improve the specific functional properties or characteristics of the coating composition or the cured composition obtained therefrom (such as adhesion to the substrate) Sex) those reagents.
- the additives that may be included are, for example, one or more selected from solvents, surfactants, UV absorbers, defoamers, dispersants, crosslinking retarders, preservatives, and bactericides.
- the content of each optional component is sufficient to achieve its intended purpose, but preferably, such content does not adversely affect the coating composition or the cured coating obtained therefrom.
- the catalyst may be a non-latent catalyst or a latent catalyst.
- the latent catalyst may be a carbon dioxide-terminated strong base catalyst, preferably a dialkyl or quaternary alkyl ammonium alkyl carbonate (as described in EP2556108). Since the catalyst generates carbon dioxide, it is preferably used in coatings with a thickness of 500, 400, 300, 200 or 150 microns.
- EP0326723 describes a homogeneous base catalyst that is more suitable for thicker coatings, which is a catalyst composed of a combination of tertiary amine and epoxide.
- a preferred homogeneous catalyst is a salt of a basic anion X- from a compound containing an acidic XH group, where X is N, P, O, S, or C, where the anion X- is reactive with the second reactive component
- the Michael addition donor, and wherein the anion X- is characterized in that the pKa value of the corresponding acid XH is two or more units lower than the pKa value of most of the first reactive components and is lower than 10.5.
- the details of this catalyst are described in PCT/EP2014/056953, which is incorporated herein by reference.
- the weight ratio of the catalyst to the film-forming resin composition can be varied in the range of 2:100 to 8:100.
- the weight ratio of the catalyst to the film-forming resin composition is less than 2:100, the curing performance of the resulting coating is poor.
- the weight ratio of the catalyst to the film-forming resin composition is greater than 8:100, the operation performance of the resulting Michael addition-cured coating and/or the mechanical properties of the resulting coating may decrease.
- an additional inert diluent that will not affect the reactivity of the above catalyst and film-forming resin composition can be added during the preparation of the catalyst and/or film-forming resin composition, for example, to reduce the viscosity of each component . Therefore, the weight ratio of the catalyst to the film-forming resin composition is not limited to the above range, and can be adjusted according to actual needs.
- the two-component curing coating composition can be prepared by simply mixing the film-forming resin composition and the catalyst in a mixing device in a predetermined weight ratio before application.
- the mixed cured coating composition can be applied using various methods familiar to those skilled in the art, including spraying (for example, air-assisted, airless or electrostatic spraying), brushing, roller coating, overflow coating, and dipping.
- the mixed cured coating composition is applied by spraying.
- the cured coating composition can be applied to various wet film thicknesses.
- the wet film thickness is preferably in the range of about 2 to about 260 ⁇ m, preferably in the range of 30-260 ⁇ m.
- the applied coating can be cured by air-drying or by using various drying devices (for example, an oven) familiar to those skilled in the art to accelerate the curing.
- the wood product can be prepared, for example, by the following steps: (1) providing a polished wood substrate; (2) using a spraying process to combine the amino and/or imino-functionalized silane-containing composition of the present invention Coating on the wood substrate to form an adhesion promoting layer; (3) Using a wet-to-dry coating process, one or more Michael addition cured coatings are sequentially coated on the adhesion promoting layer.
- the colorant may be coated on the adhesion promoting layer before step (3), so as to provide the wood substrate with the desired color.
- the wood products thus obtained can be used in the following applications, including, but not limited to: household furniture, such as tables, chairs, cabinets, etc.; bedroom and bathroom furniture; office furniture; custom furniture, such as school and children’s furniture, hospitals Furniture, restaurant and hotel furniture, kitchen cabinets and furniture; panels for interior design; indoor and outdoor windows and doors; indoor and outdoor window and door frames; outdoor and indoor wall panels and wooden floors.
- Another aspect of the present invention provides a method for improving the adhesion of a Michael addition cured coating to a wooden substrate containing an acidic substance, the method comprising directly forming an adhesion promoting layer on the wooden substrate At least one step on the main surface, wherein the adhesion promotion layer is formed of a composition containing a functionalized silane, the functionalized silane containing amino and/or imino functional groups; and wherein the Michael addition curing
- the coating is formed by a two-component curing coating composition, the two-component curing coating composition comprising:
- the second reactive component, and optional additional additives are selected from one of solvents, fillers, surfactants, defoamers, dispersants, UV absorbers, crosslinking retardants, preservatives, and bactericides. Multiple; and
- Another aspect of the present invention provides the use of an adhesion promoting layer for improving the adhesion of a Michael addition cured coating to a wood substrate containing acidic substances, wherein the adhesion promoting layer is composed of functionalized
- the functionalized silane contains amino and/or imino functional groups; and wherein the Michael addition curable coating is formed by a two-component curing coating composition, the two-component curing
- the coating composition contains:
- the second reactive component, and optional additional additives are selected from one of solvents, fillers, surfactants, defoamers, dispersants, UV absorbers, crosslinking retardants, preservatives, and bactericides. Multiple; and
- the functionalized silane may have a structure represented by general formula I:
- R 1 , R 2 and R 3 each independently represent C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 6 -C 10 aryloxy, C 1 -C 6 alkanoyloxy, C 6 -C 10 aroyloxy, C 1 -C 6 alkane oxime or C 6 -C 10 aryl ketoxime, wherein R 1 , R 2 and R 3 may be the same or different;
- R 4 represents an unsubstituted or N-substituted amino C 1 -C 6 alkyl group, wherein the substituent is selected from amino C 1 -C 6 alkyl group, C 1 -C 6 alkyl group, C 6 -C 10 aryl group , One or more of C 7 -C 14 aralkyl and C 7 -C 14 alkaryl;
- R 5 and R 6 each independently represent a C 1 -C 6 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 14 aralkyl group, or a C 7 -C 14 alkaryl group;
- p is an integer from 0 to 4, preferably 0.
- the functionalized silane may have the following structure (formula II):
- R independently represents optionally substituted C 1 -C 20 alkyl, C 6 -C 10 aryl, unsubstituted or N-substituted amino C 1 -C 6 alkyl;
- Each occurrence of X independently represents an unsubstituted or N-substituted amino C 1 -C 6 alkyl group
- n is an integer greater than or equal to 1 and less than 50
- the sum of m and n is greater than or equal to 2.
