SE429658B - MIGRATION OBJECTED LATEX MATERIAL USED AS A FIBER BINDING PIGMENT PARTICLE M.M. ALSO WAY TO MAKE THE SAME - Google Patents
MIGRATION OBJECTED LATEX MATERIAL USED AS A FIBER BINDING PIGMENT PARTICLE M.M. ALSO WAY TO MAKE THE SAMEInfo
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- SE429658B SE429658B SE7804781A SE7804781A SE429658B SE 429658 B SE429658 B SE 429658B SE 7804781 A SE7804781 A SE 7804781A SE 7804781 A SE7804781 A SE 7804781A SE 429658 B SE429658 B SE 429658B
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- latex
- silicic acid
- migration
- sio
- latex material
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/645—Impregnation followed by a solidification process
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/065—Increasing the size of dispersed rubber particles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/64—Inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Description
71804781-8 ligtvis mer utpräglad vid allt tjockare fibermaterial. Latexmigre- ring vid limning av flortyger medför att bindemedlet ej blir likfor- migt fördelat i materialet, vilket leder till ett svagare material eller att onödigt stor mängd bindemedel krävs för att uppnå önskade styrkeegenskaper. 71804781-8 more pronounced with increasingly thicker fibrous material. Latexmigre- gluing of non-woven fabrics means that the binder does not become uniform distributed in the material, which leads to a weaker material or that an unnecessarily large amount of binder is required to achieve the desired strength properties.
Det är tidigare känt att latexmigrering kan undvikas vid flortygtill- verkning genom användning av s.k. temperatursensitiv latex. En latex av detta slag kommer vid förhöjd temperatur i början av torkningen av det limmade materialet att koagulera och därmed förhindra binde- medlets benägenhet att migrera i floret. Fördelarna med s.k. tempera- tursensitiva latices är inte entydiga och en klar nackdel är att lag- ringsstabiliteten hos latexen är klart begränsad. Även vid framställning av bestruket papper är latexmigrering ett väl- känt och besvärligt problem. Vid bestrykning av papper och kartong används idag bestrykningssmetar innehållande kaolin eller andra pig- ment samt latexbindemedel. Vid applicering av smeten på papperet fås en tvåfaldig migrering. Dels migrerar vattenfasen och därmed binde- medlet (latexpartiklar) in i papperet och absorberas där, varvid en utarmning av bindemedel fås i smetskiktet. Vid intorkning av pappe- ret fås sedan ytterligare migrering, då bindemedlet vandrar ut mot bestrykningsskiktets yta och försvagar pigmentskiktets inre. Detta kommer att medföra sämre ytstyrka och sämre tryckfärgsabsorption, ge- nom att porerna mellan kaolinpartiklarna tätas till i större omfatt- ning i bestrykningsskiktets yta. På grund av bindemedelsmigrering krävs därför överskott av bindemedel för att uppnå optimal ytstyrka och därmed minskas tryckfärgsabsorptionen ytterligare. Detta ger en Sämre produkt och är dessutom olönsamt. Även i pigmenterade latexfärger förekommer migrering, i synnerhet vid industriell torkning, då bindemedlet anrikas i färgskiktets ytteryta och medför problem, bl.a. låg vattenånggenomsläpplighet, vilket le- der till blåsbildning.It is previously known that latex migration can be avoided in effect by using so-called temperature sensitive latex. A latex of this kind occurs at elevated temperature at the beginning of drying of the glued material to coagulate and thereby prevent the bonding the tendency of the agent to migrate in the floret. The advantages of so-called tempera- sensitive latices are not unambiguous and a clear disadvantage is that The stability of the latex is clearly limited. Even in the production of coated paper, latex migration is a good known and troublesome problem. When coating paper and cardboard Today, coatings containing kaolin or other pigments are used. ment and latex binder. When applying the batter on the paper is obtained a dual migration. On the one hand, the aqueous phase migrates and thus the the agent (latex particles) into the paper and is absorbed there, wherein a depletion of binder is obtained in the batter layer. When drying paperboard further migration is then obtained, as the binder migrates out towards the surface of the coating layer and weakens the interior of the pigment layer. This will result in poorer surface strength and poorer ink absorption, by clogging the pores between the kaolin particles to a greater extent in the surface of the coating layer. Due to binder migration therefore, excess binder is required to achieve optimum surface strength thus further reducing the ink absorption. This gives one Inferior product and is also unprofitable. Migration also occurs in pigmented latex paints, especially in industrial drying, when the binder is enriched in the outer surface of the paint layer and causes problems, i.a. low water vapor permeability, which to blistering.
