SE123741C1

SE123741C1 -

Info

Publication number: SE123741C1
Authority: SE
Publication date: 1948-01-01

Description

Uppfinnare: A. E. Battye, H. Corteen och J. T. Marsh. Inventors: A. E. Battye, H. Corteen, and J. T. Marsh.

Priorite4 begard fr'dn den 12 september 1943 oeh, den 21 jani, 1944 (Starbritannien). Priorite4 requested from September 12, 1943 oeh, January 21, 1944 (United Kingdom).

Foreliggande uppfinning hanfor sig till ett sitt att behandla papper eller pappershildande material, i det foljande betecknat som pappersmaterial. Med pappersbildande material avses hdr vegetabiliska eller cellulosafibrer, som aro kanda for att lampa sig for papperstillverkning, och dessa kunna behandlas i vilket som heist stadium av papperstillverkningen, t. ex. som losa fibrer, som massa 1 hollandaren, nâr massan lamnar hollandaren, som bana av vata och icke konsoliderade fibrer, nar denna kommer frail pappersmaskinens vim, eller som konsoliderande fibrer fare tombningen. - Uppfinningen bestar i ett salt att behandla papper eller pappersbildande material med en losning av en partiellt kondenserad hartsprodukt, och uppfinningen kanneteeknas i huvudsak darav, att till behandlingslosningen sattes ett motstandsformaga mot vatten medforande medel, bestaende av mindre an V, vikts-% (beraknat pa losningens vikt) av ett kvartart ammoniumsalt av foljande allmanna formel: R — Y — —N (tert) —X, I vilken R är en hOgremolekylar rest, Y Or nagon av grupperna —0—, —CO—NH— eller —0—CO—NH—, X ar en saltbildande grupp °eh N (tert) Or en tertiar kvaveatom. The present invention relates to treating paper or paper-bearing material, hereinafter referred to as paper material. By papermaking material is meant hdr vegetable or cellulosic fibers, which are known to be suitable for papermaking, and these can be processed at any heist stage of papermaking, e.g. as loose fibers, as pulp 1 the Dutchman, when the pulp leaves the Dutchman, as a web of wet and unconsolidated fibers, when it comes frail from the paper machine vim, or as consolidating fibers the emptying. The invention consists in a salt for treating paper or papermaking material with a solution of a partially condensed resin product, and the invention can be mainly characterized in that to the treatment solution was added a water-resistant agent, consisting of less than V,% by weight (calculated). on the weight of the solution) of a quaternary ammonium salt of the following general formula: R - Y - —N (tert) —X, in which R is a right molecular moiety, Y Or any of the groups —CO — NH—, X is a salt-forming group ° eh N (tert) Or a tertiary quavatome.

DE det galler att gOra papperet motstandskraftigt mot spridning av black och tryckfdrg, ban till behandlingslosningen sattas mindre On 0,1 vikts-% (beraknat pa losningens vikt) av det kvartara ammoniumsaltet. If it is necessary to make the paper resistant to the spread of black and ink, the path to the treatment solution is set to be less than 0.1% by weight (based on the weight of the solution) of the quaternary ammonium salt.

Ett exempel pa ett sadam kvartart ammoniumsalt ar den under handelsnamnet »Velan salda produkten, som bur formeln: C.R,0 CO • NH •CIL NC,HX1 Kondensationen av den partiellt kondenserade hartsprodukten fullbordas efter pappe rets behandling, foretradesvis genom att forst torka papperet och darefter upphetta det. An example of such a quarterly ammonium salt is the product sold under the trade name »Velan, bearing the formula: CR, 0 CO • NH • CIL NC, HX1 The condensation of the partially condensed resin product is completed after the treatment of the paper, preferably by first drying the paper and then heat it.

Foretradesvis anvandes en partiellt kondenserad urinamneformaldehydkondensationsprodukt och katalysatorn ban utgOras av en syra frigjord fran det kvartara ammoniumsaltet. Preferably a partially condensed urea formaldehyde condensation product is used and the catalyst is an acid liberated from the quaternary ammonium salt.