- the functionalized silane containing amino groups and/or imino groups can be coated on various wood substrates containing acidic substances, which solves the problem that the Michael addition cured coating is difficult to adhere to the wood substrate.
- the wood substrate thus treated is suitable for various applications, including, but not limited to: household furniture, such as tables, chairs, cabinets, etc.; bedroom and bathroom furniture; office furniture; custom furniture, such as school and children’s furniture, hospital furniture , Restaurant and hotel furniture, kitchen cabinets and furniture; panels for interior design; indoor and outdoor windows and doors; indoor and outdoor window and door frames; outdoor and indoor wall panels and wooden floors.
- the solid wood boards purchased from the timber market are kiln dried. Take a sample with a size of 15 cm * 15 cm * 1.5 cm from the dried board, and adjust it under the conditions of a temperature of 25°C, a relative humidity (RH) of 60% and an air flow rate of 1.8m/s To constant weight, the equilibrium moisture content of the sample is 11%.
- Article sander using, samples were prepared by grinding commercially available from 3M T Utility Cloth Sheet240 sandpaper and cleaned, backup air pressure gun.
- a functionalized silane (CAS: 919-30-2) was sprayed on the treated sample to form an adhesion promoting layer, and dried in air for 1 hour, in an oven at 70° C. for 1 hour, and in air for 7 days.
- component A Mix the components of component A in the amounts shown in Table 1 below to form component A, and then mix component A, component B and an appropriate amount of diluent in the amounts shown in Table 2 below to form Two-component coating composition of Michael addition cured coating.
- the formed coating composition was sprayed on the wood substrate treated with the adhesion promoting layer and the wood substrate not treated with the adhesion promoting layer, and the drying time, pencil hardness, and adhesion of the resulting coating were measured, as a result Shown in Table 3 below.
- the inventors conducted the following verification test. First, prepare tannin aqueous solutions with concentrations of 0%, 1%, 5%, 10%, and 15%. Then, each tannin aqueous solution was sprayed on the pine wood samples, and dried in the air for 30 minutes, in a 50-50 oven for 2 hours, and then cooled.
- Test sample Adhesion Drying time Pencil hardness Samples coated with 0% tannin aqueous solution 4B 35 B Sample coated with 1% tannin aqueous solution 4B 40 2B Sample coated with 5% tannin aqueous solution 2B 51 2B 10% tannin aqueous solution coated sample 0B 81 2B 15% tannin aqueous solution coated sample 0B 90 2B
- Example 1 the varnish prepared in Example 1 was coated on the treated oak substrate with a wet film thickness of 100 microns, and dried in the air for 1 hour, in the red line at 70°C for 1 hour, and then dried in the air 7 day.
- ASTM D3359 the cross-hatch method was used to measure the adhesion of the obtained samples. The results are summarized in Table 5 below.
