EP1487933A1 - Primary aqueous dispersion hardened by actinic radiation, method for production and use thereof - Google Patents
Primary aqueous dispersion hardened by actinic radiation, method for production and use thereofInfo
- Publication number
- EP1487933A1 EP1487933A1 EP03712053A EP03712053A EP1487933A1 EP 1487933 A1 EP1487933 A1 EP 1487933A1 EP 03712053 A EP03712053 A EP 03712053A EP 03712053 A EP03712053 A EP 03712053A EP 1487933 A1 EP1487933 A1 EP 1487933A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- primary dispersion
- dispersion according
- groups
- actinic radiation
- reactive functional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 64
- 230000005855 radiation Effects 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000524 functional group Chemical group 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 34
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 17
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- -1 cycloaliphatic Chemical group 0.000 claims description 15
- 239000013466 adhesive and sealant Substances 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- MLRCQIICAYVJHD-UHFFFAOYSA-N 1-but-1-enoxybut-1-ene Chemical group CCC=COC=CCC MLRCQIICAYVJHD-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 2
- 229940114081 cinnamate Drugs 0.000 claims description 2
- 230000000295 complement effect Effects 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 description 1
- MGONHMOLWPVQLK-UHFFFAOYSA-N CCC1C(C(=C(C(=C1C)C)C)C)(N=C=O)N=C=O Chemical compound CCC1C(C(=C(C(=C1C)C)C)C)(N=C=O)N=C=O MGONHMOLWPVQLK-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KKVKUNIBLLLFHA-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound C=CC(=O)OCC1(CO)CCCCC1 KKVKUNIBLLLFHA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated 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
- C08G2190/00—Compositions for sealing or packing joints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the present invention relates to new 5 aqueous primary dispersions curable with actinic radiation.
- the present invention also relates to a new process for the preparation of aqueous primary dispersions curable with actinic radiation.
- the present invention relates to the use of the new aqueous primary dispersions curable with actinic radiation as coating materials, adhesives and sealants or for the production of coating materials, adhesives, sealants, films and moldings.
- Aqueous secondary dispersions curable with actinic radiation are known. They are prepared in a customary and known manner by polyaddition of diisocyanates and, if appropriate, polyisocyanates, compounds having at least two isocyanate-reactive groups and compounds having at least one isocyanate-reactive group and at least one reactive functional group having at least one bond which can be activated with actinic radiation in organic solvents.
- the resulting organic solution of the polyurethanes curable with actinic radiation is dispersed in an aqueous medium, which results in the secondary dispersion (cf. for example the
- the polyurethanes curable with actinic radiation must contain cationic or anionic and / or nonionic hydrophilic groups so that they have self-dispersing properties. However, such groups can reduce the water resistance of the polyurethane films.
- the object of the present invention is to provide a new aqueous primary dispersion curable with actinic radiation which no longer has the disadvantages of the prior art, but which can be prepared in a simple manner and is essentially or completely free from organic solvents and is stable in storage ,
- the new aqueous primary dispersion curable with actinic radiation is said to be usable as coating material, adhesive and sealant.
- it is said to be very suitable for the production of coating materials, adhesives and sealing compounds which are curable with actinic radiation or thermally and with actinic radiation.
- the new aqueous primary dispersion curable with actinic radiation comprising liquid and / or solid, emulsified and / or dispersed polymer particles of a z-average particle diameter ⁇ 500 nm, producible by polyaddition in a micro- and / or mini-emulsion of at least
- (C) at least one compound with at least one isocyanate-reactive functional group and with at least one reactive functional group containing at least one bond that can be activated with actinic radiation.
- the new aqueous primary dispersion curable with actinic radiation is referred to below as the “primary dispersion according to the invention”.
- the new process for producing aqueous primary dispersions curable with actinic radiation is referred to below as the “process according to the invention”.
- the object on which the present invention is based could be achieved with the aid of the primary dispersion according to the invention and with the aid of the method according to the invention.
- the process according to the invention gave primary dispersions which were largely or completely free from organic solvents.
- the primary dispersion according to the invention could be dispersed in fine particles and was completely stable in storage, although the polymer particles contained no or only a small number of ionic or non-ionic hydrophilic groups.
- the primary dispersion according to the invention was extremely widely applicable. So it could be used directly as a coating material, adhesive and sealant. Furthermore, it was ideally suited for the production of coating materials, adhesives and sealants curable with actinic radiation or thermally and with actinic radiation, and for the production of films and molded parts.
- actinic radiation means electromagnetic radiation, such as visible light, UV radiation and X-rays, in particular UV radiation, and corpuscular radiation, such as electron beams.
- electromagnetic radiation such as visible light, UV radiation and X-rays, in particular UV radiation
- corpuscular radiation such as electron beams.
- the curing of coating materials, adhesives and sealants with heat and actinic radiation is also referred to by experts as dual-cure.
- Micro and mini emulsions are dispersions or emulsions of water, an oil phase and one or more surface-active substances which have droplet sizes of 5 to 50 nm (micro emulsions) or 50 to 500 nm (mini emulsions). Microemulsions are considered to be thermodynamically stable, whereas the mini emulsions are considered to be metastable (cf. Emulsion Polymerization and Emulsion Polymers, editors. PA Lovell and Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pages 700 and following; Mohamed S. El-Aasser, Advances in Emulsion Polymerization and Latex Technology, 30 th Annual Short Course, Volume 3, June 7-11, 1999, Emulsion Polymers Institute, Lehigh University, Bethlehem, Pennsylvania, USA).
- the primary dispersion according to the invention has a z-average particle size of ⁇ 500 nm, preferably ⁇ 400 nm.
- a z-average particle size of ⁇ 500 nm, preferably ⁇ 400 nm.
- it can be determined in a customary and known manner by means of photon correlation spectroscopy based on the principle of dynamic, quasi-elastic light scattering.
- a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments or a PCS Malvern Zetasizer 1000 can be used.
- the measurement is usually carried out on an aqueous emulsion which contains 0.01% by weight of the emulsified polymer particles.
- the primary dispersion according to the invention preferably has a z-average particle size of> 50 nm. In particular, it is between 100 and 350 nm.
- the primary dispersion according to the invention can have a monomodal or multimodal, in particular bimodal, particle size distribution.
- 0.1 to 80% by weight, in particular 1.0 to 50% by weight, of the polymer particles can have a particle size, determined using an analytical ultracentrifuge, of 20 to 500 nm, in particular 50 to 300 nm. to have. 20 to 99.9% by weight, in particular 50 to 99% by weight, of the polymer particles can have a particle size of 200 to 1,500 nm, in particular 300 to 900 nm, the particle sizes being at least 50 nm, in particular at least 100 nm, very particularly preferably differ by at least 200 nm.
- the measurement method reference is also made to lines 5 to 9, page 6 of German patent application DE 19628 142 A1.
- the solids content of the primary dispersion according to the invention can vary very widely and depends on the dispersibility of the polymer particles and the requirements of the particular use.
- the solids content is preferably 20 to 70, preferably 25 to 65, particularly preferably 30 to 60 and in particular 35 to 55% by weight.
- the dispersion according to the invention can be produced by at least polyaddition
- the miniemulsion containing the starting compounds (A), (B) and (C) can be prepared by homogenizing the mixture of the starting products and emulsifying them in an aqueous medium in a high shear field. Examples of suitable devices and methods are described in the patents DE 196 28 142 A1, page 5, lines 1 to 30, DE 196 28 143 A1, page 7, lines 30 to 58, or EP 0401 565 A1, lines 27 to 51 , described. The mixing, homogenization and emulsification of the starting products are preferably carried out with the exclusion of actinic radiation.
- the aqueous medium or the aqueous phase can contain additives, such as customary and known dispersing aids or emulsifiers, protective colloids and / or defoamers.
- the polyaddition or the process according to the invention is preferably carried out in the presence of emulsifiers and / or protective colloids.
- emulsifiers and / or protective colloids examples of suitable emulsifiers and / or protective colloids and the amounts in which they are advantageously used can be found in German patent application DE 196 28 142 A1, page 3, lines 8 to 48.
- hydrophobic compounds can also be present. These hydrophobic compounds are also called costabilizers by experts.
- the hydrophobic compounds are water-insoluble, low molecular weight, oligomeric or polymeric substances.
- hydrophobic compounds are customary and known crosslinking agents, such as aminoplast resins; blocked
- the mixture of the essential starting compounds preferably also contains customary and known additives, in particular light stabilizers, such as UV absorbers and reversible radical scavengers (HALS), and catalysts of polyaddition, such as organic dialkyltin compounds, in particular dibutyltin dilaurate, in customary and known, effective amounts.
- light stabilizers such as UV absorbers and reversible radical scavengers (HALS)
- HALS reversible radical scavengers
- catalysts of polyaddition such as organic dialkyltin compounds, in particular dibutyltin dilaurate, in customary and known, effective amounts.
- the polyaddition is preferably carried out at a temperature of 30 to 150, preferably 40 to 120 and in particular 50 to 100 ° C. At reaction temperatures> 100 ° C, pressure-tight reactors are used. Examples of suitable reactors are stirred tanks, tubular reactors, loop reactors or Taylor reactors, in particular stirred tanks.
- the polyisocyanates (A) are preferably selected from the group consisting of customary and known aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aiiphatic-aromatic, cycloaliphatic-aromatic, aliphatic-cycloaliphatic-aromatic polyisocyanates, preferably aliphatic, cycloaliphatic and aliphatic-cyclic aliphatic Polyisocyanates.
- the polyisocyanates (A) are diisocyanates. Examples of suitable polyisocyanates (A) are known from German patent application DE 199 14 896 A1, column 4, line 42, to column 5, line 33.
- the polyols (B) are preferably selected from the group consisting of low molecular weight polyols (B1) and oligomeric and polymeric Polyols (B2), in particular oligomeric and polymeric polyols (B2), selected.
- the polyols are preferably diols.
- the low molecular weight polyols (B1) preferably have a number average molecular weight ⁇ 200 Daltons and the oligomeric and polymeric polyols (B ") have a number average molecular weight> 200 Daltons.
- the molar ratio of (B1): (B2)> 1:10 is preferred.
- polyester polyols (B2) are known from German patent application DE 199 14 896 A1, column 5, line 35 to column 8, line 35 and column 15, lines 13 to 46.
- the compounds (C) are also customary and known.
- the bonds which can be activated with actinic radiation in the reactive functional groups of the compounds (C) are preferably selected from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or - double bonds.
- the double bonds are carbon-carbon double bonds (“double bonds”).
- the double bonds are preferably in reactive functional groups selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl - or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
- the reactive functional groups are acrylate groups.