Andra varmeomvandlingsbara hartser, aro de, vilka tillhora den kanda gruppen aldehydhartser, t. ex. de, som erhallas genom kondensation av formaldehyd eller andra aldehyder med dicyandiamid, fenol, kresol, acetofenol eller lampliga blandningar darav. Papperets egenskaper kunna modifieras go-nom tillsats av kanda modifierings- eller mjukgirringsmedel till det partiella kondensatet. Other heat-convertible resins are those which belong to the known group of aldehyde resins, e.g. those obtained by condensation of formaldehyde or other aldehydes with dicyandiamide, phenol, cresol, acetophenol or suitable mixtures thereof. The properties of the paper can be modified by adding kanda modifier or softening agent to the partial condensate.

Man foredrager att anvanda vattenlosningar av de partiellt kondenserade produkterna, men losningar av urinamneformaldehydhartskondensationsprodukter i alkohollosningsmedel och aven i kolvatelosningsmedel aro kanda och kunna anvandas fOr dessa andamal, liksom man aven ban anvanda losningar av etrar av mono- eller dimetylolurinamne. It is preferred to use aqueous solutions of the partially condensed products, but solutions of urea formaldehyde resin condensation products in alcohol solvents and also in hydrocarbon solvents are known and can be used for these purposes, as well as solutions of mono- or dimethylol urea ether ethers.

Det är aven mojligt att am/Linda blandningar av urinamneformaldehydkondensationsprodukter med emulsionspolymerer av termoplastiska hartser. It is also possible to mix mixtures of urea formaldehyde condensation products with thermoplastic resin emulsion polymers.

Man ban anvanda partiellt kondenserade produkter, t. ex. av fenol-formaldehyd eller urinamneformaldehyd, vilka annu aro vattenlosliga, eller i hOgre grad kondenserade produkter, I. ex. av de namnda amnena. Partially condensed products may be used, e.g. of phenol-formaldehyde or urea-formaldehyde, which are otherwise water-soluble, or highly condensed products, I. ex. of the named subjects.

Uppfinningen skall i det foljande fortydligas genom nagra utforingsexempel. The invention will be elucidated in the following by some exemplary embodiments.

Exempel 1. 60 delar urinamne, 150 viktsdelar %-ig formaldehydlOsning och 6 viktsdelar hexametylentetramin blandas och upphettas pA 2— — vattenbad, tills ett avkylt pray icke uppvisar nagon grumling. Example 1. 60 parts of urea, 150 parts by weight of formaldehyde solution and 6 parts by weight of hexamethylenetetramine are mixed and heated in a water bath until a cooled pray shows no turbidity.

Upphettningstiden kan variera mellan 45 min. och 120 min. Vid ett experiment var losningens viskositet 40 cP och dess sp. v. 1,17o. 20 cm' av denna hartslosning blandas med 6 g stearoxykarbamidometylpyridiniumklorid. He-la valskemangden utspddes darpa till ungefar 200 cm', och det kan bliva nodvandigt att tillsatta litet teknisk sprit for att halln hartset losning. Papperet behandlas med denna 15s-fling pa ovan beskrivet sat, torkas och upphettas. The heating time can vary between 45 min. and 120 min. In one experiment, the viscosity of the solution was 40 cP and its sp. v. 1.17o. 20 cm 3 of this resin solution is mixed with 6 g of stearoxycarbamidomethylpyridinium chloride. The whole rolling pin was diluted to about 200 cm 3, and it may be necessary to add a little technical spirit to keep the resin from dissolving. The paper is treated with this 15s flake in the manner described above, dried and heated.

Exempel 2. Example 2.

En reaktionsblandning beredes genom losning av 25 delar urinfimne och 5 delar tiourinamne i 75 delar neutraliserad 40 %-ig formaldehydlosning. 3,5 delar ammoniumhydroxid (0,88) tillsattas, och losningen kokas under aterflode under 3 min. 5 delar borsyra losas darpa i 25 delar vatten och tillsattas ovannamnda losning, som kokas ytterligare 60 min. under aterflode. delar Velan P.F. beredas till en pasta med 5 delar metylalkohol och sattas till 40 delar av ovannamnda blandning. Losningen utspades darefter till 300 delar med vatten, soon, om sa erfordras, kan innehalla nagot litet teknisk sprit for underlattande av 15sligheten. A reaction mixture is prepared by dissolving 25 parts of urea and 5 parts of thiourea in 75 parts of neutralized 40% formaldehyde solution. 3.5 parts of ammonium hydroxide (0.88) are added, and the solution is boiled under reflux for 3 minutes. 5 parts of boric acid are dissolved in 25 parts of water and added to the above solution, which is boiled for a further 60 minutes. during floods. shares Velan P.F. is prepared into a paste with 5 parts of methyl alcohol and added to 40 parts of the above mixture. The solution is then diluted to 300 parts with water, which, if required, may contain some small technical spirits to facilitate digestion.