- amino and/or imino-functionalized silanes specifically improve the adhesion of Michael addition cured coatings to wood substrates containing acidic substances. It was difficult to predict before.
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Abstract
一种木制品，包含含有酸性物质的木质基材，其具有至少一个主表面；直接涂覆在该木制基材的主表面上的粘附促进层；和涂覆在该粘附促进层上的迈克尔加成固化涂层，其中，粘附促进层是由包含官能化硅烷的组合物形成的，官能化硅烷包含氨基和/或亚氨基官能团；迈克尔加成固化涂层是由双组分固化涂料组合物形成的。该木制品的制备方法，包括如下步骤：(a)提供含有酸性物质的木质基材，其具有至少一个主表面；(b)在该木制基材的主表面上直接涂覆包含官能化硅烷的组合物，以形成粘附促进层；和(c)在该粘附促进层上涂覆双组分固化涂料组合物，以形成迈克尔加成固化涂层。
Description
相关申请的交叉引用
本申请要求享有于2019年01月29日提交的名称为“木制品及其制备方法”的中国专利申请201910085603.9的优先权，该申请的全部内容通过引用并入本文中。
本发明涉及一种含有迈克尔加成固化涂层的木制品，更具体地，本发明涉及利用含有氨基或亚氨基的官能化硅烷形成粘附促进层，提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性，以及经由该粘附促进层辅助形成的含有迈克尔加成固化涂层的木制品。
木器产品包括木质家具是生产、生活中最常用的产品，其主要由木质基材制成。公知地，木质基材具有特殊的纹理、自然的材色等其他材料所无法比拟的魅力。但是，木质基材不可避免地具有组织构造复杂、材质不均匀、多孔、遇水膨缩以及含有诸如油脂、单宁和其它有色杂质的不期望物质等特点，并不是一种理想的工业材料。因此，能够为木质基材提供保护层的木器漆的研究特别引人关注。
低挥发性有机化合物(VOC)的迈克尔加成固化涂层体系近年来受到特别的关注，其有望在船舶、航天、建筑、金属型材等领域中替代双组分聚氨酯(PU)固化涂层。特别吸引人的是，这种涂层体系具有诸多优点，包括可以在室温下、甚至更低温度下施工，溶剂含量非常低(例如小于250g/L)，活化期很长(例如在23℃下大于8小时)，优异的外观性能(例如在60°下的光泽度大于90，DOI大于90)，优异的机械性能(包括优异的耐化学品性、优异的耐刮性、优异的柔韧性、良好的户外耐受性 等)，并且不含诸如异氰酸酯、甲醛和有机锡等有害化学品。因此，市场上对这种迈克尔加成固化涂层体系的需求是旺盛的。然而，这种体系在木质基材上的应用却不尽如人意。迄今为止，市场上还没有采用这种低VOC的迈克尔加成固化涂层体系涂覆的木器产品。
涂料工业中需要采用这种低VOC的迈克尔加成固化涂层体系涂覆的木器产品。
发明内容
本发明一方面公开了一种木制品，其包含，i)含有酸性物质的木质基材，所述木质基材具有至少一个主表面；ii)直接涂覆在所述木制基材的主表面上的粘附促进层；和iii)涂覆在所述粘附促进层上的迈克尔加成固化涂层，其中，所述粘附促进层是由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。优选地，所述木制品具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。
在本发明的另一方面提供了一种用于制备上述木制品的方法，所述方法包括如下步骤：(a)提供含有酸性物质的木质基材，其具有至少一个主表面；(b)在所述木制基材的主表面上直接涂覆包含官能化硅烷的组合物，以形成粘附促进层；和(c)在所述粘附促进层上涂覆双组分固化涂料组合物，以形成迈克尔加成固化涂层。
本发明的另一方面公开了用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的方法，所述方法包括将粘附促进层直接涂覆在所述木质基材的至少一个主表面上的步骤，其中，所述粘附促进层由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自溶剂、填料、表面活性 剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
本发明的还要另一方面公开了粘附促进层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，其中，所述粘附促进层由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自溶剂、填料、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
在本发明的一个实施方式中，官能化硅烷具有通式I所表示的结构：
其中
R
1、R
2和R
3各自独立地表示C
1-C
6烷氧基、C
2-C
6烯氧基、C
6-C
10芳氧基、C
1-C
6烷酰氧基、C
6-C
10芳酰氧基、C
1-C
6烷酮肟基或C
6-C
10芳酮肟基，其中R
1、R
2和R
3可以是相同的或不同的；
R
4表示未取代的或N取代的氨基C
1-C
6烷基，其中所述取代基选自氨基C
1-C
6烷基，C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基和C
7-C
14烷芳基中的一种或多种；
R
5和R
6各自独立地表示C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基或C
7-C
14烷芳基；并且
p为0至4的整数，优选为0。
在本发明的另一个实施方式中，官能化硅烷包含一个或多个化学键合到所述官能化硅烷的分子骨架上的硅羟基。作为示例性说明，这种官能化硅烷具有下式结构(通式II)：
其中，
R在每次出现时独立地表示可选被取代的C
1-C
20烷基、C
6-C
10芳基、未取代的或N取代的氨基C
1-C
6烷基；
X在每次出现时独立地表示未取代的或N取代的氨基C
1-C
6烷基；
m是大于或等于1且小于50的整数，n是大于或等于1且小于50的整数，且m与n的和大于等于2。
在本发明中，申请人开创性地将含有氨基和/或亚氨基官能化硅烷的组合物直接涂覆到含有酸性物质的木质基材的表面上作为粘附促进层，为迈克尔加成固化涂层在含有酸性物质的木质基材上的应用提供了新思路。该粘附促进层的存在显著地减少了或消除了木质基材中的酸性物质例如单宁对迈克尔加成固化涂层的不利影响，这在本发明之前从未被认识到。