- the isocyanate-reactive functional groups present in the compounds (C) are preferably selected from the group consisting of hydroxyl groups, thiol groups and primary and secondary amino groups. In particular, the isocyanate-reactive functional groups are hydroxyl groups.
- the compounds (C) are particularly preferably selected from the group consisting of hydroxyalkyl and hydroxycycloalkyl acrylates.
- suitable compounds (C) of this type are 2-hydroxyethyl, 2 and 3-hydroxypropyl and 4-hydroxybutyl acrylate and cyclohexanedimethanol monoacrylate.
- compounds (D) which are different from the compounds (B) and (C) and contain at least one, preferably at least two and in particular two of the isocyanate-reactive functional groups described above.
- the compounds (D) may contain no or at least one customary and known reactive functional group which can undergo crosslinking reactions “with itself” and / or also with complementary reactive functional groups other than isocyanate groups.
- the compounds (D) can contain at least one hydrophilic functional group selected from the group consisting of (potentially) anionic groups, such as carboxyl or sulfonic acid groups, or (potentially) cationic groups , such as amino groups, and non-ionic hydrophilic functional groups, such as polyalkylene oxide groups, in particular polyethylene oxide groups.
- hydrophilic functional group selected from the group consisting of (potentially) anionic groups, such as carboxyl or sulfonic acid groups, or (potentially) cationic groups , such as amino groups, and non-ionic hydrophilic functional groups, such as polyalkylene oxide groups, in particular polyethylene oxide groups.
- the compounds (D) are preferably added during the polyaddition of the aqueous phase. If, for example, polyamines, in particular diamines, (D) are added, the polyurethanes present in the polymer particles can be chain-extended in this way.
- the equivalent ratio of free isocyanate groups in the polyisocyanates (A) to the sum of the isocyanate-reactive groups in the starting compounds (B) and (C) and, if appropriate, (D) is preferably chosen such that there are no longer any free isocyanate groups in the polymer particles.
- the equivalent ratio is therefore preferably ⁇ 1, in particular ⁇ 0.9.
- the equivalent ratio should not be chosen so small that free starting compounds (B) and (C) and, if appropriate, (D) are still present after the polyaddition has ended.
- the polymer particles of the primary dispersion according to the invention are irradiated with actinic radiation, in particular UV radiation, before, during and / or after, in particular after, the polyaddition.
- actinic radiation in particular UV radiation
- This increases the number average and mass average molecular weight of the polyurethanes in the polymer particles.
- the irradiation can also be carried out until the polymer particles are partially or completely crosslinked and are present as crosslinked microparticles.
- the crosslinked microparticles can still be hardened with actinic radiation if they still contain a certain number of the reactive functional groups described above which can be activated with actinic radiation.
- the primary dispersion according to the invention has numerous particular advantages. So it is essentially or completely free of organic solvents. “Essentially free” means that the solvent content is ⁇ 5, preferably ⁇ 2 and in particular ⁇ 1% by weight. “Completely free” means that the solvent content is below the detection limits of the usual and known methods for analyzing organic solvents.
- the primary dispersion according to the invention is outstandingly suitable as a coating material and adhesive curable with actinic radiation and as a sealing compound curable with actinic radiation. It is also ideal for the production of coating materials, adhesives and sealants, in particular coating materials, that can be hardened with actinic radiation or dual-cure. Last but not least, it is ideal for the production of films and molded parts, especially optical molded parts.
- the coating materials according to the invention can be used as clear lacquers for the production of clear lacquers, in particular in multi-layer lacquers which give color and / or effects. You can also use it as a filler or as a coloring and / or effect agent
- Solid color finishes or basecoats can be used.
- they can be mixed with customary and known pigments, optics, optically, electrically conductive, magnetically shielding, fluorescent, corrosion-inhibiting and / or filling pigments.
- the primary dispersion according to the invention can also be coated with thermally curable primary dispersions based on mini-emulsions, as described in patent applications DE 199 59 927 A1, DE 199 59 928 A1, DE 199 59 923 A1 or DE 100 05 819 A1 are known.
- the production of the coating materials according to the invention does not require any special features in terms of method, but rather the customary and known devices and methods can be used. Examples of suitable processes are spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used.
- the applied coating materials are cured with actinic radiation or thermally and with actinic radiation, in particular UV radiation, in a customary and known manner, if appropriate after flashing off and drying.
- the pigmented coating materials are preferably cured thermally and with actinic radiation and the unpigmented coating materials with actinic radiation.
- a radiation dose of 10 3 to 4x10 4 , preferably 2x10 3 to 3x10 4 , preferably 3x10 3 to 2.5x10 4 and in particular 5x10 3 to 2x10 4 Jm "2 is preferably used for curing with actinic radiation.
- the radiation intensity is 1x10 ° to 3x10 5 , preferably 2x10 ° to 2x10 5 , preferably 3x10 ° to 1.5x10 5 and in particular 5x10 ° to 1.2x10 5 Wm "2 .
- Curing with actinic radiation is preferably carried out under an oxygen-depleted atmosphere.
- the resulting coatings according to the invention have excellent performance properties. They are smooth and free from surface defects, high-gloss, brilliant, hard, flexible, scratch-resistant, chemical-resistant, water-resistant and weather-resistant. They adhere firmly to coated and uncoated substrates made of wood, metal, glass, leather, plastics, ceramics, natural stone, artificial stone or paper as well as composites of these materials.
- the adhesive layers according to the invention have a permanently high adhesive strength even under extreme conditions.
- the seals according to the invention permanently seal substrates of the type mentioned above, even against aggressive substances.
- the films of molded parts according to the invention have a profile of properties that corresponds fully to that of the coatings according to the invention.
- TXDI ® tetramethylxylylidene diisocyanate
- Photoinitiator 0.44 parts by weight of Tinuvin ® 400 (commercially available UV absorber from Ciba Specialty Chemicals, 85 percent in methoxy-2-propanol),
- Tinuvin ® 292 commercially available UV absorber from Ciba Specialty Chemicals
- HALS 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxyl
- the resulting suspensions were then converted into a miniemulsion (z-average particle size: 200 nm; measured with a PCS Malvern Zetasizer 1000) by ⁇ -minute dispersion using a Wagner jet homogenizer at a pressure of 180 bar.
- the mini emulsion was stirred at 80 ° C. until the theoretical solids content of 40% by weight was reached.
- the mini emulsion or primary dispersion was stable on storage. As such, it could be used as a UV-curable coating material and adhesive and as a UV-curable sealant. As a coating material, it delivered hard, scratch-resistant, flexible, chemical-resistant and weather-resistant clear coats after application to substrates. However, it could also be used for the production of coating materials, adhesives and sealing compounds which are curable thermally and with actinic radiation.
- the mini emulsion was mixed with conventional and known dispersions of thermally curable coating materials, adhesives and sealants. Because of its advantageous properties, the mini emulsion could also be used very well for the production of foils, in particular lacquer foils, and molded parts. Since the miniemulsion was essentially free of organic solvents, no special safety measures, such as the extraction of volatile organic solvents or the dissipation of static electricity, had to be taken in its manufacture, applications and curing.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Abstract
Primary aqueous dispersion hardened by actinic radiation, comprising liquid and/or solid, emulsified and/or dispersed polymer particles with a Z-average mean particle size of ≤ 500 nm, which may be produced by polyaddition in a micro- and/or mini-emulsion with at least: (A) at least one polyisocyanate, (B) at least one polyol and (C) at least one compound with at least one functional group reactive with isocyanate groups and at least one reactive functional group having at least one bond which may be activated by actinic radiation. The invention further relates to a method for production and use thereof.
Description
T AKTINISCHER STRAHLUNG HÄRTBARE, WÄSSERIGE PRIMAERDISPERSIONEN, VERFAHREN ZU IHRER HERSTELLUNG UND IHRE VERWENDUNGT ACTINIC RADIATION CURABLE, AQUEOUS PRIMARY DISPERSIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE
Die vorliegende Erfindung betrifft neue, mit aktinischer Strahlung härtbare, 5 wässrige Primärdispersionen. Außerdem betrifft die vorliegende Erfindung ein neues Verfahren zur Herstellung von mit aktinischer Strahlung härtbaren, wässrigen Primärdispersionen. Des weiteren betrifft die vorliegende Erfindung die Verwendung der neuen, mit aktinischer Strahlung härtbaren, wässrigen Primärdispersionen als 0 Beschichtungsstoffe, Klebstoffe und Dichtungsmassen oder zur Herstellung von Beschichtungsstoffen, Klebstoffen, Dichtungsmassen, Folien und Formteilen.The present invention relates to new 5 aqueous primary dispersions curable with actinic radiation. The present invention also relates to a new process for the preparation of aqueous primary dispersions curable with actinic radiation. Furthermore, the present invention relates to the use of the new aqueous primary dispersions curable with actinic radiation as coating materials, adhesives and sealants or for the production of coating materials, adhesives, sealants, films and moldings.
Mit aktinischer Strahlung härtbare, wässrige Sekundärdispersionen sind 5 bekannt. Sie werden in üblicher und bekannter Weise durch Polyaddition von Diisocyanaten sowie gegebenenfalls Polyisocyanaten, Verbindungen mit mindestens zwei isocyanatreaktiven Gruppen und Verbindungen mit mindestens einer isocyanatreaktiven Gruppe und mindestens einer reaktiven funktionellen Gruppe mit mindestens einer mit aktinischer 0 Strahlung aktivierbaren Bindung in organischen Lösemitteln hergestellt.Aqueous secondary dispersions curable with actinic radiation are known. They are prepared in a customary and known manner by polyaddition of diisocyanates and, if appropriate, polyisocyanates, compounds having at least two isocyanate-reactive groups and compounds having at least one isocyanate-reactive group and at least one reactive functional group having at least one bond which can be activated with actinic radiation in organic solvents.
Die resultierende organische Lösung der mit aktinischer Strahlung härtbaren Polyurethane wird in einem wässrige Medium dispergiert, wodurch die Sekundärdispersion resultiert (vgl. beispielsweise dieThe resulting organic solution of the polyurethanes curable with actinic radiation is dispersed in an aqueous medium, which results in the secondary dispersion (cf. for example the
Patentanmeldungen EP 0401 565 A 1 , EP 0 522420 A 1 , EP 0 522 419 A 5 2, EP 0 755 946 A 1 , EP 0 608 021 A 1 , EP 0 708 788 A 1; EP 0 730 613Patent applications EP 0401 565 A 1, EP 0 522420 A 1, EP 0 522 419 A 5 2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 ; EP 0 730 613
A 1, DE 199 14 896 A 1 , DE 199 53 446 A 1 oder DE 199 53 203 A 1).A 1, DE 199 14 896 A 1, DE 199 53 446 A 1 or DE 199 53 203 A 1).