Papper kan behandlas med denna losning det i exempel 1 beskrivna sattet. Paper can be treated with this solution in the manner described in Example 1.

Oavsett om man begagnar svagt eller kraftigt kondenserade hartsprodukter, utgor halten kvartart ammoniumsalt Ifimpligen mind-re an 1 %, ehuru denim halt kan uppga till 2 vikts-% av losningarna. Till den i exempel 3 beskrivna fOrmagan att hindra black eller tryckfarg att sprida sig i papperet bor halten vanligen vara mindre an 1/, -vikts-% och kan vara sa lag somvikts-% av lOsningen. Regardless of whether weak or heavily condensed resin products are used, the content of quarter quaternary ammonium salt is usually less than 1%, although denim content may amount to 2% by weight of the solutions. For the ability to prevent black or ink from spreading in the paper described in Example 3, the content should usually be less than 1% by weight and may be as low as% by weight of the solution.

Da papperet skall tryckas med tryckfarg kan det vara mindre onskvart att begagna Aven '/, % kvartart ammoniumsalt, ty tryckfargen absorberas icke oklanderligt, om papperet hr alltfor hydrofobt. Det har visat sig, att mycket fordelaktiga resultat kunna uppnas genom begagnade av konstharts i sam- band med mindre an 7,kvartfirt ammo- niumsalt och vardefulla resultat kunna uppnas med mindre an en tiondels %, t. ex. 0,61— 0,02 %. Since the paper is to be printed with ink, it may be less desirable to use even / /% quarter ammonium salt, for the ink is not impeccably absorbed if the paper is too hydrophobic. It has been found that very advantageous results can be obtained by using synthetic resins in conjunction with less than 7, quaternary ammonium salt and valuable results can be achieved with less than one tenth%, e.g. 0.61— 0.02%.

Exempel 3. 60 viktsdelar urinamne (1 nool) losas i 159 viktsdelar 40 % -ig formaldehydlosning (2 mol), som neutraliserats med natriumhydroxidlosning. Denna losning kokas under en aterflodeskondensator med 3 % (beraknat pa losningens totala vikt )ammoniak (spec. vikt 0,88) under 3 min. och kyles darpa snabbt. Losningen utspades till 10 % styrka med vat-ten, i vilket 3 vikts-% (beraknat pa mangden fast harts i den outspadda losningen) monoammoniumfosfat losts. Till den utspadda Idsningen sattas 0,033 vikts-% (berfiknat ph den totala vikten av losningen) av Velan P.F., soon dessThrinnan berelis till en pasta med en lika stor viktsmangd metylalkohol. Example 3. 60 parts by weight of urea (1 nool) are dissolved in 159 parts by weight of 40% formaldehyde solution (2 moles), which is neutralized with sodium hydroxide solution. This solution is boiled under a reflux condenser with 3% (based on the total weight of the solution) ammonia (spec. Weight 0.88) for 3 minutes. and cool darpa quickly. The solution was diluted to 10% strength with water, in which 3% by weight (based on the amount of solid resin in the undiluted solution) monoammonium phosphate was dissolved. To the diluted icing was added 0.033% by weight (calculated ph the total weight of the solution) of Velan P.F., soon thereafter Thrinnan berelis to a paste with an equal amount of methyl alcohol by weight.

Ett kraftpapper med en tjocklek av 0,6675 m/m och en sp. v. av 0,6 impregneras med denna vfitska, pressas omsorgsfullt for avlagsnande av sa onycket Overskottsvatska som mOjligt, torkas vid 70° C och upphettas under 2 min. till 160° C. Darpa tvattas papperet under 2 mm. vid 80° C i en vattenlosning av en fjardedels procent tval och en fjardedels procent natriumkarbonat, varph papperet tor-has. Papperet visar sig harefter hava formaga att motsta spridning av black och tryckfarg och har aven en star hallfasthet i vatt till-stand. A kraft paper with a thickness of 0.6675 m / m and a sp. v. of 0.6 is impregnated with this vfitska, pressed carefully for removal of as much excess liquid as possible, dried at 70 ° C and heated for 2 min. to 160 ° C. Darpa is washed the paper under 2 mm. at 80 ° C in an aqueous solution of one quarter percent whey and one quarter percent sodium carbonate, warp the paper tor-has. The paper then turns out to be able to resist the spread of black and ink and also has a rigid half-strength in the water state.