本发明的一个或多个实施方案的细节在以下的说明书中阐明。根据说明书和权利要求，本发明其它特征、目的和优点将变得清楚。
定义
在本文中使用时，不使用数量词、“至少一种”和“一种或多种”可互换使用。因此，例如包含添加剂的组分可以被解释为表示该组分包含“一种或多种”添加剂。
在组合物被描述为包括或包含特定组分的情况下，预计该组合物中并不排除本发明未涉及的可选组分，并且预计该组合物可由所涉及的组分构成或组成，或者在方法被描述为包括或包含特定工艺步骤的情况下，预计该方法中并不排除本发明未涉及的可选工艺步骤，并且预计该方法可由所涉及的工艺步骤构成或组成。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
当在木质基材的上下文中使用时，术语“主表面”是由木质基材的长度和宽度尺寸形成的用于提供装饰的表面。
当本文中使用时，术语“粘附促进层”是由含有官能化硅烷的组合物形成的，其在微观上可以是连续的或不连续的，这取决于所使用的官能化硅烷。在使用分子量较小的氨基和/或亚氨基官能化的硅烷形成粘附促进层的实施方式中，粘附促进层是不连续的。在使用分子量较高的氨基和/或亚氨基官能化的硅烷形成粘附促进层的实施方式中，粘附促进层是连续的。
在本文中，术语“粘附性”是用于衡量迈克尔加成固化涂层能否在木质基材上形成可接受涂层的参数。粘附性越高表明，迈克尔加成固化涂层在木质基材上的成膜稳定性越好。
在“迈克尔加成固化涂层涂覆在粘附促进层上”的上下文中使用时，术语“在...上”包括该固化涂层直接地或间接地涂覆在粘附促进层上。在本发明的一些实施方式中，迈克尔加成固化涂层直接涂覆在粘附促进层上，与粘附促进层直接接触。在本发明的一些实施方式中，迈克尔加成固化涂层和粘附促进层之间可以存在一种或多种着色剂层，从而获得想要的颜色。
当出现在本说明书和权利要求中时，术语“包含”和“包括”及其变体不具有限制性含义。
术语“优选的”和“优选地”是指在某些情况下可提供某些益处的本发明实施方案。然而，在相同或其他情况下，其它实施方案也可能是优选的。另外，一个或多个优选的实施方案的叙述不意味着其他实施方案是不可用的，并且不旨在将其他实施方案排除在本发明范围外。
图1表示根据本发明的实施例1制备涂布有迈克尔加成固化涂层的木质基材的划格粘附性测试结果图，其中上栏为未涂覆硅烷粘附促进层的木质基材，下栏为涂覆有硅烷粘附促进层的木质基材。在图1A中，迈克尔加成固化涂层的厚度为30微米；在图1B中，迈克尔加成固化涂层的厚度为100微米；在图1C中，迈克尔加成固化涂层的厚度为200微米。
本发明一方面提供了一种木制品，其包含，i)含有酸性物质的木质基材，所述木质基材具有至少一个主表面；ii)直接涂覆在所述木制基材的主表面上的粘附促进层；和iii)涂覆在所述粘附促进层上的迈克尔加成固化涂层，其中，所述粘附促进层是由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。
优选地，根据本发明的木制品具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。在本发明的迈克尔加成固化涂层的厚度具有30微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在本发明的迈克尔加成固化涂层的厚度具有100微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在本发明的迈克尔加成固化涂层的厚度具有200微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。
木质基材
作为用于制造本发明木制品的木质基材，可以使用本领域已知的任何合适的木质基材。在本申请中，术语“木质基材”指的是任何来源于树木或其它木本植物的茎和根中的坚硬、纤维状结构组织的纤维素/木质素材料。木材包括，例如从树木直接切下的硬木和软木木材，以及由木材条、木材碎料、木材纤维或木材薄板制成的工程木材复合材料。木材复合材料 的实例包括但不限于胶合板、定向刨花板(OSB)、中密度纤维板(MDF)、碎料板等。
本发明的木制品包含具有酸性物质的木质基材，作为示例，所述酸性物质包含单宁、醛类和/或半缩醛类物质。在本发明某些实施例中，所述木质基材具有至少0.1wt％的单宁含量，优选具有至少1wt％的单宁含量，更优选具有至少5wt％的单宁含量，还要更优选具有至少10wt％的单宁含量，甚至还要更优选具有至少30wt％的单宁含量，所述单宁含量是通过CNS4716-2005测定的。作为示例性的木质基材，可以使用坚木、栗木、栎木、红钩栗、油茶、按木、花旗松、日本柳杉、美国扁柏、日本赤松、日本扁柏、水胡桃、黑胡桃、槭木、日本山毛榉、日本泡桐、桦木、婆罗双、木兰、白蜡树、柚木、柞木、楸木、山樟木、杉木、橡木、橡胶木中的一种或多种。
根据本发明，木质基材具有至少一个、优选两个彼此相对的主表面。当在本文中使用时，“主表面”是由木质基材的长度和宽度尺寸形成的用于装饰的表面。优选地，木质基材的主表面上可以带有羟基、氨基、巯基等极性基团，结果当将本发明的含有官能化硅烷的组合物涂覆到其上时，连接到官能化硅烷的硅原子上的烷氧基或羟基可以与木质基材表面的羟基基团发生键合反应，从而形成粘附促进层。木质基材表面的羟基基团来自木质基材中的纤维素，或者通过表面处理方法使得木质基材获得具有羟基的主表面，例如通过电晕处理进行氧化，从而在木质基材的表面引入羟基。
粘附促进层
在本发明的木制品中，粘附促进层直接形成在木质基材的主表面上，由包含氨基和/或亚氨基官能化硅烷的组合物形成。
在本发明的实施方式中，氨基和/或亚氨基官能化硅烷可以具有通式1所表示的结构：
其中R
1、R
2和R
3各自独立地表示C
1-C
6烷氧基、C
2-C
6烯氧基、C
6-C
10芳氧基、C
1-C
6烷酰氧基、C
6-C
10芳酰氧基、C
1-C
6烷酮肟基或C
6-C
10芳酮肟基，其中R
1、R
2和R
3可以是相同的或不同的；R
4表示未取代的或N取代的氨基C
1-C
6烷基，其中所述取代基选自氨基C
1-C
6烷基，C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基和C
7-C
14烷芳基中的一种或多种；R
5和R
6各自独立地表示C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基或C
7-C
14烷芳基；并且p为0至4的整数，优选为0。
优选地，具有上述结构的官能化硅烷选自氨基C
1-C
6烷基三甲氧基硅烷、氨基C
1-C
6烷基三乙氧基硅烷、氨基C
1-C
6烷基三丙氧基硅烷、氨基C
1-C
6烷基三丁氧基硅烷、氨基C
1-C
6烷基三异丙烯氧硅烷、氨基C
1-C