Nachteilig hierbei ist, dass die Sekundärdispersionen vergleichsweise große Mengen an organischen Lösemitteln enthalten, die durch 0 Destillation oder azeotrope Destillation entfernt werden müssen, wenn dieThe disadvantage here is that the secondary dispersions contain comparatively large amounts of organic solvents, which have to be removed by distillation or azeotropic distillation if the
Sekundärdispersionen im wesentlichen oder völlig von organischen
Lösemitteln frei sein sollen. Dies stellt aber einen erheblichen zusätzlichen verfahrenstechnischen Aufwand dar. Außerdem müssen die mit aktinischer Strahlung härtbaren Polyurethane kationische oder anionische und/oder nichtionische hydrophile Gruppen enthalten, damit sie selbstdispergierende Eigenschaften aufweisen. Solche Gruppen können aber die Wasserbeständigkeit der Polyurethanfilme verringern.Secondary dispersions essentially or entirely of organic Solvents should be free. However, this represents a considerable additional outlay in terms of process technology. In addition, the polyurethanes curable with actinic radiation must contain cationic or anionic and / or nonionic hydrophilic groups so that they have self-dispersing properties. However, such groups can reduce the water resistance of the polyurethane films.
Aufgabe der vorliegenden Erfindung ist es, eine neue, mit aktinischer Strahlung härtbare, wässrige Primärdispersion bereitzustellen, die die Nachteile des Standes der Technik nicht mehr aufweist, sondern die sich in einfacher Weise herstellen lässt und im wesentlichen oder völlig frei von organischen Lösemitteln und lagerstabil ist. Die neue, mit aktinischer Strahlung härtbare, wässrige Primärdispersion soll als Beschichtungsstoff, Klebstoff und Dichtungsmasse verwendbar sein. Außerdem soll sie sich sehr gut zur Herstellung von mit aktinischer Strahlung oder thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen eignen. Nicht zuletzt soll sie auch sehr gut für die Herstellung von Folien und Formteilen geeignet sein.The object of the present invention is to provide a new aqueous primary dispersion curable with actinic radiation which no longer has the disadvantages of the prior art, but which can be prepared in a simple manner and is essentially or completely free from organic solvents and is stable in storage , The new aqueous primary dispersion curable with actinic radiation is said to be usable as coating material, adhesive and sealant. In addition, it is said to be very suitable for the production of coating materials, adhesives and sealing compounds which are curable with actinic radiation or thermally and with actinic radiation. Last but not least, it should also be very suitable for the production of foils and molded parts.
Demgemäß wurde die neue, mit aktinischer Strahlung härtbare, wässrige Primärdispersion gefunden, enthaltend flüssige und/oder feste, emulgierte und/oder dispergierte Polymerpartikel eines z-mittleren Teilchendurchmessers < 500 nm, herstellbar durch Polyaddition in einer Mikro- und/oder Miniemulsion von zumindestAccordingly, the new aqueous primary dispersion curable with actinic radiation has been found, comprising liquid and / or solid, emulsified and / or dispersed polymer particles of a z-average particle diameter <500 nm, producible by polyaddition in a micro- and / or mini-emulsion of at least
(A) mindestens einem Polyisocyanat,(A) at least one polyisocyanate,
(B) mindestens einem Polyol und(B) at least one polyol and
(C) mindestens einer Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe und mit mindestens einer
reaktiven funktionellen Gruppe, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung.(C) at least one compound with at least one isocyanate-reactive functional group and with at least one reactive functional group containing at least one bond that can be activated with actinic radiation.
Im Folgenden wird die neue, mit aktinischer Strahlung härtbare, wässrige Primärdispersion als »erfindungsgemäße Primärdispersion« bezeichnet.The new aqueous primary dispersion curable with actinic radiation is referred to below as the “primary dispersion according to the invention”.
Außerdem wurde das neue Verfahren zur Herstellung von mit aktinischer Strahlung härtbaren, wässrigen Primärdispersionen, enthaltend flüssige und/oder feste, emulgierte und/oder dispergierte Polymerpartikel eines z- mittleren Teilchendurchmessers < 500 nm, gefunden, bei dem manIn addition, the new process for the preparation of aqueous primary dispersions curable with actinic radiation, comprising liquid and / or solid, emulsified and / or dispersed polymer particles of a z-average particle diameter <500 nm, was found, in which
(1) eine Mikro- oder Miniemulsion aus zumindest(1) a micro or miniemulsion of at least
(A) mindestens einem Polyisocyanat,(A) at least one polyisocyanate,
(B) mindestens einem Polyol und(B) at least one polyol and
(C) mindestens einer Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe und mit mindestens einer reaktiven funktionellen Gruppe, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung,(C) at least one compound with at least one isocyanate-reactive functional group and with at least one reactive functional group containing at least one bond which can be activated with actinic radiation,
herstellt undmanufactures and
(2) durch Polyaddition polymerisiert.(2) polymerized by polyaddition.
Im Folgenden wird das neue Verfahren zur Herstellung von mit aktinischer Strahlung härtbaren, wässrigen Primärdispersionen als »erfindungsgemäßes Verfahren« bezeichnet.
Im Hinblick auf den Stand der Technik war es überraschend und für den Fachmann nicht vorhersehbar, dass die Aufgabe, die der vorliegenden Erfindung zugrundelag, mit Hilfe der erfindungsgemäßen Primärdispersion und mit Hilfe des erfindungsgemäßen Verfahrens gelöst werden konnte. Insbesondere war es überraschend, dass mit Hilfe des erfindungsgemäßen Verfahrens Primärdispersionen erhalten wurden, die weitgehend oder völlig frei von organischen Lösemitteln waren. Außerdem war es überraschend, dass die erfindungsgemäße Primärdispersion sich feinteilig dispergieren ließ und völlig lagerstabil war, obwohl die Polymerpartikel keine oder nur eine geringe Anzahl von ionischen oder nicht-ionischen hydrophilen Gruppen enthielt. Nicht zuletzt war es überraschend, dass die erfindungsgemäße Primärdispersion außerordentlich breit anwendbar war. So konnte sie direkt als Beschichtungsstoff, Klebstoff und Dichtungsmasse verwendet werden. Des Weiteren eignete sie sich hervorragend für die Herstellung von mit aktinischer Strahlung oder thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen und für die Herstellung von Folien und Formteilen. Die aus den erfindungsgemäßen Beschichtungsstoffen, Klebstoffen und Dichtungsmassen hergestellten Beschichtungen, Klebschichten und Dichtungen sowie die Folien und Formteile wiesen hervorragende anwendungstechnische Eigenschaften auf. Insbesondere wiesen sie eine sehr hohe Wasserbeständigkeit auf.The new process for producing aqueous primary dispersions curable with actinic radiation is referred to below as the “process according to the invention”. In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention is based could be achieved with the aid of the primary dispersion according to the invention and with the aid of the method according to the invention. In particular, it was surprising that the process according to the invention gave primary dispersions which were largely or completely free from organic solvents. It was also surprising that the primary dispersion according to the invention could be dispersed in fine particles and was completely stable in storage, although the polymer particles contained no or only a small number of ionic or non-ionic hydrophilic groups. Last but not least, it was surprising that the primary dispersion according to the invention was extremely widely applicable. So it could be used directly as a coating material, adhesive and sealant. Furthermore, it was ideally suited for the production of coating materials, adhesives and sealants curable with actinic radiation or thermally and with actinic radiation, and for the production of films and molded parts. The coatings, adhesive layers and seals produced from the coating materials, adhesives and sealants according to the invention, and also the foils and moldings, had outstanding performance properties. In particular, they had very high water resistance.
Hier und im Folgenden ist unter aktinischer Strahlung elektromagnetische Strahlung, wie sichtbares Licht, UV-Strahlung und Röntgenstrahlung, insbesondere UV-Strahlung, und Korpuskularstrahlung, wie Elektronenstrahlung, zu verstehen.
Die Härtung von Beschichtungsstoffen, Klebstoffen und Dichtungsmassen mit Hitze und aktinischer Strahlung wird von der Fachwelt auch als Dual- Cure bezeichnet.Here and below, actinic radiation means electromagnetic radiation, such as visible light, UV radiation and X-rays, in particular UV radiation, and corpuscular radiation, such as electron beams. The curing of coating materials, adhesives and sealants with heat and actinic radiation is also referred to by experts as dual-cure.
Mikro- und Miniemulsionen sind Dispersionen oder Emulsionen aus Wasser, einer Ölphase und einer oder mehreren oberflächenaktiven Substanzen, die eine Tröpfchengrößen von 5 bis 50 nm (Mikroemulsionen) oder von 50 bis 500 nm (Miniemulsionen) aufweisen. Dabei gelten Mikroemulsionen als thermodynamisch stabil, wogegen die Miniemulsionen als metastabil angesehen werden (vgl. Emulsion Polymerization and Emulsion Polymers, Editoren. P. A. Lovell und Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, Seiten 700 und folgende; Mohamed S. El-Aasser, Advances in Emulsion Polymerization and Latex Technology, 30th Annual Short Course, Volume 3, June 7-11, 1999, Emulsion Polymers Institute, Lehigh University, Bethlehem, Pennsylvania, U.S.A).Micro and mini emulsions are dispersions or emulsions of water, an oil phase and one or more surface-active substances which have droplet sizes of 5 to 50 nm (micro emulsions) or 50 to 500 nm (mini emulsions). Microemulsions are considered to be thermodynamically stable, whereas the mini emulsions are considered to be metastable (cf. Emulsion Polymerization and Emulsion Polymers, editors. PA Lovell and Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pages 700 and following; Mohamed S. El-Aasser, Advances in Emulsion Polymerization and Latex Technology, 30 th Annual Short Course, Volume 3, June 7-11, 1999, Emulsion Polymers Institute, Lehigh University, Bethlehem, Pennsylvania, USA).
Die erfindungsgemäße Primärdispersion weist eine z-mittlere Teilchengröße von < 500 nm , vorzugsweise < 400 nm auf. Sie kann beispielsweise in üblicher und bekannter Weise mittels der Photonenkorrelationsspektroskopie nach dem Prinzip der dynamischen, quasielastischen Lichtstreuung bestimmt werden. Hierfür können beispielsweise ein Coulter N4 Plus Particle Analyzer der Firma Coulter Scientific Instruments oder ein PCS Malvern Zetasizer 1000 benutzt werden. Üblicherweise wird die Messung an einer wäßrigen Emulsion, welche 0,01 Gew.-% der emulgierten Polymerpartikel enthält, durchgeführt. Bevorzugt weist die erfindungsgemäße Primärdispersion eine z-mittlere Teilchengröße von > 50 nm auf. Insbesondere liegt sie zwischen 100 und 350 nm.
