BE717432A - - Google Patents

Description

  

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  Brooô ± 6 of fabriaa-ëion da filma, leaves ,, wires ot ar lii- cles with large surface.
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  1 & aiJ i, Jti.é = in plastics d0 (Il -ùoaz #> Jii les: àats> ù: # "es c ii, Lù, aj, ùos M iozpoaéJ po3, yhyù? Rzyàé /: qui úotio0nt des cmoupoeni; fl oat ;?> rio -0 ty.lF, q> go are à.ljà eonn-eso cnvot Stinai that the 'broTets 6iQGin n 2.933.473, 2' 2.933.477 nq 3.051.687 n 3w &. <, 0> 730 ot No. 2,333,639 describes the preparation of poJ, yiwéthe.ne 3 pro.venan% polyoondenssts proson both hydroxyl groups .. which have been prepared by polycondonzation of lactones having at least 4 carbon atonies in the nucleus, or by copolyondensation of the genus of lactones with polyols, polyamines and aminoaloools According to the methods described in German Patent No. 1,109,881 and United States Patents No. 2.

   962.455 and No. 2.990.379, are prepared from polyhydroxy compounds containing hydro- ester groups

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 EMI2.1
 alcoyiao'-sarboxyliquo ôV0ntel1cu0nt alcyl-eubotitu6 collulaireo The n6arlandi6 patent No. 6,610,501.3 describes the use of disveroionc, enuluionot "sp'enDion #, colmions and presnuo anhydrous gels of diicooynotolacnocnatoo diicooynotolocnatoo in organic solvants ùpolynotola16natoo as a binder and as an osduct for materials in toieona, As however, the organic solvents used for co-process are intlammablos, of composition forming of solvents and the lino: tion of the solvents represent a coniue complioatioa on the operation with the use of the materials plana -% 5> qt.ç- pelytaotose-polyrëthanat The use of formulationa lion 9osbu.stibloa do! J () l:

  lle \ C "1a ,,,! jol3" 'J! olJru.I'Gthne' for C.1! D: ';, QC :: l.CM: ;;: fseqhn-gt; e> ;, tcàr . osempio POUl 'the manufacture ûa 1: 1.c # a.h, i D.J1J: fleeces o <1 endiii% o quo àea 00l, l), 0l10f.



  0 \ 0 <;;; ri; .oaiùuio - * n na # J.ôrv plastAques op; z? Oaponù denc! A3 'tachnic boscia preùsaat. Des maii; ièron plastiquas de yo], jm, i? Ô'ihano i d == '- ivmn.1 of component polj- hyàroxylài xivoo 1 ## oiiDc <Jn.Yo oste? "d'osyeleoylaf3-eas'bo:! yliquet yes J> n% Li.; 1a: f? t: tl '] .o lo.te: 11Q.1.:1em pr, 1.00 on foFEie no séµ2" 1 oe.s oseorci <jlionàns É> 1-'haia% o oc'ëu.olle.



  J1; ozo = ntn'J; oc;!:! U '), 1; o:' '1 -7: li # ;? ào ti6co>; 11 - # ;: lzm eo as z> im> 1; make dec foillos ± fl.l:.: # iq wires and ar'ëicles 1.



  {1To.n ;; 1 () rrwfaeo r:,: i.11i que dos m: H1t1: t-to des'- iaiprss'a'ëionsg ùea eouchco S, nt = 1Jé <1: 1-t.: M1 # o% of oollagep with à, 'exoel3Le; tos w <oppi <jt6a ù'izydroJ, irz ei; aging ot au-ssi tino great flexibility ei éj,? z "tiqij.Éô as well as qt \ 1 aV00 des rG3it: J.nocs f), the traotioa ot daa! ve.lou.rB de atruoturo Qtaarquably good, lorzqttlon occD "o aqucus latos of polyxrethanes for the manufacture of which has been used
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 es
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 as polyhydroxylated compounds of polylacton7ou that one elicinates for example water by evaporation optionally at t ± r: 95ratu; e high and optionally in the presence of known agents.