6烷基三丁酮肟基硅烷、N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三甲氧基硅烷、N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三乙氧基硅烷、N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三丙氧基硅烷、N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三丁氧基硅烷、N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三异丙烯氧硅烷和N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基三丁酮肟基硅烷中的一种或多种。更优选地，具有上述结构的官能化硅烷选自氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、N-氨乙基-氨丙基三甲氧基硅烷、N-氨乙基-氨丙基三乙氧基硅烷、苯胺基甲基三乙氧基硅烷、苯胺基甲基三甲氧基硅烷中的一种或多种。
上述官能化硅烷与木质基材表面的羟基通过如下实现连接：官能化硅烷中的缩合性官能团，诸如烷氧基、烯氧基、芳氧基、烷酰氧基、芳酰氧基、烷酮肟基或芳酮肟基，与木质基材表面的羟基，形成互补的反应性链接基团对；这样的互补反应性链接基团通过缩合反应进行偶联反应，同时释放出小分子物质，诸如醇类、酯类、酮肟类等，从而在木质基材的表面形成粘附促进层。更重要的是，本发明的发明人惊讶地发现，上述官能化硅烷中的氨基(-NH
2)和/或亚氨基(-NH-)可以与木质基材所包含的酸性物质发生反应，减轻了或消除了木材表面的的酸性，从而实现了有利于碱催化的迈克尔加成固化反应，提高了迈克尔加成固化涂层对木质基材的粘附。
由于木质基材表面的羟基分布是非均匀的，而且这种官能化硅烷是低分子量的，因此由其形成的粘附促进层在微观条件下可能是非连续的。即 便如此，根据本发明的这种粘附促进层仍然具有非常有益的粘附促进效果，其能够显著改善迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性。
在本发明的一个实施方式中，含有这种官能化硅烷的组合物为有机溶剂体系形式。在本发明中，官能化硅烷的有机溶剂体系是指溶解在有机溶剂包括醇类、酮类、酯类溶剂或其组合，优选溶解在丙酮中的官能化硅烷。作为官能化硅烷的实例，可以使用任意适当的可商购产品，诸如迈图公司的氨基硅烷，如A-1100、A-1102、A-1106、A-1110、A-1120、A-1128、A-1130、A-1170/Y-9627、A-1387、A-1637、A-2120、A-2639、Y-9669、A-15。
在本发明的另一个实施方式中，包含氨基和/或亚氨基官能化硅烷的组合物为水性分散体形式。在本发明中，官能化硅烷的水性分散体是指分散在水性溶剂包括水、与水混溶的溶剂或其组合，优选分散在水中的官能化硅烷，其不含挥发性有机组分。
根据本发明一种实施方式，水性分散体中的官能化硅烷是指分子骨架中包含-Si-O-结构单元的聚合物，即硅氧烷，其包含化学键合到所述硅氧烷的分子骨架上的一个或多个氨基和/或亚氨基官能团和一个或多个疏水性基团。进一步地，所述硅氧烷还可以包含一个或多个硅醇基。
“疏水性基团”是指对水无亲和力、不溶于水或溶解度极小的原子或原子团。常见的疏水基团包括但不限于C
1-C
20的烃基，包括烷基或芳基。在本发明的实施方式中，所述疏水性基团包括C
1-C
20烷基或C
6-C
10芳基。作为疏水性基团的实例，可以选自甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一碳烷基、十二碳烷基、十三碳烷基、十四碳烷基、十五碳烷基、十六碳烷基、十八碳烷基和二十碳烷基中的一种或多种，优选地被卤素取代，更优选被氟取代。可选地，所述疏水性基团中的一个或多个还可以是选自未被取代的或N-取代的氨基C1-C6烷基中的一种或多种的基团。
“硅醇基”是指具有-Si-OH结构的官能团。该基团的存在使得硅烷可以自身发生交联或者与其他物质上的羟基等活性官能团发生反应。在本发明 的实施方式中，硅烷上的硅醇基也可以与木质基材上的羟基官能团发生反应，从而形成粘附促进层。
优选地，适用于本发明的水性分散体具有较低的粘度。在本发明的一个实施方式中，所述水性分散体具有在20℃下50mPa.s或更低的粘度，优选具有在20℃下30mPa.s或更低的粘度，更优选具有在20℃下20mPa.s或更低的粘度，还要更优选具有在20℃下10mPa.s或更低的粘度，最优选具有在20℃下5mPa.s或更低的粘度。业已观察到，具有低粘度的水性分散体可以更方便地渗入木质基材的孔隙和纹理中，从而在木质基材的表面上形成基本上完整的粘附促进层。
优选地，适用于本发明的水性分散体具有较高的pH。在本发明的一个实施方式中，所述水性分散体在20℃下具有10或更高的pH，优选在20℃下具有10.5或更高的pH，更优选在20℃下具有11或跟高的pH。业已观察到，pH在上述范围内的含有官能化硅烷的水性分散体在形成粘附促进层之后不会对其上方的迈克尔加成固化涂层的形成造成不利影响。
在根据本发明的实施方式中，具有氨基和/或亚氨基的官能化硅烷可以具有下式结构(通式II)：
其中，
R在每次出现时独立地表示可选被取代的C
1-C
20烷基、C
6-C
10芳基、或未取代的或N取代的氨基C
1-C
6烷基；
X在每次出现时独立地表示未取代的或N取代的氨基C
1-C
6烷基；
m是大于或等于1且小于50的整数，n是大于或等于1且小于50的整数，且m与n的和大于等于2。
优选地，所述R在每次出现时独立地表示甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一碳烷基、十二碳烷基、十三碳烷基、十四碳烷基、十五碳烷基、十六碳烷基、十八碳烷基、二十碳烷基、氨基C
1-C
6烷基或N-(氨基C
1-C
6烷基)-氨基C
1-C
6烷基。而且，优选地，所述X在每次出现时独立地表示氨基C
1-C
6烷基或N-(氨基C
1-C
6烷 基)-氨基C
1-C
6烷基。
优选地，所述硅烷包括具有通式II的结构的硅氧烷分子的混合物，所述混合物具有在0.8:1至1.2:1的范围内m与n的比值，优选具有在0.9:1至1.1:1的范围内的m与n的比值，还要更优选具有在0.95:1至1.05:1的范围内的m与n的比值，甚至更优选具有在0.98:1至1.02:1的范围内的m与n的比值。业已观察到，具有上述m与n比值的硅氧烷具有有益的分散稳定性，含有这种硅烷的水性分散体当被涂覆在木质基材上时可以获得特别有益的成膜效果。
含有官能化硅烷的水性分散体可以采用本领域普通技术人员所熟知的适当的方法制备，例如通过用凝胶-溶胶法进行硅烷化合物的缩合。或者，可以使用任意适当的可商购产品，诸如德国赢创公司的硅氧烷分散体，如
Hydrosil 2627，Hydrosil 2776，Hydrosil 1151。
根据本发明，所述具有氨基和/或亚氨基的官能化硅烷可以通过本领域普通技术人员已知的常规涂覆方法进行涂布。所述涂覆方法包括浸涂、旋涂、喷涂、帘涂、刷涂、辊涂以及本领域已知的其他涂覆方法。在本发明的一个实施方式中，利用喷涂工艺来实施涂覆。