Die erfindungsgemäße Primärdispersion kann eine monomodale oder multimodale, insbesondere bimodale, Teilchengrößenverteilung aufweisen. Im Falle einer bimodalen Teilchengrößenverteilung können 0,1 bis 80 Gew.-%, insbesondere 1,0 bis 50 Gew.-%, der Polymerpartikel eine Teilchengröße, bestimmt mit einer analytischen Ultrazentrifuge, von 20 bis 500 nm, insbesondere 50 bis 300 nm, haben. 20 bis 99,9 Gew.-%, insbesondere 50 bis 99 Gew.-%, der Polymerpartikel können eine Teilchengröße von 200 bis 1.500 nm, insbesondere 300 bis 900 nm, haben, wobei sich die Teilchengrößen um mindestens 50 nm, insbesondere um mindestens 100 nm, ganz besonders bevorzugt um mindestens 200 nm unterscheiden. Hinsichtlich der Messmethode wird ergänzend auf die Zeilen 5 bis 9, der Seite 6 der deutschen Patentanmeldung DE 19628 142 A 1 verwiesen.The primary dispersion according to the invention has a z-average particle size of <500 nm, preferably <400 nm. For example, it can be determined in a customary and known manner by means of photon correlation spectroscopy based on the principle of dynamic, quasi-elastic light scattering. For example, a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments or a PCS Malvern Zetasizer 1000 can be used. The measurement is usually carried out on an aqueous emulsion which contains 0.01% by weight of the emulsified polymer particles. The primary dispersion according to the invention preferably has a z-average particle size of> 50 nm. In particular, it is between 100 and 350 nm. The primary dispersion according to the invention can have a monomodal or multimodal, in particular bimodal, particle size distribution. In the case of a bimodal particle size distribution, 0.1 to 80% by weight, in particular 1.0 to 50% by weight, of the polymer particles can have a particle size, determined using an analytical ultracentrifuge, of 20 to 500 nm, in particular 50 to 300 nm. to have. 20 to 99.9% by weight, in particular 50 to 99% by weight, of the polymer particles can have a particle size of 200 to 1,500 nm, in particular 300 to 900 nm, the particle sizes being at least 50 nm, in particular at least 100 nm, very particularly preferably differ by at least 200 nm. With regard to the measurement method, reference is also made to lines 5 to 9, page 6 of German patent application DE 19628 142 A1.
Der Festkörpergehalt der erfindungsgemäßen Primärdispersion kann sehr breit variieren und richtet sich nach der Dispergierbarkeit der Polymerpartikel und den Erfordernissen des jeweiligen Verwendungszwecks. Vorzugsweise liegt der Festkörpergehalt bei 20 bis 70, bevorzugt 25 bis 65, besonders bevorzugt 30 bis 60 und insbesondere 35 bis 55 Gew.-%.The solids content of the primary dispersion according to the invention can vary very widely and depends on the dispersibility of the polymer particles and the requirements of the particular use. The solids content is preferably 20 to 70, preferably 25 to 65, particularly preferably 30 to 60 and in particular 35 to 55% by weight.
Die erfindungsgemäße Dispersion ist herstellbar durch Polyaddition von zumindestThe dispersion according to the invention can be produced by at least polyaddition
(A) mindestens einem, insbesondere einem, Polyisocyanat,(A) at least one, in particular one, polyisocyanate,
(B) mindestens einem, insbesondere einem, Polyol und(B) at least one, especially one, polyol and
(C) mindestens einer, insbesondere einer, Verbindung mit mindestens einer, insbesondere einer, isocyanatreaktiven funktionellen Gruppe und mit mindestens einer, insbesondere einer, reaktiven
funktionellen Gruppe, enthaltend mindestens eine, insbesondere eine, mit aktinischer Strahlung aktivierbare Bindung(C) at least one, in particular one, compound with at least one, in particular one, isocyanate-reactive functional group and with at least one, in particular one, reactive functional group containing at least one, in particular one, bond which can be activated with actinic radiation
in einer Mini- oder Mikroemulsion, vorzugsweise in einer Miniemulsion.in a mini or micro emulsion, preferably in a mini emulsion.
Die Miniemulsion, enthaltend die Ausgangsverbindungen (A), (B) und (C), ist herstellbar, in dem man die Mischung der Ausgangsprodukte homogenisiert und in einem wässrigen Medium in einem hohen Scherfeld emulgiert. Beispiele geeigneter Vorrichtungen und Verfahren werden in den Patentschriften DE 196 28 142 A 1, Seite 5, Zeilen 1 bis 30, DE 196 28 143 A 1 , Seite 7, Zeilen 30 bis 58, oder EP 0401 565 A 1 , Zeilen 27 bis 51 , beschrieben. Vorzugsweise werden das Vermischen, Homogenisieren und Emulgieren der Ausgangsprodukte unter Ausschluss von aktinischer Strahlung durchgeführt.The miniemulsion containing the starting compounds (A), (B) and (C) can be prepared by homogenizing the mixture of the starting products and emulsifying them in an aqueous medium in a high shear field. Examples of suitable devices and methods are described in the patents DE 196 28 142 A1, page 5, lines 1 to 30, DE 196 28 143 A1, page 7, lines 30 to 58, or EP 0401 565 A1, lines 27 to 51 , described. The mixing, homogenization and emulsification of the starting products are preferably carried out with the exclusion of actinic radiation.
Das wässrige Medium oder die wässrige Phase kann Zusatzstoffe, wie übliche und bekannte Dispergierhilfsmittel oder Emulgatoren, Schutzkolloide und/oder Entschäumer, enthalten.The aqueous medium or the aqueous phase can contain additives, such as customary and known dispersing aids or emulsifiers, protective colloids and / or defoamers.
Vorzugsweise wird die Polyaddition bzw. das erfindungsgemäße Verfahren in der Gegenwart von Emulgatoren und/oder Schutzkolloiden durchgeführt. Beispiele geeigneter Emulgatoren und/oder Schutzkolloide sowie die Mengen, in denen sie vorteilhafterweise angewandt werden, gehen aus der deutschen Patentanmeldung DE 196 28 142 A1, Seite 3, Zeilen 8 bis 48, hervor.The polyaddition or the process according to the invention is preferably carried out in the presence of emulsifiers and / or protective colloids. Examples of suitable emulsifiers and / or protective colloids and the amounts in which they are advantageously used can be found in German patent application DE 196 28 142 A1, page 3, lines 8 to 48.
Außerdem können auch noch hydrophobe Verbindungen zugegen sein. Diese hydrophoben Verbindungen werden von der Fachwelt auch als Costabilisatoren bezeichnet.
Bei den hydrophoben Verbindungen handelt sich um wasserunlösliche niedermolekulare, oligomere oder polymere Substanzen.In addition, hydrophobic compounds can also be present. These hydrophobic compounds are also called costabilizers by experts. The hydrophobic compounds are water-insoluble, low molecular weight, oligomeric or polymeric substances.
Beispiele geeigneter hydrophober Verbindungen sind übliche und bekannte Vernetzungsmittel, wie Aminoplastharze; blockierteExamples of suitable hydrophobic compounds are customary and known crosslinking agents, such as aminoplast resins; blocked
Polyisocyanate, oder Tris(alkoxycarbonylamino)triazine, Ester von 3 bis 6 Kohlenstoffatomen aufweisenden alpha.beta-monoolefinisch ungesättigten Carbonsäuren mit Alkoholen mit 12 bis 30 Kohlenstoffatomen im Alkylrest; Ester von Vinyl- und/oder Allylalkohol mit 12 bis 30 Kohlenstoffatome im Molekül aufweisenden Alkanmonocarbon-, -sulfon- und/oder - phosphonsäuren; Amide von 3 bis 6 Kohienstoffatome aufweisenden alpha.beta-monoolefinisch ungesättigten Carbonsäuren mit Alkylaminen mit 12 bis 30 Kohlenstoffatomen im Alkylrest; Makromomere auf der Basis olefinisch ungesättigter Verbindungen mit im statistischen Mittel mindestens einer, insbesondere endständigen, olefinisch ungesättigten Gruppe im Molekül; Polysiloxanmakromonomere mit im statstischen Mittel mindestens einer, insbesondere endständigen, olefinisch ungesättigten Gruppe im Molekül; oligomere und/oder polymere Polymerisations-, Polykondensations- und/oder Polyadditionsprodukte; wasserunlösliche Molekulargewichtsregler, insbesondere Mercaptane; aliphatische, cycloaliphatische und/oder aromatische halogenierte und/oder nicht halogenierte Kohlenwasserstoffe; Alkanole und/oder Alkylamine mit mindestens 12 Kohlenstoffatomen im Alkylrest; Organosilane und/oder - siloxane; pflanzliche, tierische, halbsynthetische und/oder synthetische Öle; hydrophobe Farbstoffe. Weitere Beispiele geeigneter hydrophober Verbindungen bzw. Costabilisatoren sowie die Mengen, in denen sie vorteilhafterweise angewandt werden, sind aus der deutschen Patentanmeldung DE 196 28 142 A 1, Seite 4, Zeilen 37 bis 59, bekannt.Polyisocyanates, or tris (alkoxycarbonylamino) triazines, esters of 3 to 6 carbon atoms containing alpha.beta-monoolefinically unsaturated carboxylic acids with alcohols with 12 to 30 carbon atoms in the alkyl radical; Esters of vinyl and / or allyl alcohol with 12 to 30 carbon atoms in the molecule having alkane monocarboxylic, sulfonic and / or phosphonic acids; Amides of 3 to 6 carbon atoms-containing alpha.beta-monoolefinically unsaturated carboxylic acids with alkylamines with 12 to 30 carbon atoms in the alkyl radical; Macromomers based on olefinically unsaturated compounds with an average of at least one, in particular terminal, olefinically unsaturated group in the molecule; Polysiloxane macromonomers with an average of at least one, in particular terminal, olefinically unsaturated group in the molecule; oligomeric and / or polymeric polymerization, polycondensation and / or polyaddition products; water-insoluble molecular weight regulators, especially mercaptans; aliphatic, cycloaliphatic and / or aromatic halogenated and / or non-halogenated hydrocarbons; Alkanols and / or alkylamines with at least 12 carbon atoms in the alkyl radical; Organosilanes and / or - siloxanes; vegetable, animal, semi-synthetic and / or synthetic oils; hydrophobic dyes. Further examples of suitable hydrophobic compounds or costabilizers and the amounts in which they are advantageously used are known from German patent application DE 196 28 142 A1, page 4, lines 37 to 59.