   Polylactones used .mme

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 EMI3.1
 Polyhydroxy compounds are characterized in that they contain one or more or a series of optionally alkyl-substituted hydroxyalkylene-carboxylic carboxylic groups having 448 carbon atoms in the alkylene chain. In this case, the poly-C-hydroxy-caprolaotona is particularly taken into consideration.



   Textile finishes, coatings? and the polylactone-polyurethane impregnations prepared by the use
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 or the joint use of A r ''.: - s & ve) only alkyl-substituted have a warm, supple and pleasant feel; they are distinguished by outstanding water resistance and solvent resistance.



   The object of the invention is therefore a process for the preparation of sheets, films, threads and articles with a large surface area, including coatings, impregnations, intermediate layers and bondings by shaping.
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 polyurethane latex prepared in a manner known per se by the polyaddition process z the iaoyanate from polyhydroxy compounds having a molecular weight of 300 to 10,0009 of polyisocyanates and optionally from chain extenders used together, by co-gulation or elimination of the water by evaporation, optionally at high temperature and optionally in the presence of known crosslinking agents,

     characterized in that polyurethane texes are used for the preparation
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 tion of which were used as polyhydroxyl compounds those which contain one or more or a series of groups
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 hydroxyalkylene-oarboxylic ester pements optionally; alkyl-substituted having 4 h 8 carbon atoms in the alkylene chain. The products of the process therefore contain structural units of formula -0-R-C00 in which R represents an alooyl residue, possibly alooyl-substituted having 4 to 8 carbon atoms.

   In the products of the process prepared from

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 de.polylaotones, polylaooyanatee, chain extenders and optionally other polyhydroxy compounds to be used together having a molecular weight of 300 to 10,000, the proportions of the constituents can vary within wide limits depending on the need. preparing flexible, flexible or elastic or very hard thermoplastic plastics.

   A preferred embodiment consists in employing as polyurethane latex those for the preparation of which mixtures of polyhydroxy compounds have been used which consist in an amount of at least 10% of polyhydroxy compounds containing
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 optionally aloyl-substituted hydroxyalkylene-oarboxylic ester groups having 4 to 8 carbon atoms
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 in the aloy7ene chain.



   In accordance with the invention, use is made of polyhydroxy compounds having one or more or a series of groups.
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 Optionally α7Lcoy1-substituted hydroxyalkylene-carboxylic ester pements having 4 to 8 carbon atoms in the alkyl chain, which have a molecular weight between 300 and 10,000, preferably from 600 to 3000. The preparation of these compounds is for example described in the
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 American patents n ° 2,914,556, nO2333-639, n 2,878,236, n 2,890,208 and in German patent n 1,247,019, as well as in French patent n 1,174,207. Polylactones suitable for the process, which are modified by epoxies, are listed in US Patent No. 2,962,524.

   Other suitable polylaotones are described in U.S. Patent No. 3,186,971. The preparation of polyhydroxylea compounds having one or more or one
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 series of hydroxyalkylene carboxylic ester groups optionally alkyl-oubatitud having 4 to 8 atoms of oar.- bone in the aloyiene chain is made by polycondensation of glyools, polyamines and aminoa1oools as the starting moléoulo with lactones which contain 4 to 8 atoms

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 of carbon in the laotoas nucleus such as E-oaprolactono, 3.'oatyl-.aaprolaotono, lu-dimethyl-6-oaprolaotone, trimethyl- -caprolaotona # ethyl-e-0aprolacton and methyl-.uthyl - & - 'oaprolaotono , prop3,.-oaprolaatone and their mixtures isombrec,

   in the presence of the catalyst, only dialkyltin oxides, sine borate, calcium methoxide, a
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 alkyl titanate, lead oxide, etc.



  As polyhydroxy compounds considered oonfermdment with the invention, preferably considered the polvhydroxyoaprolaotones optionally alooyl-subs% ita6oJ.