迈克尔加成固化涂层
在根据本发明的木制品中，可以在具有粘附促进层的木质基材的表面上形成迈克尔加成固化涂层。迈克尔加成固化涂层可以直接涂覆到粘附促进层上，与粘附促进层直接接触。可供选择地，该迈克尔加成固化涂层和粘附促进层之间可以存在一种或多种其它涂层，如着色剂层，从而获得想要的颜色。
如此形成的迈克尔加成固化涂层对木质基材显示非常优异的粘附性。优选地，根据本发明的木制品具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。在根据本发明的迈克尔加成固化涂层的厚度具有30微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在根据本发明的迈克尔加成固化涂层的厚度具有100微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在根据本发明的迈克 尔加成固化涂层的厚度具有200微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。
根据本发明，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。在本发明的一个实施方式中，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自溶剂、表面活性剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
US5084536,US5565525,EP2556108和EP2764035详细地描述了成膜树脂组合物、催化剂及迈克尔加成固化涂层的制备方法。除非另有说明，上述专利申请描述的内容通过引用并入本文并且在本文中可适用。
根据本发明的一种实施方式，第一反应性组分具有丙二酸酯或乙酰乙酸酯官能团作为第一反应性官能团，优选主要具有丙二酸酯官能团。优选地，第一反应性组分主要包含一种类型的第一反应性官能团，优选大于50、75、90并且最优选100％的第一反应性官能团来自一种类型的第一反应性官能团，优选地来自丙二酸酯或乙酰乙酸酯，最优选地来自丙二酸酯。根据本发明，第二反应性组分具有丙烯酰基作为第二反应性官能团。
第一反应性组分和第二反应性组分中的第一反应性官能团和第二反应性官能团优选构建在聚合物主链中或悬挂在聚合物主链上的侧链或末端。优选地，第一反应性组分和第二反应性组分分别是在其主链、侧链、末端或其组合中具有第一反应性官能团和第二反应性官能团的聚酯、醇酸树脂、聚氨酯、聚丙烯酸酯、环氧树脂、聚酰胺和聚乙烯基树脂的组。
第一反应性组分和第二反应性组分可以是单体的，但至少一种，优选至少两种反应性组分是重均分子量(Mw)至少为250g/mol的聚合物，优选Mw为在250、300与5000之间，更优选为在400与4000或500与3000g/mol之间的聚合物，所述重均分子量是通过GPC测定的。
选择第一反应性组分和第二反应性组分的相对量，使得第二反应性组 分中的活化的不饱和反应性基团C＝C与第一反应性组分中的活化的酸性反应性基团C-H的摩尔比为在0.5与2之间，并且优选地在0.75与1.5之间，更优选地，在0.8与1.2之间。
所述第一反应性组分和第二反应性组分均是可商购的，例如商购自Allnex resin的Acure 510-170，固含量为85％作为第一反应性组分，商购自Allnex resin的Acure 550-100，固含量为85％作为第二反应性组分。
本发明的成膜树脂组合物可以任选地包含一种或多种填料。本文使用的术语“填料”指适用于涂料的任何体积增量剂，其可以是有机的或无机的例如颗粒形式。对颗粒的形状没有特殊限制，其可以具有任何适当的形状。填料的平均粒径可以在宽范围内变化，例如在约10纳米至约50微米的范围内变化。一些填料除了起到涂料的体积增量剂的作用以外还赋予组合物和/或由该组合物形成的涂层一种或多种所需性质。例如，一些填料可以赋予组合物以及由该组合物得到的涂层所需颜色。在这种情况下，这种填料也被称为“颜料”。一些填料可以改善化学和/或物理性质，特别可以改善由该组合物得到的涂层的机械性质。在这种情况下，这种填料也被称为“增强填料”。
本发明的成膜树脂组合物还可以任选地进一步包含常用在涂料组合物中的其它附加添加剂，这些添加剂不会不利地影响涂层组合物或由其得到的固化涂层。适当的添加剂包括例如会改善组合物的加工性能或制造性能、增强组合物的美感、或改善涂层组合物或由其得到的固化组合物的特定功能性质或特性(诸如对基材的粘附性)的那些试剂。可以包含的添加剂例如选自溶剂、表面活性剂、UV吸收剂、消泡剂、分散剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种。各个可选成分的含量足以起到其意欲达到目的，但优选地，这样的含量不会不利地影响涂层组合物或由其得到的固化涂层。
在根据本发明的双组分固化涂料组合物中，催化剂可以是非潜伏型催化剂，也可以是潜伏型催化剂。其中，潜伏型催化剂可以是二氧化碳封端的强碱催化剂，优选二烷基或烷基碳酸季烷基铵(如EP2556108中所述的)。由于该催化剂产生二氧化碳，因此其优选用于厚度达500、400、 300、200或150微米的涂层中。
EP0326723中描述了更适合较厚涂层的均相碱催化剂，其是由叔胺和环氧化物的组合组成的催化剂。优选的均相催化剂是来自含酸性X-H基团的化合物的碱性阴离子X-的盐，其中X是N、P、O、S或C，其中阴离子X-是与第二反应性组分可反应的迈克尔加成供体，并且其中阴离子X-的特征在于，相应的酸X-H的pKa值比大多数第一反应性组分的pKa值低两个以上单位，且低于10.5。该催化剂的细节描述于PCT/EP2014/056953中，其通过引用并入本文。
优选地，根据本发明，催化剂与成膜树脂组合物的重量比可以在2：100至8：100的范围内变化。一般而言，当催化剂与成膜树脂组合物的重量比小于2：100时，所得涂层的固化性能不良。一般而言，当催化剂与成膜树脂组合物的重量比大于8：100时，那么所得迈克尔加成固化涂层的操作性能以及/或者所得涂层的机械性质可能会下降。根据实际需要，可以在催化剂和/或成膜树脂组合物的制备期间添加额外的不会对以上催化剂和成膜树脂组合物的反应性造成影响的惰性稀释剂，以例如降低各组分的粘度。因而，催化剂与成膜树脂组合物的重量比并不局限于上述范围，可以根据实际需要调整。
根据本发明，双组分固化涂料组合物可以通过如下制备：应用前，将成膜树脂组合物与催化剂以预定重量比在混合装置中进行简单混合。混合的固化涂料组合物可使用本领域技术人员熟悉的各种方法来涂覆，包括喷涂(例如，空气辅助、无空气或静电喷涂)、刷涂、辊涂、溢涂和浸渍。在本发明的一个实施方式中，混合的固化涂料组合物通过喷涂来进行涂覆。固化涂料组合物可被涂成各种湿膜厚度。在本发明的实施方式中，湿膜厚度优选地在约2至约260μm的范围内，优选在30-260μm的范围内。可以通过使涂覆的涂层风干或通过使用本领域技术人员熟悉的各种干燥装置(例如，烘箱)加速固化来使其固化。