Vorzugsweise enthält die Mischung der wesentlichen Ausgangsverbindungen noch übliche und bekannte Zusatzstoffe,
insbesondere Lichtschutzmittel, wie UV-Absorber und reversible Radikalfänger (HALS), und Katalysatoren der Polyaddition, wie organische Dialkylzinnverbindungen, insbesondere Dibutylzinndilaurat, in üblichen und bekannten, wirksamen Mengen.The mixture of the essential starting compounds preferably also contains customary and known additives, in particular light stabilizers, such as UV absorbers and reversible radical scavengers (HALS), and catalysts of polyaddition, such as organic dialkyltin compounds, in particular dibutyltin dilaurate, in customary and known, effective amounts.
Vorzugsweise wird die Polyaddition bei einer Temperatur von 30 bis 150, bevorzugt 40 bis 120 und insbesondere 50 bis 100 °C durchgeführt. Bei Reaktionstemperaturen > 100 °C werden druckdichte Reaktoren angewandt. Beispiele geeigneter Reaktoren sind Rührkessel, Rohrreaktoren, Schleifenreaktoren oder Taylorreaktoren, insbesondere Rührkessel.The polyaddition is preferably carried out at a temperature of 30 to 150, preferably 40 to 120 and in particular 50 to 100 ° C. At reaction temperatures> 100 ° C, pressure-tight reactors are used. Examples of suitable reactors are stirred tanks, tubular reactors, loop reactors or Taylor reactors, in particular stirred tanks.
Als Ausgangsverbindungen (A), (B) und (C) können alle Verbindungen verwendet werden, wie sie üblicherweise für die Herstellung von Polyurethanen eingesetzt werden. Es ist ein außerordentlicher Vorteil der erfindungsgemäßen Primärdispersion und des erfindungsgemäßen Verfahrens, dass so zahlreiche und leicht zugängliche Verbindungen angewandt werden können.As starting compounds (A), (B) and (C), all compounds can be used as are usually used for the production of polyurethanes. It is an extraordinary advantage of the primary dispersion and the method according to the invention that so many and easily accessible compounds can be used.
So werden die Polyisocyanate (A) vorzugsweise aus der Gruppe, bestehend aus üblichen und bekannten aliphatischen, cycloaliphatischen, aromatischen, aliphatisch-cycloaliphatischen, aiiphatisch-aromatischen, cycloaliphatisch-aromatischen, aliphatisch-cycloaliphatisch-aromatischen Polyisocyanaten, bevorzugt aliphatischen, cycloaliphatischen und aliphatisch-cycloaliphatischen Polyisocyanaten, ausgewählt. Insbesondere handelt es sich bei den Polyisocyanaten (A) um Diisocyanate. Beispiele geeigneter Polyisocyanate (A) sind aus der deutschen Patentanmeldung DE 199 14 896 A 1, Spalte 4, Zeile 42, bis Spalte 5, Zeile 33, bekannt.Thus, the polyisocyanates (A) are preferably selected from the group consisting of customary and known aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aiiphatic-aromatic, cycloaliphatic-aromatic, aliphatic-cycloaliphatic-aromatic polyisocyanates, preferably aliphatic, cycloaliphatic and aliphatic-cyclic aliphatic Polyisocyanates. In particular, the polyisocyanates (A) are diisocyanates. Examples of suitable polyisocyanates (A) are known from German patent application DE 199 14 896 A1, column 4, line 42, to column 5, line 33.
Die Polyole (B) werden vorzugsweise aus der Gruppe, bestehend aus niedermolekularen Polyolen (B1) sowie oligomeren und polymeren
Polyolen (B2), insbesondere oligomeren und polymeren Polyolen (B2), ausgewählt. Vorzugsweise handelt es sich bei den Polyolen um Diole. Vorzugsweise weisen die niedermolekularen Polyole (B1) ein zahlenmittleres Molekulargewicht < 200 Dalton und die oligomeren und polymeren Polyole (B") ein zahlenmittleres Molekulargewicht > 200 Dalton auf. Bevorzugt ist das Molverhältnis von (B1) : (B2) > 1 : 10. Beispiele geeigneter Polyole (B) sind aus der deutschen Patentanmeldung DE 199 14 896 A 1, Spalte 5, Zeile 35, bis Spalte 8, Zeile 35 und Spalte 15, Zeilen 13 bis 46, bekannt. Ganz besonders bevorzugt werden die Polyester-Polyole (B2), insbesondere die aliphatischen, cycloaliphatischen und aliphatisch-cycloaliphatischen Polyester-Polyole (B2).The polyols (B) are preferably selected from the group consisting of low molecular weight polyols (B1) and oligomeric and polymeric Polyols (B2), in particular oligomeric and polymeric polyols (B2), selected. The polyols are preferably diols. The low molecular weight polyols (B1) preferably have a number average molecular weight <200 Daltons and the oligomeric and polymeric polyols (B ") have a number average molecular weight> 200 Daltons. The molar ratio of (B1): (B2)> 1:10 is preferred. Examples Suitable polyols (B) are known from German patent application DE 199 14 896 A1, column 5, line 35 to column 8, line 35 and column 15, lines 13 to 46. The polyester polyols (B2 ), especially the aliphatic, cycloaliphatic and aliphatic-cycloaliphatic polyester polyols (B2).
Auch die Verbindungen (C) sind üblich und bekannt. Vorzugsweise werden die in den reaktiven funktionellen Gruppen der Verbindungen (C) vorhandenen mit aktinischer Strahlung aktivierbaren Bindungen aus der Gruppe, bestehend aus Kohlenstoff-Wasserstoff-Einzelbindungen oder Kohlenstoff-Kohlenstoff-, Kohlenstoff-Sauerstoff-, Kohlenstoff-Stickstoff-, Kohlenstoff-Phosphor- oder Kohlenstoff-Silizium-Einzelbindungen oder - Doppelbindungen, ausgewählt. Insbesondere sind die Doppelbindungen Kohlenstoff-Kohlenstoff-Doppelbindungen („Doppelbindungen").The compounds (C) are also customary and known. The bonds which can be activated with actinic radiation in the reactive functional groups of the compounds (C) are preferably selected from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or - double bonds. In particular, the double bonds are carbon-carbon double bonds (“double bonds”).
Vorzugsweise liegen die Doppelbindungen in reaktiven funktionellen Gruppen, ausgewählt aus der Gruppe, bestehend aus (Meth)Acrylat-, Ethacrylat-, Crotonat-, Cinnamat-, Vinylether-, Vinylester-, Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-, Isopropenyl-, Allyl- oder Butenylgruppen; Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-, Isopropenyl-, Allyl- oder Butenylethergruppen oder Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-, Isopropenyl-, Allyl- oder Butenylestergruppen, vor. Insbesondere sind die reaktiven funktionellen Gruppen Acrylatgruppen.
Vorzugsweise werden die in den Verbindungen (C) vorhandenen isocyanatreaktiven funktionellen Gruppen aus der Gruppe, bestehend aus Hydroxylgruppen, Thiolgruppen sowie primären und sekundären Aminogruppen, ausgewählt. Insbesondere sind die isocyanatreaktiven funktionellen Gruppen Hydroxylgruppen.The double bonds are preferably in reactive functional groups selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl - or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups. In particular, the reactive functional groups are acrylate groups. The isocyanate-reactive functional groups present in the compounds (C) are preferably selected from the group consisting of hydroxyl groups, thiol groups and primary and secondary amino groups. In particular, the isocyanate-reactive functional groups are hydroxyl groups.
Besonders bevorzugt werden die Verbindungen (C) aus der Gruppe, bestehend aus Hydroxyalkyl- und Hydroxycycloalkylacrylaten, ausgewählt. Beispiele geeigneter Verbindungen (C) dieser Art sind 2-Hydroxyethyl-, 2- und 3- Hydroxypropyl- und 4-Hydroxybutylacrylat und Cyclohexandimethanolmonoacrylat.The compounds (C) are particularly preferably selected from the group consisting of hydroxyalkyl and hydroxycycloalkyl acrylates. Examples of suitable compounds (C) of this type are 2-hydroxyethyl, 2 and 3-hydroxypropyl and 4-hydroxybutyl acrylate and cyclohexanedimethanol monoacrylate.
Außer den vorstehend beschriebenen wesentlichen Ausgangsprodukten können noch Verbindungen (D) verwendet werden, die von den Verbindungen (B) und (C) verschieden sind und mindestens eine, bevorzugt mindestens zwei und insbesondere zwei der vorstehend beschriebenen isocyanatreaktiven funktionellen Gruppen enthalten. Die Verbindungen (D) können keine oder mindestens eine übliche und bekannte reaktive funktionelle Gruppe, die „mit sich selbst" und/oder auch noch mit anderen komplementären reaktiven funktionellen Gruppen als Isocyanatgruppen, Vernetzungsreaktionen eingehen kann, enthalten. Beispiele geeigneter Gruppen dieser Art sind Carboxylgruppen, Epoxidgruppen oder Alkoxymethylengruppen. Zusätzlich zu diesen Gruppen oder anstelle von diesen können die Verbindungen (D) mindestens eine hydrophile funktionelle Gruppe, ausgewählt aus der Gruppe, bestehend aus (potenziell) anionischen Gruppen, wie Carboxyl- oder Sulfonsäuregruppen, oder (potenziell) kationischen Gruppen, wie Aminogruppen, und nicht-ionischen hydrophilen funktionellen Gruppen, wie Polyalkylenoxidgruppen, insbesondere Polyethylenoxidgruppen, enthalten.
Beispiele geeigneter Verbindungen (D) sind aus der deutschen Patentanmeldung DE 199 14 896 A 1, Spalte 9, Zeilen 36 bis 67, bekannt.In addition to the essential starting products described above, it is also possible to use compounds (D) which are different from the compounds (B) and (C) and contain at least one, preferably at least two and in particular two of the isocyanate-reactive functional groups described above. The compounds (D) may contain no or at least one customary and known reactive functional group which can undergo crosslinking reactions “with itself” and / or also with complementary reactive functional groups other than isocyanate groups. Examples of suitable groups of this type are carboxyl groups In addition to or instead of these groups, the compounds (D) can contain at least one hydrophilic functional group selected from the group consisting of (potentially) anionic groups, such as carboxyl or sulfonic acid groups, or (potentially) cationic groups , such as amino groups, and non-ionic hydrophilic functional groups, such as polyalkylene oxide groups, in particular polyethylene oxide groups. Examples of suitable compounds (D) are known from German patent application DE 199 14 896 A1, column 9, lines 36 to 67.