I alla de ovanstaende exemplen liar det kvartara ammoniumsaltet beraknats i vikts-% av den vattenhaltiga losningen av den partiellt kondenserade hartsprodukten. In all of the above examples, the quaternary ammonium salt has been calculated in% by weight of the aqueous solution of the partially condensed resin product.

Mangden kalatalysator utgor lampligen icke mera an 1-2 %, beraknat pa den fasta mangden av den partiellt kondenserade hartsprodukten i vattenlosningen. The amount of catalytic catalyst is suitably not more than 1-2%, calculated on the fixed amount of the partially condensed resin product in the aqueous solution.

Katalysatorn kan emellertid besth av syra, soon frigjorts frau det kvartara ammoniumsaltet. I det senare fallet frigores exempelvis vid begagnande av Velan-produkten saltsyra frail det kvartara saltet, och denna syra kan verka sasom katalysator. I detta fall skall natriumacetatet, som ofta tillsattes ett kvartart ammuniumsalt for neutralisering av den frigjorda sran, icke begagnas. However, the catalyst may consist of acid, soon liberated from the quaternary ammonium salt. In the latter case, for example, when the Velan product is used, hydrochloric acid is released from the quaternary salt, and this acid can act as a catalyst. In this case, the sodium acetate, which was often added with a quarter of an ammonium salt to neutralize the liberated acid, should not be used.

Reagenserna kunna begagnas fOr porOst material, och ph grund av den hOga hastigheten vid papperstillverkningen hr det nodvandigt att framstalla stora mangder reagens, och vanligen maste losningens stabilitet vara avsevard, t. ex. upp till tio timmar. Om den angivna halten katalysator Ras mycket, blir processen oekonomisk, emedan det finnes risk for angrepp ph cellulosan genom hydrolys och papperets egenskaper i torrt tillstand kunna bliva forsamrade. The reagents can be used for porous materials, and due to the high speed of papermaking it is necessary to produce large amounts of reagents, and usually the stability of the solution must be considerable, e.g. up to ten hours. If the stated content of catalyst is greatly reduced, the process becomes uneconomical, because there is a risk of attack by the cellulose by hydrolysis and the properties of the paper in the dry state can be disintegrated.

Vid tillverkningen och behandlingen av olimmat papper bestar den foredragna typen latent katalysator (om det forutom det kvartara ammuniumsaltet erfordras en sadan) av ammoniumsalter av syror, men det fir ocksa mojligt att anvanda losliga salter av polyvalenta metaller, och andra pot entiella katalysatorer, t. ex. ett halogenerat och acylerat urinamne, en halogenerad nitril, en halogenerad amid, en halogenerad keton, ett nitrerat urinamne och aminoamidsalter eller aminonitrilsalter av oorganiska syror. In the manufacture and treatment of glued paper, the preferred type of latent catalyst (if required in addition to the quaternary ammonium salt) consists of ammonium salts of acids, but it is also possible to use soluble salts of polyvalent metals, and other potential catalysts, e.g. ex. a halogenated and acylated urea name, a halogenated nitrile, a halogenated amide, a halogenated ketone, a nitrated urea name and aminoamide salts or aminonitrile salts of inorganic acids.

En lamplig losning med lag molekylarvikt och lag viskositet kan framstallas av urinamne och formaldehyd i molekylarforhallandet 1: 1,6. Okning av halten formaldehyd ha bendgenhet att forsamra papperets fysikaliska eller — —a mekaniska egenskaper i torrt tillstand, ehuru ,okningen av sagda halt kan medfora fordelar betraffande papperets egenskaper i vatt till-stand. A suitable solution with low molecular weight and low viscosity can be prepared from urine name and formaldehyde in the molecular ratio 1: 1.6. Increasing the formaldehyde content tends to degrade the physical or mechanical properties of the paper in the dry state, although the increase in said content can bring benefits to the properties of the paper in the wet state.