根据本发明，所述木制品可以例如通过如下步骤制备：(1)提供经打磨的木质基材；(2)利用喷涂工艺，将本发明的含有氨基和/或亚氨基官能化硅烷的组合物涂覆到木质基材上，从而形成粘附促进层；(3)利 用湿对干涂覆工艺，在所述粘附促进层上依次涂覆一个或多个迈克尔加成固化涂层。可选地，可以在步骤(3)之前将着色剂涂覆在粘附促进层上，从而为木质基材提供所需的颜色。
根据本发明，由此得到的木制品可用于如下应用，包括，但不限于：家用家具，例如桌子、椅子、橱柜等；卧室和浴室家具；办公家具；定制家具，例如学校和儿童家具、医院家具、餐厅和酒店家具、厨房橱柜和家具；室内设计用的板；室内和室外的窗户和门；室内和室外的窗框和门框；室外和室内的护墙板以及木地板。
本发明的另一方面提供了用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的方法，所述方法包括将粘附促进层直接形成在所述木质基材的至少一个主表面上的步骤，其中，所述粘附促进层由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自溶剂、填料、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
本发明的还要另一方面提供了粘附促进层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，其中，所述粘附促进层由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自溶剂、填料、表面活性 剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
在本发明的一个实施方式中，官能化硅烷可以具有通式I所表示的结构：
其中
R
1、R
2和R
3各自独立地表示C
1-C
6烷氧基、C
2-C
6烯氧基、C
6-C
10芳氧基、C
1-C
6烷酰氧基、C
6-C
10芳酰氧基、C
1-C
6烷酮肟基或C
6-C
10芳酮肟基，其中R
1、R
2和R
3可以是相同的或不同的；
R
4表示未取代的或N取代的氨基C
1-C
6烷基，其中所述取代基选自氨基C
1-C
6烷基，C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基和C
7-C
14烷芳基中的一种或多种；
R
5和R
6各自独立地表示C
1-C
6烷基、C
6-C
10芳基、C
7-C
14芳烷基或C
7-C
14烷芳基；并且
p为0至4的整数，优选为0。
在本发明的另一个实施方式中，官能化硅烷可以具有下式结构(通式II)：
其中，
R在每次出现时独立地表示可选被取代的C
1-C
20烷基、C
6-C
10芳基、未取代的或N取代的氨基C
1-C
6烷基；
X在每次出现时独立地表示未取代的或N取代的氨基C
1-C
6烷基；
m是大于或等于1且小于50的整数，n是大于或等于1且小于50的整数，且m与n的和大于等于2。
这种含有氨基和/或亚氨基的官能化硅烷可以涂覆到各种含有酸性物质的木质基材上，解决了迈克尔加成固化涂层难以粘附到木质基材上的问题。由此处理过的木质基材适用于各种应用，包括，但不限于：家用家具，例如桌子、椅子、橱柜等；卧室和浴室家具；办公家具；定制家具，例如学校和儿童家具、医院家具、餐厅和酒店家具、厨房橱柜和家具；室内设计用的板；室内和室外的窗户和门；室内和室外的窗框和门框；室外和室内的护墙板以及木地板。
下述实施例更具体地描述了本发明公开的内容，这些实施例仅仅用于阐述性说明，因为在本发明公开内容的范围内进行各种修正和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购并且可直接使用而无需进一步处理。
实施例
实施例1
处理木质基材
将购自木材市场的实木板进行窑炉干燥。从烘干的板材上截取尺寸为15厘米*15厘米*1.5厘米的样本，并将其置于温度为25℃、相对湿度(RH)为60％且空气流速为1.8m/s的条件下调节至恒重，其中该样品的平衡水分含量为11％。采用条式打磨机，通过购自3M
T Utility Cloth Sheet240号砂纸打磨样品，并用气压枪进行清洁，备用。
形成粘附促进剂
在经处理的样品上喷涂官能化硅烷(CAS：919-30-2)，从而形成粘附促进层，并在空气干燥1小时，在70℃的烘箱中1小时，并且空气中干燥7天。
形成迈克尔加成固化涂层
将下表1所示用量的A组分的各组分混合，从而形成A组分，然后将组分A、组分B以及适量稀释剂以下表2所示用量进行混合，从而形成 适用于形成迈克尔加成固化涂层的双组分涂料组合物。
表1：
表2：
然后，将所形成的涂料组合物分别喷涂到经由粘附促进层处理的和未经粘附促进层处理的木质基材上，并测定所得涂层的干燥时间、铅笔硬度和粘附性，结果示于下表3中。
表3
由上表结果可见，与未涂布官能化硅烷作为粘附促进层的木制品相比，迈克尔加成固化涂层对涂布有官能化硅烷形成的粘附促进层的木质基材的粘附性明显更优，具体地，根据ASTM D3359采用划格法测定的粘附性可以达到5B级。
实施例2
为了寻找迈克尔加成固化涂层在木质基材上的粘附性较差的原因，发明人实施了如下验证试验。首先，配制浓度分别为0％、1％、5％、10％和15％的单宁水溶液。然后，将各个单宁水溶液分别喷涂到松木样板上，并在空气中干燥30分钟，在50的烘箱中2小时，接着冷却。
然后，将以上实施例1所配制的用于形成迈克尔加成固化涂层的清漆以120微米的湿膜厚度涂覆到经处理的木质上，并在空气中干燥4天，然后测试。测试结果汇总在下表4中。
表4.
| 测试样 | 粘附性 | 干燥时间(min) | 铅笔硬度 |
| 经0％单宁水溶液涂覆的样板 | 4B | 35 | B |
| 1％单宁水溶液涂覆的样板 | 4B | 40 | 2B |
| 5％单宁水溶液涂覆的样板 | 2B | 51 | 2B |
| 10％单宁水溶液涂覆的样板 | 0B | 81 | 2B |
| 15％单宁水溶液涂覆的样板 | 0B | 90 | 2B |
由上表4结果可见，木质基材中的单宁会影响迈克尔加成固化涂层的粘附问题，导致划格粘附性显著下降，并且导致干燥时间延长。在本发明之前，还未有现有技术揭示木质基材中单宁的存在是导致迈克尔加成固化涂层在木质基材上的粘附问题的根本原因。
实施例3
使用不同种类的官能化硅烷作为粘附促进剂，进行性能测试。
首先，将不同种类的官能化硅烷涂覆到经处理的橡木基材上，以形成粘附促进层。经处理的橡木基材在空气中干燥1小时，在50℃的烘箱中干燥1小时，冷却后用600号砂纸打磨。
然后，在经处理的橡木基材上以100微米的湿膜厚度涂覆实施例1配制的清漆，并且在空气中干燥1小时，在70℃的红线中干燥1小时，然后在空气中干燥7天。接着，根据ASTM D3359采用划格法，测定所得样品的粘附性，结果汇总在下表5中。
表5.