Vorzugsweise werden die Verbindungen (D) bei dem erfindungsgemäßen Verfahren während der Polyaddition der wässrigen Phase zugesetzt. Werden beispielsweise Polyamine, insbesondere Diamine, (D) zugesetzt, können die in den Polymerpartikeln vorliegenden Polyurethane in dieser Weise kettenverlängert werden.In the process according to the invention, the compounds (D) are preferably added during the polyaddition of the aqueous phase. If, for example, polyamines, in particular diamines, (D) are added, the polyurethanes present in the polymer particles can be chain-extended in this way.
Vorzugsweise wird das Äquivalentverhältnis von freien Isocyanatgruppen in den Polyisocyanaten (A) zu der Summe der isocyanatreaktiven Gruppen in den Ausgangverbindungen (B) und (C) sowie gegebenenfalls (D) so gewählt, dass in den Polymerpartikeln keine freien Isocyanatgruppen mehr vorliegen. Bevorzugt ist daher das Äquivalentverhältnis < 1 , insbesondere < 0,9. Allerdings sollte das Äquivalentverhältnis nicht so klein gewählt werden, dass nach der Beendigung der Polyaddition noch freie Ausgangsverbindungen (B) und (C) sowie gegebenenfalls (D) vorliegen.The equivalent ratio of free isocyanate groups in the polyisocyanates (A) to the sum of the isocyanate-reactive groups in the starting compounds (B) and (C) and, if appropriate, (D) is preferably chosen such that there are no longer any free isocyanate groups in the polymer particles. The equivalent ratio is therefore preferably <1, in particular <0.9. However, the equivalent ratio should not be chosen so small that free starting compounds (B) and (C) and, if appropriate, (D) are still present after the polyaddition has ended.
In einer weiteren erfindungsgemäßen Ausführungsform werden die Polymerpartikel der erfindungsgemäßen Primärdispersion vor, während und/oder nach, insbesondere nach, der Polyaddition mit aktinischer Strahlung, insbesondere UV-Strahlung, bestrahlt. Dadurch wird das zahlenmittlere und massenmittlere Molekulargewicht der Polyurethane in den Polymerpartikeln erhöht. Die Bestrahlung kann auch solange durchgeführt werden, bis die Polymerpartikel teilweise oder vollständig vernetzt sind und als vernetzte Mikropartikel vorliegen. Die vernetzten Mikropartikel sind noch mit aktinischer Strahlung härtbar, wenn sie noch eine gewisse Anzahl der vorstehend beschriebenen reaktiven funktionellen Gruppen enthalten, die mit aktinischer Strahlung aktivierbar sind.
Die erfindungsgemäße Primärdispersion weist zahlreiche besonderer Vorteile auf. So ist sie im wesentlichen oder völlig frei von organischen Lösemitteln. »Im wesentlichen frei« bedeutet, dass der Lösemittelgehalt < 5, vorzugsweise < 2 und insbesondere < 1 Gew.-% ist. »Völlig frei« bedeutet, dass der Lösemittelgehalt unterhalb Nachweisgrenzen der üblichen und bekannten Verfahren zur Analyse organischer Lösemittel liegt.In a further embodiment according to the invention, the polymer particles of the primary dispersion according to the invention are irradiated with actinic radiation, in particular UV radiation, before, during and / or after, in particular after, the polyaddition. This increases the number average and mass average molecular weight of the polyurethanes in the polymer particles. The irradiation can also be carried out until the polymer particles are partially or completely crosslinked and are present as crosslinked microparticles. The crosslinked microparticles can still be hardened with actinic radiation if they still contain a certain number of the reactive functional groups described above which can be activated with actinic radiation. The primary dispersion according to the invention has numerous particular advantages. So it is essentially or completely free of organic solvents. “Essentially free” means that the solvent content is <5, preferably <2 and in particular <1% by weight. “Completely free” means that the solvent content is below the detection limits of the usual and known methods for analyzing organic solvents.
Die erfindungsgemäße Primärdispersion ist hervorragend als mit aktinischer Strahlung härtbarer Beschichtungsstoff und Klebstoff und mit aktinischer Strahlung härtbare Dichtungsmasse geeignet. Außerdem eignet sie sich hervorragend für die Herstellung von mit aktinischer Strahlung oder Dual-Cure-härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen, insbesondere Beschichtungsstoffen. Nicht zuletzt eignet sie sich hervorragend für die Herstellung von Folien und Formteilen, insbesondere optischen Formteilen.The primary dispersion according to the invention is outstandingly suitable as a coating material and adhesive curable with actinic radiation and as a sealing compound curable with actinic radiation. It is also ideal for the production of coating materials, adhesives and sealants, in particular coating materials, that can be hardened with actinic radiation or dual-cure. Last but not least, it is ideal for the production of films and molded parts, especially optical molded parts.
Die erfindungsgemäßen Beschichtungsstoffe können als Klarlacke zur Herstellung von Klarlackierungen, insbesondere in färb- und/oder effektgebenden Mehrschichtlackierungen, verwendet werden. Sie können aber auch als Füller oder färb- und/oder effektgebendeThe coating materials according to the invention can be used as clear lacquers for the production of clear lacquers, in particular in multi-layer lacquers which give color and / or effects. You can also use it as a filler or as a coloring and / or effect agent
Unidecklackierungen oder Basislackierungen verwendet werden. Zu diesem Zweck können ihnen übliche und bekannte farbgebende, optisch effektgebende, elektrisch leitfähige, magnetisch abschirmende, fluoreszierende, korrosionshemmende und/oder füllende Pigmente zugesetzt werden. Zur Herstellung von erfindungsgemäßen Dual-Cure-Solid color finishes or basecoats can be used. For this purpose, they can be mixed with customary and known pigments, optics, optically, electrically conductive, magnetically shielding, fluorescent, corrosion-inhibiting and / or filling pigments. For the production of dual-cure according to the invention
Beschichtungsstoffen können der erfindungsgemäßen Primärdispersion auch thermisch härtbare Primärdispersionen auf der Basis von Miniemulsionen, wie sie aus den Patentanmeldungen DE 199 59 927 A 1,
DE 199 59 928 A 1, DE 199 59 923 A 1 oder DE 100 05 819 A 1 bekannt sind, zugesetzt werden.The primary dispersion according to the invention can also be coated with thermally curable primary dispersions based on mini-emulsions, as described in patent applications DE 199 59 927 A1, DE 199 59 928 A1, DE 199 59 923 A1 or DE 100 05 819 A1 are known.
Die Herstellung der erfindungsgemäßen Beschichtungsstoffe erfordert keine methodischen Besonderheiten, sondern es können die üblichen und bekannten Vorrichtungen und Verfahren angewandt werden. Beispiele geeigneter Verfahren sind Spritzen, Rakeln, Streichen, Gießen, Tauchen, Träufeln oder Walzen. Bevorzugt werden Spritzapplikationsverfahren angewandt.The production of the coating materials according to the invention does not require any special features in terms of method, but rather the customary and known devices and methods can be used. Examples of suitable processes are spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used.
Die applizierten Beschichtungsstoffe werden, gegebenenfalls nach dem Ablüften und dem Trocknen, in üblicher und bekannter Weise mit aktinischer Strahlung oder thermisch und mit aktinischer Strahlung, insbesondere UV-Strahlung, gehärtet.The applied coating materials are cured with actinic radiation or thermally and with actinic radiation, in particular UV radiation, in a customary and known manner, if appropriate after flashing off and drying.
Vorzugsweise werden die pigmentierten Beschichtungsstoffe thermisch und mit aktinischer Strahlung und die nicht pigmentierten Beschichtungsstoffe mit aktinischer Strahlung gehärtet.The pigmented coating materials are preferably cured thermally and with actinic radiation and the unpigmented coating materials with actinic radiation.
Für die thermische Härtung können übliche und bekannte Vorrichtungen, wie Umluftöfen oder Heizstrahler, verwendet werden.Conventional and known devices such as convection ovens or radiant heaters can be used for thermal curing.
Für die Härtung mit aktinischer Strahlung können übliche und bekannte Lichtquellen, wie UV-Strahler, eingesetzt werden. Vorzugsweise wird bei der Härtung mit aktinischer Strahlung eine Strahlendosis von 103 bis 4x104, vorzugsweise 2x103 bis 3x104, bevorzugt 3x103 bis 2,5x104 und insbesondere 5x103 bis 2x104 Jm"2 eingesetzt. Dabei liegt die Strahlenintensität bei 1x10° bis 3x105, vorzugsweise 2x10° bis 2x105, bevorzugt 3x10° bis 1,5x105 und insbesondere 5x10° bis 1,2x105 Wm"2.
Bevorzugt wird die Härtung mit aktinischer Strahlung unter einer sauerstoffabgereicherten Atmosphäre durchgeführt.Conventional and known light sources, such as UV lamps, can be used for curing with actinic radiation. A radiation dose of 10 3 to 4x10 4 , preferably 2x10 3 to 3x10 4 , preferably 3x10 3 to 2.5x10 4 and in particular 5x10 3 to 2x10 4 Jm "2 is preferably used for curing with actinic radiation. The radiation intensity is 1x10 ° to 3x10 5 , preferably 2x10 ° to 2x10 5 , preferably 3x10 ° to 1.5x10 5 and in particular 5x10 ° to 1.2x10 5 Wm "2 . Curing with actinic radiation is preferably carried out under an oxygen-depleted atmosphere.
Die resultierenden erfindungsgemäßen Beschichtungen haben hervorragende anwendungstechnische Eigenschaften. Sie sind glatt und frei von Oberflächenstörungen, hochglänzend, brillant, hart, flexibel, kratzfest, chemikalienbeständig, wasserbeständig und witterungsbeständig. Sie haften fest auf beschichteten und unbeschichteten Substraten aus Holz, Metall, Glas, Leder, Kunststoffen, Keramik, Naturstein, Kunststein oder Papier sowie Verbunden dieser Materialien.The resulting coatings according to the invention have excellent performance properties. They are smooth and free from surface defects, high-gloss, brilliant, hard, flexible, scratch-resistant, chemical-resistant, water-resistant and weather-resistant. They adhere firmly to coated and uncoated substrates made of wood, metal, glass, leather, plastics, ceramics, natural stone, artificial stone or paper as well as composites of these materials.
Die erfindungsgemäßen Klebschichten haben auch unter extremen Bedingungen eine dauerhaft hohe Klebkraft. Die erfindungsgemäßen Dichtungen dichten Substrate der vorstehend genannten Art dauerhaft auch gegen aggressive Stoffe ab. Die erfindungsgemäßen Folien von Formteilen weisen ein Eigenschaftsprofil auf, dass demjenigen der erfindungsgemäßen Beschichtungen in vollem Umfang entspricht.The adhesive layers according to the invention have a permanently high adhesive strength even under extreme conditions. The seals according to the invention permanently seal substrates of the type mentioned above, even against aggressive substances. The films of molded parts according to the invention have a profile of properties that corresponds fully to that of the coatings according to the invention.