  According to the invention, use is made of aqueous dispersions of polyurethanes having dry matter contents generally between 10 and 60%, which may also contain incorporated salt groups).



  Examples for the preparation of dispersions of uses
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 polyurethaïlea in the preparation of which are used or / jointly according to the invention polyhydroxy- compounds having uster hydroxyoarboxyliqua groups are found in German Patents No. 1,097,678, No. 1,187,012, No. 1,184,946, No. 1,178,586, n 1,179,363 and Belgian patents n 653,223, n 658,026, British patent n 883,568, French patent n 1,108,785,
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 in Polymer Reprints 6 (1965), n 1, p. 156 to 162, in Belgian patents n 688.299, n 669.954, n 673,432, n 639. 107 and n 691,354, in Dutch patents n 6,612,430, n 6,614,585 and in the patent
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 American No. 3.178.'310.



   In the preparation of the aqueous dispersions of polylotone polyurethane to be used according to the invention, in general, first of all, polyhydroxy compounds with reactive hydrogen atoms having
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 a molecular weight of 300 to 10,000.

   ., = .lyisacyairtec and optionally chain extenders to

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   use, a pre-product oontonant of isocyanato groups and it is dispersed in organic solution, optionally there is the presence of emulsifier and agents for extending the bansic chain, in water, or, conversely, it is added to water containing emulsifiers with formation of a dispersion and the organic solvent removed if necessary.



   In accordance with the invention, dispersions prepared without emulsifiers are particularly suitable, in this case dispersions without emulsifier of anionic polylactones-polyurethanes with salt groups which are preferred.



   In the preparation of dispersions of anionic and cationic polylactonespolyurethanes containing salt gnoups. the salt groups of which are defined according to the teachings of Belgian Patent No. 653,223 and of which the content of salt groups can vary from 0.05 to 10% by weight, preferably from 0.1 to 3% by weight relative to the mass of polyurethane, the pre-product containing isocyanate groups can be reacted in organic solution with a salt-like constituent or capable of forming a salt and added to water optionally after conversion of the groups capable of forming a salt into the salt form , then the organic solvent is removed by distillation.

   In principle, it is also possible to proceed in reverse by putting in advance the water which optionally contains the constituent salt type or the counter-constituent necessary for the formation of salt, then by diluting the pre-product containing isocyanate groups or the polyurethane with groups capable of salification.



   Saline or salifying constituents suitable for incorporation are, for example, taurine, methyltaurine, tartaric acid, glycine, lysine, 6-aminocaproic acid, diaminobeneoic acid, hydrazine acid.
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 riita9fnr, inv, a o-.4 a i4 - <-..- A-- ## j <-. j-

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 of unsaturated acids and sultones on aliphatic or aromatic diamines, triamines, diaminoaloools or aminodiols, in addition to hydrogenated adducts of unsaturated nitriles such as aorylonitrile on amino acids such as glycine or taurine, or their salts, as well as methyldiethanolamine, n-butyldiisopropanolamine, 1,3-amino-
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 N, N-dimethylaminopropane or bis- (N, N- -aminopropyl)

  -metylamine.



   Examples of salt-forming counter-constituents which react with the groups capable of forming a salt with the formation of salt are likewise contained in Belgian Patent No. 653,223.



   For the preparation of polylaotone polyurethane dispersions, for example high molecular weight polylaotone polyurethanes can subsequently be reacted with substances which give the polyurethane mass a saline character, for example with sultans, laotones, cyclic sulphates or anhydrides of dioarboxylic aids. In a particular embodiment, the groups capable of forming a salt are only partially converted to the salt form, hence. there are still free groups not transformed into the salt form.

   By the proportion of free groups, for example acidic vis-à-vis the groups converted into the salt form, it is possible, according to the law of action of the masses, to set a desired pH value a priori.