由上表结果可见，较之其他官能化硅烷，氨基和/或亚氨基官能化硅烷特异性地提高了迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性，这在本申请之前难以预期。
尽管本发明参照大量实施方式和实施例进行描述，但是本领域普通技术人员根据本发明公开的内容能够认识到可以设计其它实施方式，这并未脱离本发明的保护范围和精神。
Claims (19)
- 一种木制品，其包含含有酸性物质的木质基材，其具有至少一个主表面；直接涂覆在所述木制基材的主表面上的粘附促进层；和涂覆在所述粘附促进层上的迈克尔加成固化涂层，其中，所述粘附促进层是由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中所述迈克尔加成固化涂层由双组分固化涂料组合物形成的。
- 如权利要求1所述的木制品，其中，所述官能化硅烷具有通式I所表示的结构：
其中R 1、R 2和R 3各自独立地表示C 1-C 6烷氧基、C 2-C 6烯氧基、C 6-C 10芳氧基、C 1-C 6烷酰氧基、C 6-C 10芳酰氧基、C 1-C 6烷酮肟基或C 6-C 10芳酮肟基，其中R 1、R 2和R 3可以是相同的或不同的；R 4表示未取代的或N取代的氨基C 1-C 6烷基，其中所述取代基选自氨基C 1-C 6烷基，C 1-C 6烷基、C 6-C 10芳基、C 7-C 14芳烷基和C 7-C 14烷芳基中的一种或多种；R 5和R 6各自独立地表示C 1-C 6烷基、C 6-C 10芳基、C 7-C 14芳烷基或C 7-C 14烷芳基；并且p为0至4的整数，优选为0。 - 如权利要求1所述的木制品，其中，所述官能化硅烷包含选自氨基C 1-C 6烷基三甲氧基硅烷、氨基C 1-C 6烷基三乙氧基硅烷、氨基C 1-C 6烷基三丙氧基硅烷、氨基C 1-C 6烷基三丁氧基硅烷、氨基C 1-C 6烷基三异丙烯氧硅烷、氨基C 1-C 6烷基三丁酮肟基硅烷、N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基三甲氧基硅烷、N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基三乙氧基硅烷、N- (氨基C 1-C 6烷基)-氨基C 1-C 6烷基三丙氧基硅烷、N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基三丁氧基硅烷、N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基三异丙烯氧硅烷和N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基三丁酮肟基硅烷中的一种或多种。
- 如权利要求1所述的木制品，其中，所述官能化硅烷还包含一个或多个化学键合到所述官能化硅烷的分子骨架上的硅羟基。
- 如权利要求1和4中任意一项所述的木制品，其中，所述官能化硅烷具有下式结构(通式II)：
其中，R在每次出现时独立地表示可选被取代的C 1-C 20烷基、C 6-C 10芳基、未取代的或N取代的氨基C 1-C 6烷基；X在每次出现时独立地表示未取代的或N取代的氨基C 1-C 6烷基；m是大于或等于1且小于50的整数，n是大于或等于1且小于50的整数，且m与n的和大于等于2。 - 如权利要求5所述的木制品，其中，所述R在每次出现时独立地表示甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一碳烷基、十二碳烷基、十三碳烷基、十四碳烷基、十五碳烷基、十六碳烷基、十八碳烷基、二十碳烷基、氨基C 1-C 6烷基或N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基。
- 如权利要求5所述的木制品，其中，所述X在每次出现时独立地表示氨基C 1-C 6烷基或N-(氨基C 1-C 6烷基)-氨基C 1-C 6烷基。
- 如权利要求1所述的木制品，其中，所述官能化硅烷包括具有通式II的硅氧烷分子的混合物，所述混合物具有在0.8:1至1.2:1的范围内m与n的比值。
- 如权利要求1所述的木制品，其中，所述包含官能化硅烷的组合物是所述官能化硅烷的有机溶剂体系，或所述官能化硅烷的水性分散体。
- 如权利要求9所述的木制品，其中，所述水性分散体在20℃下具 有10或更高的pH。
- 如权利要求9所述的木制品，其中，所述水性分散体在20℃下具有5mPa.s或更低的粘度。
- 如权利要求1所述的木制品，其中，所述酸性物质含有单宁，所述木质基材具有至少0.1wt％的单宁含量，优选具有至少1wt％的单宁含量，更优选具有至少5wt％的单宁含量，还要更优选具有至少10wt％的单宁含量，甚至更优选具有至少30wt％的单宁含量，所述单宁含量是通过CNS4716-2005测定的。
- 如权利要求1所述的木制品，其中，所述木质基材选自坚木、栗木、栎木、红钩栗、油茶、按木、花旗松、日本柳杉、美国扁柏、日本赤松、日本扁柏、水胡桃、黑胡桃、槭木、日本山毛榉、日本泡桐、桦木、婆罗双、木兰、白蜡树、柚木、柞木、楸木、山樟木、杉木、橡木、橡胶木中的一种或多种。
- 如权利要求1所述的木制品，其中，所述双组分固化涂料组合物包含：A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自填料、溶剂、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
- 如权利要求14所述的木制品，其中，所述成膜树脂组合物与所述催化剂的重量比在100:2-100:8的范围内。
- 如权利要求1所述的木制品，其中，所述迈克尔加成固化涂层具有30微米或更厚的厚度，优选具有100微米或更厚的厚度。
- 如权利要求1所述的木制品，其具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。
- 一种用于制备权利要求1-17中任意一项所述木制品的方法，其包 括如下步骤：(a)提供含有酸性物质的木质基材，其具有至少一个主表面；(b)在所述木制基材的主表面上直接涂覆包含官能化硅烷的组合物，以形成粘附促进层；和(c)在所述粘附促进层上涂覆双组分固化涂料组合物，以形成迈克尔加成固化涂层。
- 粘附促进层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，其中，所述粘附促进层由包含官能化硅烷的组合物形成的，所述官能化硅烷包含氨基和/或亚氨基官能团；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：A)成膜树脂组合物，其包含具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，具有至少两个活化的不饱和C＝C基团的第二反应性组分，和任选的附加添加剂，选自填料、溶剂、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
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| US17/424,331 US20220089839A1 (en) | 2019-01-29 | 2020-01-14 | Wood article and process for the preparation of the wood article |
| PL20749741.3T PL3919189T3 (pl) | 2019-01-29 | 2020-01-14 | Produkt drewniany i sposób jego przygotowania |
| DK20749741.3T DK3919189T3 (da) | 2019-01-29 | 2020-01-14 | Træprodukt og fremgangsmåde til fremstilling deraf |
| FIEP20749741.3T FI3919189T3 (fi) | 2019-01-29 | 2020-01-14 | Puutuote ja sen valmistusmenetelmä |
| EP20749741.3A EP3919189B1 (en) | 2019-01-29 | 2020-01-14 | Wood product and preparation method therefor |
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| CN111349393A (zh) * | 2020-02-25 | 2020-06-30 | 江西科技师范大学 | 一种新型植物油基的有机-无机杂化涂层材料的制备方法 |
| CN114561144B (zh) * | 2021-12-28 | 2023-06-13 | 无锡华东锌盾科技有限公司 | 一种环保型高固含面漆涂料及其制备方法 |
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| Publication number | Publication date |
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| EP3919189B1 (en) | 2024-03-13 |
| EP3919189A1 (en) | 2021-12-08 |
| PL3919189T3 (pl) | 2024-05-13 |
| CN109909138A (zh) | 2019-06-21 |
| US20220089839A1 (en) | 2022-03-24 |
| FI3919189T3 (fi) | 2024-04-04 |
| EP3919189A4 (en) | 2022-11-23 |
| DK3919189T3 (da) | 2024-04-08 |
| CN109909138B (zh) | 2022-07-12 |
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