Beispielexample
Die Herstellung einer mit UV-Strahlung härtbaren, wässrigen PrimärdispersionThe preparation of an aqueous primary dispersion curable with UV radiation
In einem Edelstahlreaktor wurdenIn a stainless steel reactor
12,33 Gewichtsteile Tetramethylxylylidendiisocyanat (TMXDI ® der Firma CYTEC),12.33 parts by weight of tetramethylxylylidene diisocyanate (TMXDI ® from CYTEC),
- 0,545 Gewichtsteiie Irgacure ® 184 (handelsüblicher- 0.545 parts by weight Irgacure ® 184 (commercially available
Fotoinitiator),
0,44 Gewichtsteile Tinuvin ® 400 (handelsüblicher UV-Absorber der Firma Ciba Specialty Chemicals, 85prozentig in Methoxy-2- propanol),Photoinitiator) 0.44 parts by weight of Tinuvin ® 400 (commercially available UV absorber from Ciba Specialty Chemicals, 85 percent in methoxy-2-propanol),
0,364 Tinuvin ® 292 (handelsüblicher UV-Absorber der Firma Ciba Specialty Chemicals),0.364 Tinuvin ® 292 (commercially available UV absorber from Ciba Specialty Chemicals),
0,182 Gewichtsteile 4-Hydroxyl-2,2,6,6-tetramethylpiperidin-1-oxyl (HALS),0.182 parts by weight of 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxyl (HALS),
18,28 Gewichtsteile eines Polyesters aus, bezogen auf den Polyester, 41 ,906 Gew.-% Hexahydrophthalsäureanhydrid, 13,951 Gew.-% Hexandiol und 44,144 Gew.-% Ethylbutylpropandiol; Kennzahlen: Hydroxylzahl: 153,7 mg18.28 parts by weight of a polyester, based on the polyester, 41.906% by weight of hexahydrophthalic anhydride, 13.951% by weight of hexanediol and 44.144% by weight of ethylbutylpropane diol; Key figures: Hydroxyl number: 153.7 mg
KOH/g; Säurezahl: 10,7 mg KOH/g; zahlenmittleres Molekulargewicht 682 Dalton,KOH / g; Acid number: 10.7 mg KOH / g; number average molecular weight 682 daltons,
7,27 Gewichtsteile Hydroxybutylacrylat und7.27 parts by weight of hydroxybutyl acrylate and
0,018 Gewichtsteile Dibutylzinndilaurat0.018 parts by weight of dibutyltin dilaurate
eingewogen, miteinander vermischt und homogenisiert.weighed, mixed and homogenized.
In einem separaten Behälter wurden 55,207 Gewichtsteile deionisiertes Wasser, 5,106 Gewichtsteile des handelsüblichen Emulgators Abex® EP 110 der Firma Rhone Poulenc Surfactants & Specialties und 0,159 Gewichtsteile des handelsüblichen Entschäumers Agitan ® 281 miteinander vermischt und homogenisiert.
Die wässrige Emulgator-Entschäumer-Lösung wurde unter Rühren zu der organischen Mischung hinzugegeben. Die resultierende Mischung wurde mit einem Ultraturrax der 30 Sekunden bei 10.000 U/min homogenisiert. Die resultierende Suspensionen wurde anschließend durch δminütiges Dispergieren mittels eines Düsenstrahlhomogenisators der Firma Wagner bei einem Druck von 180 bar in eine Miniemulsion (z-mittlere Teilchengröße: 200 nm; gemessen mit einem PCS Malvern Zetasizer 1000) überführt. Die Miniemulsion wurde solange bei 80 °C gerührt, bis der theoretische Festkörpergehalt von 40 Gew.-% erreicht war.55.207 parts by weight of deionized water, 5.106 parts by weight of the commercially available emulsifier Abex® EP 110 from Rhone Poulenc Surfactants & Specialties and 0.159 parts by weight of the commercially available defoamer Agitan® 281 were mixed and homogenized in a separate container. The aqueous emulsifier-defoamer solution was added to the organic mixture with stirring. The resulting mixture was homogenized with an Ultraturrax at 10,000 rpm for 30 seconds. The resulting suspensions were then converted into a miniemulsion (z-average particle size: 200 nm; measured with a PCS Malvern Zetasizer 1000) by δ-minute dispersion using a Wagner jet homogenizer at a pressure of 180 bar. The mini emulsion was stirred at 80 ° C. until the theoretical solids content of 40% by weight was reached.
Die Miniemulsion oder Primärdispersion war lagerstabil. Sie konnte als solche als UV-härtbarer Beschichtungsstoff und Klebstoff sowie als UV- härtbare Dichtungsmasse verwendet werden. Als Beschichtungsstoff lieferte sie nach der Applikation auf Substrate harte, kratzfeste, flexible, chemikalienbeständige und witterungsbeständige Klarlackierungen. Sie konnte aber auch zur Herstellung von thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen verwendet werden. Zu diesem Zweck wurde die Miniemulsion mit üblichen und bekannten Dispersionen von thermisch härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen vermischt. Wegen ihrer vorteilhaften Eigenschaften konnte die Miniemulsion auch sehr gut für die Herstellung von Folien, insbesondere Lackfolien, und Formteilen verwendet werden. Da die Miniemulsion im wesentlichen von organischen Lösemitteln frei war, mussten bei ihrer Herstellung, Applikationen und Härtung keine besonderen Sicherheitsmaßnahmen, wie die Absaugung flüchtiger organischen Lösemittel oder die Ableitung statischer Elektrizität, getroffen werden.
The mini emulsion or primary dispersion was stable on storage. As such, it could be used as a UV-curable coating material and adhesive and as a UV-curable sealant. As a coating material, it delivered hard, scratch-resistant, flexible, chemical-resistant and weather-resistant clear coats after application to substrates. However, it could also be used for the production of coating materials, adhesives and sealing compounds which are curable thermally and with actinic radiation. For this purpose, the mini emulsion was mixed with conventional and known dispersions of thermally curable coating materials, adhesives and sealants. Because of its advantageous properties, the mini emulsion could also be used very well for the production of foils, in particular lacquer foils, and molded parts. Since the miniemulsion was essentially free of organic solvents, no special safety measures, such as the extraction of volatile organic solvents or the dissipation of static electricity, had to be taken in its manufacture, applications and curing.
Claims
1. Mit aktinischer Strahlung härtbare, wässrige Primärdispersion, enthaltend flüssige und/oder feste, emulgierte und/oder dispergierte Polymerpartikel eines z-mittleren Teilchendurchmessers < 500 nm, herstellbar durch Polyaddition in einer Mikro- und/oder Miniemulsion von zumindest1. Aqueous primary dispersion curable with actinic radiation, comprising liquid and / or solid, emulsified and / or dispersed polymer particles of a z-average particle diameter <500 nm, producible by polyaddition in a micro- and / or miniemulsion of at least
(A) mindestens einem Polyisocyanat,(A) at least one polyisocyanate,
(B) mindestens einem Polyol und(B) at least one polyol and
(C) mindestens einer Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe und mit mindestens einer reaktiven funktionellen Gruppe, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung.(C) at least one compound with at least one isocyanate-reactive functional group and with at least one reactive functional group containing at least one bond which can be activated with actinic radiation.
2. Primärdispersion nach Anspruch 1, dadurch gekennzeichnet, dass sie einen z-mittleren Teilchendurchmesser > 50 nm aufweist.2. Primary dispersion according to claim 1, characterized in that it has a z-average particle diameter> 50 nm.
3. Primärdispersion nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie einen z-mittleren Teilchendurchmesser < 400 nm aufweist.3. Primary dispersion according to claim 1 or 2, characterized in that it has a z-average particle diameter <400 nm.
4. Primärdispersion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie einen z-mittleren Teilchendurchmesser von 100 bis 350 nm aufweist.4. Primary dispersion according to one of claims 1 to 3, characterized in that it has a z-average particle diameter of 100 to 350 nm.
5. Primärdispersion nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Polyisocyanate (A) Diisocyanate sind. 5. Primary dispersion according to one of claims 1 to 4, characterized in that the polyisocyanates (A) are diisocyanates.
6. Primärdispersion nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Polyisocyanate (A) aus der Gruppe, bestehend aus aliphatischen, cycloaliphatischen, aromatischen, aliphatisch-cycloaliphatischen, aliphatisch-aromatischen, cycloaliphatisch-aromatischen, aliphatisch-cycloaliphatisch- aromatischen Polyisocyanaten, ausgewählt werden.6. Primary dispersion according to one of claims 1 to 5, characterized in that the polyisocyanates (A) from the group consisting of aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aliphatic-aromatic, cycloaliphatic-aromatic, aliphatic-cycloaliphatic-aromatic polyisocyanates , to be selected.
7. Primärdispersion nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Polyole (B) aus der Gruppe, bestehend aus niedermolekularen Polyolen (B1) sowie oligomeren und polymeren Polyolen (B2), ausgewählt sind.7. Primary dispersion according to one of claims 1 to 6, characterized in that the polyols (B) are selected from the group consisting of low molecular weight polyols (B1) and oligomeric and polymeric polyols (B2).
8. Primärdispersion nach Anspruch 7, dadurch gekennzeichnet, dass die niedermolekularen Polyole (B1) ein zahlenmittleres Molekulargewicht < 200 Dalton und die oligomeren und polymeren8. Primary dispersion according to claim 7, characterized in that the low molecular weight polyols (B1) have a number average molecular weight <200 Daltons and the oligomeric and polymeric
Polyole (B2) ein zahlenmittleres Molekulargewicht > 200 haben.Polyols (B2) have a number average molecular weight> 200.
9. Primärdispersion nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Molverhältnis von (B1) : (B2) > 1 : 10 ist.9. Primary dispersion according to claim 7 or 8, characterized in that the molar ratio of (B1): (B2)> 1:10.
10. Primärdispersion nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass die Polyole (B2) Polyester-Polyole sind.10. Primary dispersion according to one of claims 7 to 9, characterized in that the polyols (B2) are polyester polyols.
11 Primärdispersion nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die in den reaktiven funktionellen Gruppen der Verbindungen (C) vorhandenen mit aktinischer Strahlung aktivierbaren Bindungen aus der Gruppe, bestehend aus aus Kohlenstoff-Wasserstoff-Einzelbindungen oder Kohlenstoff- Kohlenstoff-, Kohlenstoff-Sauerstoff-, Kohlenstoff-Stickstoff-, Kohlenstoff-Phosphor- oder Kohlenstoff-Silizium-Einzelbindungen oder -Doppelbindungen, ausgewählt sind. 11 primary dispersion according to one of claims 1 to 10, characterized in that the bonds present in the reactive functional groups of the compounds (C) can be activated with actinic radiation from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon -Oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds are selected.