   Aqueous dispersions of polylotone polyurethanes which contain salt groups can also be obtained because the polyhydroxy compounds with reactive hydrogen atoms having a molecular weight of 300 to 10,000 contain salt or suitable groups. salt diet.
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  The aqueous polylaotoned-polyurethane8 dispersions to be used according to the invention are stable,

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   storable and transportable and they can be converted into sheets, wires, films or large-area items. The isolation of the masses of polylaotones-polyurethanes from the dispersions is carried out, for example, by coagulation or elimination of water by evaporation optionally at high temperature, obtaining, depending on the composition, clear, transparent or elastic masses.



   To this end, the dispersions are applied, for example, by means of a spray gun or a doctor blade on the substrates to be coated or impregnated, such as strips of natural or synthetic leather, of paper or of textile, and it is dried at room temperature or at 80-160 C, optionally in the presence of retioulation agents.



   The conversion into sheets, films, threads or articles with a large surface area can also be carried out in the presence of known cross-linking agents. For this, dispersions are used for the preparation of which, during or after this, polyfunctional substances with crosslinking aotion have been used together which, after evaporation of water at room temperature or at elevated temperature, producing a chemical crosslinking. .

   Mention will be made, for example, of sulfur from sulfur sols, formaldehyde, substances releasing formaldehyde or reacting such as formaldehyde, polymethylol compounds of melamines, ureas or melamines, epoxy compounds such as polyglycidyl ethers of polyvalent alools such as as glyool, diethylene glycol, glycerin or sorbitol, free or partially or completely concealed polyisooyanates, carbodiimides, polyamides, polyacids, polyhalides, compounds of bi or polyvalent metals such as for example oxides, carbonates, hydroxides or chlorides of aluminum , zinc or magnesium, organic or mineral peroxides.

   Finally, we can

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 also incorporate fillers, plasticizers, pigments, fluosilicic or silicic acid sols, dispersions of aluminum, clay and asbestos in the polylactone-urethane dispersions, adding them during preparation of the dispersion or the completed dispersion. the dispersions can before their use in accordance with the invention be cut with dispersions of the same filler, such as, for example, with dispersions of polyvinyl chloride, polyethylene, polystyrene, polybutadiene and comolymers.



   The products of the process, which show good resistance to water, oil and chemical cleaning, are mainly used as coatings, intermediate coats, adhesion promoters, binders or impregnations for the most difficult substrates. varies and for the manufacture of films, sheets, threads and coatings. The plastics which can be prepared in accordance with the invention can also be used for the plasticization of a wide variety of materials such as gelatin and plastics.

     Example 1 -
250 g of poly - # - caprolactone (OH index 56) are reacted after dehydration for half an hour at 120 C under vacuum with 38 g of 1,6-hexane-diisooyanate for 2 hours at 120 C. After cooling the melt of prepolymer, 770 cm3 of acetone is added. When the melt is dissolved, a solution of 9.2 g of potassium lysinate (molecular weight 184) in 120 cm3 of water is added. Pais, we introduce 345 cm3 of water and we distill! acetone.

   The acetone-free latex which is thus obtained and which has a dry matter content of 42%,
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 is stable 8't, .¯>., ... ", 'u.186 -....' .¯ ':"' rr '"1" \. ----- - latex on a glass support using a hand scraper to form a film and the latter is dried at 120 C for

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 1 denies. A clear film is obtained ot trancparant ayost de. good cleanliness & o mechanics. The so-called .1im¯guo film is produced by good old properties and by good stability to hyolith ', (1.



  : ''. ' dil es We roprond in 770 om3 of naetone a prpo2, yrc propalù from 294 g of 1> oly ... 6 .... oaprolaotono (indiC0 OH 56) ot due 39tut- g of 1,6-hex n -diisooyanato in the manner (1úori to li Example 1 and one ssatatc 50 0 a 001ution of â, 3, a do taur.nut sodium which ooatient 0.20 mol of reactive nitrogen in 100 g of the solution. Then 540 am 3 of water is introduced into the reaction mixture and 50-6000 ctona is distilled under a water pump vacuum. The latex which remains is 43% and has a tClle1. The acetone residue is 0.5 µm by weight The latex is diluted to a dry matter content of 10% and mixed with a 10% solution of a photographic gelatin in water in the ratio 1: 2, The mixture is poured onto a glass plate of aoryl resin and dried at 60 C.