Andra impregneringsmedel kunna begagnas samtidigt med kondensationsprodukten med lag molekylarvikt, forutsatt att bildningen av hartskondensationsprodukten icke stores. Foljaktligen kan man begagna konstgjorda eller naturliga kolloider, t. ex. emulsionspolymerer av termoplastiska hartser, dispersioner av varmehardnande hartser med hog molekylarvikt, dispersioner av bitumen och liknande substanser, losningar av cellulosaetrar och hydroxyetrar, losningar av starkelse, dextrin, gummi, lim, gelatin, kasein, hartslimningsme- o. s. v. Det bar papekas, att det med vanligt ostabiliserat papper joke är mojligt att anvanda enkla, kontinuerliga forfaranden for impregnering med vattenlosningar, emulsioner eller dispersioner pa grund av den stora vattenuppsugningsfOrmagan, som ibland medfor, att papperet gar sonder. Other impregnating agents can be used simultaneously with the low molecular weight condensation product, provided that the formation of the resin condensation product is not disturbed. Consequently, one can use artificial or natural colloids, e.g. emulsion polymers of thermoplastic resins, dispersions of high molecular weight thermosetting resins, dispersions of bitumen and similar substances, solutions of cellulose ethers and hydroxy ethers, solutions of starch, dextrin, rubber, glue, gelatin, casein, resin sizing agents, etc. Ordinary unstabilized paper joke is possible to use simple, continuous procedures for impregnation with aqueous solutions, emulsions or dispersions due to the large water absorption capacity, which sometimes causes the paper to probe.

I manga av de ovannamnda fallen, dar det tillsatta materialet normalt ãr vattenlosligt, ut5var hartskondensationsprodukten en bindningsverkan, som medfdr, att det anvanda materialet blir motstandskraftigt mot vatten. In many of the above cases, where the added material is normally water-soluble, the resin condensation product has a binding effect which causes the material used to become water resistant.

Kvartara ammoniumsalter, som aro lampliga for anvandning i enlighet med foreliggande uppfinning aro t. ex. stearamidometylpyridiniumklorid och oktadekoxymetylpyricliniumklorid, som aro kanda for att giva eellulosamaterial hydrofoba egenskaper. Quaternary ammonium salts which are suitable for use in accordance with the present invention are e.g. stearamidomethylpyridinium chloride and octadecoxymethylpyriclinium chloride, which are known to impart hydrophobic properties to cellulosic materials.

Efter impregnering och fore den slutliga upphettningen for kondensering ay hartset kan papperet kalendreras, glattas, goffreras, veckas eller pa annat satt mekaniskt behandlas eller deformeras. Efter den slutliga upphettningen hava de mekaniskt astadkomna effekterna Rad motstandsformaga mot inverkan av vatten och andra svallningsmedel. Det ar exempelvis majligi att pa detta satt framstalla krappapper eller korrugerat papper, som joke forlorar sina vagor eller rynkor vid befuktning. After impregnation and before the final heating for condensation on the resin, the paper can be calendered, smoothed, embossed, pleated or otherwise mechanically treated or deformed. After the final heating, the mechanically produced effects have Rad resistance to the action of water and other swelling agents. It is, for example, possible to produce crap paper or corrugated paper in this way, which jokes lose their vaginas or wrinkles when moistened.

Claims

Patent claim:

A method of treating paper or papermaking material with a solution of a partially condensed resin product, which is then further condensed by heating the material, can be clarified that a water-resistant agent was added to the treatment solution, consisting of less. 1/4% by weight (based on the weight of the solution) of a quaternary ammonium salt of the following formula: R — Y — CH2 ---- N (tert) —X, in which It is a high molecular weight residue, Y Or any of the groups - 0 ----, —CO ---- NH— or —0 —CO — NH -----, X is a salt-forming group and N (tert) is a tertiary nitrogen atom.

2. sat according to patent claim 1 for all gra paper resp. the paper produced from the papermaking material is resistant to the spread of black and ink, characterized in that to the treatment solution was added 'Madre 0.1% by weight (based on the weight of the solution) of the quaternary ammonium salt. Stockholm 1948. Kungl. Boktr. P. A. Norstedt 4 Siiner 480089