12. Primärdispersion nach Anspruch 11 , dadurch gekennzeichnet, dass die Doppelbindungen Kohlenstoff-Kohlenstoff-Doppelbindungen („Doppelbindungen") sind.12. Primary dispersion according to claim 11, characterized in that the double bonds are carbon-carbon double bonds ("double bonds").
13. Primärdispersion nach Anspruch 12, dadurch gekennzeichnet, dass die Doppelbindungen in reaktiven funktionellen Gruppen, ausgewählt aus der Gruppe, bestehend aus (Meth)Acrylat-, Ethacrylat-, Crotonat-, Cinnamat-, Vinylether-, Vinylester-, Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-, Isopropenyl-, Allyl- oder Butenylgruppen; Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-13. Primary dispersion according to claim 12, characterized in that the double bonds in reactive functional groups selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl -, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl
Isopropenyl-, Allyl- oder Butenylethergruppen oderIsopropenyl, allyl or butenyl ether groups or
Dicyclopentadienyl-, Norbornenyl-, Isoprenyl-, Isopropenyl-, Allyl- oder Butenylestergruppen, vorliegen.Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups are present.
14. Primärdispersion nach Anspruch 13, dadurch gekennzeichnet, dass die reaktiven funktionellen Gruppen Acrylatgruppen sind.14. Primary dispersion according to claim 13, characterized in that the reactive functional groups are acrylate groups.
15. Primärdispersion nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass die in den Verbindungen (C) vorhandenen isocyanatreaktiven funktionellen Gruppen aus der Gruppe, bestehend aus Hydroxylgruppen, Thiolgruppen sowie primären und sekundären Aminogruppen, ausgewählt sind.15. Primary dispersion according to one of claims 1 to 14, characterized in that the isocyanate-reactive functional groups present in the compounds (C) are selected from the group consisting of hydroxyl groups, thiol groups and primary and secondary amino groups.
16. Primärdispersion nach Anspruch 15, dadurch gekennzeichnet, dass die isocyanatreaktiven funktionellen Gruppen Hydroxylgruppen sind.16. Primary dispersion according to claim 15, characterized in that the isocyanate-reactive functional groups are hydroxyl groups.
17. Primärdispersion nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass die Verbindungen (C) aus der Gruppe, bestehend aus Hydroxyalkyl- und Hydroxycycloalkylacrylaten, ausgewählt sind.17. Primary dispersion according to one of claims 14 to 16, characterized in that the compounds (C) from the group, consisting of hydroxyalkyl and hydroxycycloalkyl acrylates are selected.
18. Primärdispersion nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass ihre Polymerpartikel unter Verwendung von18. Primary dispersion according to one of claims 1 to 17, characterized in that its polymer particles using
(D) mindestens einer von (B) und (C) verschiedenen Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe(D) at least one compound different from (B) and (C) with at least one isocyanate-reactive functional group
herstellbar sind.are producible.
19. Primärdispersion nach Anspruch 18, dadurch gekennzeichnet, dass die in den Verbindungen (D) vorhandenen isocyanatreaktiven funktionellen Gruppen aus der Gruppe, bestehend aus19. Primary dispersion according to claim 18, characterized in that the isocyanate-reactive functional groups present in the compounds (D) from the group consisting of
Hydroxylgruppen, Thiolgruppen sowie primären und sekundären Aminogruppen, ausgewählt sind.Hydroxyl groups, thiol groups and primary and secondary amino groups are selected.
20. Primärdispersiόn nach Anspruch 18 oder 19, dadurch gekennzeichnet, dass die Verbindungen (D) keine oder mindestens eine funktionelle Gruppe, ausgewählt aus der Gruppe, bestehend aus reaktiven funktionellen Gruppen, die „mit sich selbst" und/oder mit komplementären reaktiven funktionellen Gruppen Reaktionen eingehen können, sowie hydrophilen funktionellen Gruppen, enthalten.20. Primary dispersion according to claim 18 or 19, characterized in that the compounds (D) have no or at least one functional group selected from the group consisting of reactive functional groups which are “with themselves” and / or with complementary reactive functional groups May react, as well as contain hydrophilic functional groups.
21. Primärdispersion nach Anspruch 20, dadurch gekennzeichnet, dass die hydrophilen funktionellen Gruppen aus der Gruppe, bestehend aus (potenziell) anionischen oder (potenziell) kationischen Gruppen und nicht-ionischen hydrophilen funktionellen Gruppen, ausgewählt sind. 21. The primary dispersion as claimed in claim 20, characterized in that the hydrophilic functional groups are selected from the group consisting of (potentially) anionic or (potentially) cationic groups and non-ionic hydrophilic functional groups.
22. Primärdispersion nach einem der Ansprüche 18 bis 21, dadurch gekennzeichnet, dass sie durch Zugabe mindestens einer Verbindung (D) während der Polyaddition zur wässrigen Phase herstellbar ist.22. Primary dispersion according to one of claims 18 to 21, characterized in that it can be prepared by adding at least one compound (D) during the polyaddition to the aqueous phase.
23. Primärdispersion nach einem der Ansprüche 1 bis 22, dadurch gekennzeichnet, dass sie durch -Bestrahlen der Polymerpartikel mit aktinischer Strahlung vor, während und/oder nach der Polyaddition herstellbar ist23. Primary dispersion according to one of claims 1 to 22, characterized in that it can be prepared by irradiating the polymer particles with actinic radiation before, during and / or after the polyaddition
24. Primärdispersion nach einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, dass sie einen Festkörpergehalt von 5 bis 70 Gew.-% hat.24. Primary dispersion according to one of claims 1 to 23, characterized in that it has a solids content of 5 to 70 wt .-%.
25. Verfahren zur Herstellung von mit aktinischer Strahlung härtbaren, wässrigen Primärdispersionen gemäß einem der Ansprüche 1 bis 24, enthaltend flüssige und/oder feste, emulgierte und/oder dispergierte Polymerpartikel eines z-mittleren Teilchendurchmessers < 500 nm, dadurch gekennzeichnet, dass man25. A process for the preparation of aqueous primary dispersions curable with actinic radiation according to one of claims 1 to 24, comprising liquid and / or solid, emulsified and / or dispersed polymer particles having a z-average particle diameter <500 nm, characterized in that
(1) eine Mikro- oder Miniemuision aus zumindest(1) a micro or mini mision from at least
(A) mindestens einem Polyisocyanat,(A) at least one polyisocyanate,
(B) mindestens einem Polyol und(B) at least one polyol and
(C) mindestens einer Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe und mit mindestens einer reaktiven funktionellen Gruppe, enthaltend mindestens eine mit aktinischer Strahlung aktivierbare Bindung,(C) at least one compound with at least one isocyanate-reactive functional group and with at least one reactive functional group, containing at least one bond that can be activated with actinic radiation,
herstellt undmanufactures and
(2) durch Polyaddition polymerisiert.(2) polymerized by polyaddition.
26. Verfahren nach Anspruch 25, dadurch gekennzeichnet, dass man die Mikro- oder Miniemuision unter Verwendung von26. The method according to claim 25, characterized in that using the micro or mini muition
(D) mindestens einer von (B) und (C) verschiedenen Verbindung mit mindestens einer isocyanatreaktiven funktionellen Gruppe(D) at least one compound different from (B) and (C) with at least one isocyanate-reactive functional group
herstellt.manufactures.
27. Verfahren nach Anspruch 26, dadurch gekennzeichnet, dass die Verbindung (D) während der Polyaddition der wässrigen Phase zugesetzt wird.27. The method according to claim 26, characterized in that the compound (D) is added during the polyaddition of the aqueous phase.
28. Verfahren nach einem der Ansprüche 25 bis 27, dadurch gekennzeichnet, dass die Mini- oder Mikroemulsion vor, während und/oder nach der Polyaddition mit aktinischer Strahlung bestrahlt wird.28. The method according to any one of claims 25 to 27, characterized in that the mini or micro emulsion is irradiated with actinic radiation before, during and / or after the polyaddition.
29. Verfahren nach einem der Ansprüche 25 bis 28, dadurch gekennzeichnet, dass die Polyaddition bei einer Temperatur von 30 bis 150 °C durchgeführt wird.29. The method according to any one of claims 25 to 28, characterized in that the polyaddition is carried out at a temperature of 30 to 150 ° C.
30. Verwendung der Primärdispersionen gemäß einem der Ansprüche 1 bis 24 und der nach dem Verfahren gemäß einem der Ansprüche 25 oder 29 hergestellten Primärdispersionen als mit aktinischer Strahlung härtbare Beschichtungsstoffe, Klebstoffe und Dichtungsmassen, zur Herstellung von mit aktinischer Strahlung und thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen und zur Herstellung von Folien und Formteilen. 30. Use of the primary dispersions according to one of claims 1 to 24 and according to the method according to one of the claims 25 or 29 primary dispersions prepared as coating materials, adhesives and sealants curable with actinic radiation, for the production of coating materials, adhesives and sealants curable with actinic radiation and thermally and with actinic radiation and for the production of films and moldings.
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DE10213970 | 2002-03-28 | ||
PCT/EP2003/002853 WO2003083004A1 (en) | 2002-03-28 | 2003-03-19 | Primary aqueous dispersion hardened by actinic radiation, method for production and use thereof |
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DE10106567A1 (en) * | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Aqueous primary dispersion essentially or completely free of volatile organic substances, process for their preparation and their use |
DE10322266A1 (en) * | 2003-05-16 | 2004-12-02 | Basf Ag | Self-emulsifying aqueous polyurethane dispersion |
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- 2002-03-28 DE DE10213970A patent/DE10213970A1/en not_active Ceased
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2003
- 2003-03-19 US US10/505,538 patent/US20050124757A1/en not_active Abandoned
- 2003-03-19 EP EP03712053A patent/EP1487933A1/en not_active Withdrawn
- 2003-03-19 WO PCT/EP2003/002853 patent/WO2003083004A1/en not_active Application Discontinuation
- 2003-03-19 AU AU2003218791A patent/AU2003218791A1/en not_active Abandoned
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CN107964375A (en) * | 2016-10-19 | 2018-04-27 | 迪睿合株式会社 | The manufacture method of connector |
Also Published As
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DE10213970A1 (en) | 2003-10-23 |
AU2003218791A1 (en) | 2003-10-13 |
US20050124757A1 (en) | 2005-06-09 |
WO2003083004A1 (en) | 2003-10-09 |
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