   The peeled sheet is then adjusted to a climate of 30% relative air humidity and is compared to a gelatin sheet conditioned in the same way. While the gelatin sheet, without the addition of latex, breaks immediately upon sharp bending, the sheet which contains an addition of 50% polylaotonepolyurethane is elastic and flexible.



  Example 3 -
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 250 g of poly¯e-oaprolactone (OH 56 index) are dehydrated under a water pump vacuum at 120 ° C. and reacted with 38 g of 1,6-hexane-diisooyanate for 2 hours at 120 ° C. )VS. The melt is cooled to 70 0 and.
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 it is taken up in 770 em3 diacetone '. The acetonic solution, which is at a temperature of 50 ° C., is added to an aqueous solution of 50 om3 of water, 3.8 g of ethylene
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 diamine, 7.6, 6; de 'DrOnane-: m1t: nnA n 1' "fP <7 #. * ----

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 than aqueous at 10, eu. Then we incorporate 375 om3 of water and
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 on & 1L'3F3 '9à3 i 5000 under the vacuum of a': '' l e1. \.

   The i '.; Â 9.45% is' .7.,' In a film out âi - '' Q'1G r, 1.?o o. / The film ëetmhé of the glass holder is olair. resistant ù
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 the fraction and very elastic, CLAIMS
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 ........, .... w ... m ....,. ¯ ..



  ?, n Proceeds of preparation of sheets, films, yarns and articles, large surface including coatings impregnated- "% ions, intermediate gouohss and bondings by placing on formed lates of J? olr! J. ::. '6thanes prepared in a manner known per se by the process of polyaddition to 5.xoayanate, 1 fu base of compounds poljrh3 "droxyl <é-ù having a molecular weight of 300 10,000 of aflu; 4oat;: s'c and ezo. rarav of agents Gta..â.âéaGs'2., from o1: no to use Q: l, a ... LAW! up by "'Qçi (i..J ..'- ßâ or elimination of water by evaporation, evenP.? C'." 31'.1'â el at high tempcraturo ot possibly os pressa- * ce d ' Known reticti-1-ation agents, characterized by the fact that polyurdthaaos latex is used in the preparation c10fJR 'Quel-- bzz a.iiJ.5.z6 ccsrse coEiposed polyhydroJïylé8 COï,.' 1, X which fsFS ,, s :

  ? F ... '1U a 1) 1), j7.Sü.a. $.' 3iÂ'é üâ a serio of hydroxy ester groupûscats: l1coylèl'1cc; \ r'boJ, rl.t1 \ l (; 4 > vent; lelleze?.:> 1 "ooyl" "sib,? t; Lt; a6 r ,, 7n2 m. 's: 3 carbon in the oak lQoylènl3 2. Prooéd6 sole :!'! la claim in oQrQct6riÓ that what one uses the te :: of l) olyv.:rthe.no (1 in the preparation "" tion d: ytacl one has used toes ro61n6ca of poJ.irhydroxylated compounds which consist of at least J .0yl de composas polyhydroxylëu eontensat des; z'Ol \ p@r.1! NtJ cotor hyùro? J9nlooj,?, ÔnecQ! 'Boxy11que v0n'imolJ.omnt nlcoyl ...; ublJti tu6e having 4 to a carbon atoms in the aloylêno chain.



  3. Proceeds according to claims 1 and 2t carme 'tér1 ::; é in that as polyhydroxyldc compounds OOl1ten ±' nt; deo gI'oupements ester hydroxyalkyl no "'(H \: t''boxyl: l.q1. \ o r

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 tuo21men '! ï alooyl-su.bst1 killed we use poly ... E: .... hydrosyeaprclaotones ve, .. mn a: aa; 3, -. bo.taaaa