Målet för uppfinningen var att undanröja bristerna hos tidigare använ- da latexsystem och få fram en produkt, varigenom latexmigreringen effektivt förhindras.The object of the invention was to eliminate the shortcomings of previous uses. latex system and produce a product, whereby the latex migration effectively prevented.
Detta uppnås enligt uppfinningen med användning av ett latexmaterial av inledningsvis nämnt slag, som kännetecknas av att kiselsyrasolen 7804781-8 är en alkaliskt stabiliserad kiselsyrasol med ett molratio Si02/M20 (där M är Na, K, Li eller NH4) 5-500 och en partikelstorlek mellan 1-50 nm, varvid vätebindningar från kiselsyrapartiklarna sammanhåller aggregat av latexpartiklar, vilka aggregat vid materialets användning som bindemedel ej migrerar vid torkning utan likformig fördelning upprätthâlles även i de torkade fiber- eller pigmentskiktens tvärsnitt.This is achieved according to the invention using a latex material of the kind mentioned in the introduction, which is characterized by the silicic acid sun 7804781-8 is an alkaline stabilized silicic acid sol with a molar ratio of SiO2 / M2O (where M is Na, K, Li or NH 4) 5-500 and a particle size between 1-50 nm, whereby hydrogen bonds from the silicic acid particles coalesce aggregates of latex particles, which aggregates during the use of the material as binder does not migrate on drying without uniform distribution is also maintained in the cross section of the dried fiber or pigment layers.
Uppfinnnrfims omfattning framgår av efterföljande patentkrav. Det er- hållna nya latexmaterialet uppvisar oväntat goda styrkeegenskaper vid non-wovenlimning och pappersbestrykning. Betingelserna vid modifie- ringen av latexen innebär att kiselsyrans karakteristika, såsom al- kalitet och partikelstorlek, avpassas så att i närvaro av speciella kopplingssubstanser en kontrollerad agglomerering av latexpartiklar- na fås i suspensionen. Lämpliga kopplingssubstanser är härvid ytak- tiva föreningar med en hydrofob kolvätedel och en hydrofil del bestå- ende av grupper, såsom eter, amin, amid eller alkohol, som har egen- skapen att utbilda vätebindningar med OH-grupper hos kiselsyran. Ut- märkta föreningar för detta ändamål är nonjoniska tensider med en hydrofil del bestående av polyetylenglykol. En kiselsyra med sådan alkalitet och åtföljande specifik yta väljes att ett pH av 2-9 er- hålles i den modifierade latexen. Vid detta relativt låga pH kommer vätebindningar att bildas mellan kiselsyrapartiklarna och de eter- grupper etc. i tensiden som vänds utåt från de hydrofoba polymerpar- tiklarna. Den polynæra kiselsyran kommer härvid att fungera som bryg- ga mellan latexpartiklarna i suspensionen. Latexpartiklarna bildar väldefinierade aggregat, som hålls samman med vätebindningar från kiselsyrapartiklarna. Den modifierade latexen är på detta sätt fin- flockulerad på ett unikt sätt genom att agglomereringen är styrd till önskad nivå. Genom modifieringen erhålles migreringsobafimna latex- aggregat av mikroskopiska dimensioner 0,1-50 pm.The scope of the invention is set forth in the appended claims. It is- held new latex material exhibits unexpectedly good strength properties at non-woven gluing and paper coating. The conditions for modification the latex means that the characteristics of the silicic acid, such as quality and particle size, adjusted so that in the presence of special coupling substances a controlled agglomeration of latex particles are available in the suspension. Suitable coupling substances in this case are surface compounds having a hydrophobic hydrocarbon moiety and a hydrophilic moiety groups, such as ether, amine, amide or alcohol, which have to form hydrogen bonds with OH groups of silicic acid. Out- labeled compounds for this purpose are nonionic surfactants with a hydrophilic moiety consisting of polyethylene glycol. A silicic acid with such alkalinity and the accompanying specific surface area is selected so that a pH of 2-9 kept in the modified latex. At this relatively low pH comes hydrogen bonds to be formed between the silicic acid particles and the ether groups etc. in the surfactant facing outwards from the hydrophobic polymer tiklarna. The polynaric silicic acid will act as a bridge. between the latex particles in the suspension. The latex particles form well-defined aggregates, which are held together by hydrogen bonds from the silicic acid particles. The modified latex is in this way finely divided. flocculated in a unique way by the agglomeration being controlled to desired level. The modification obtains the migration-free latex aggregates of microscopic dimensions 0.1-50 pm.
Den i systemen använda kiselsyran är kolloidal kiselsyra, dvs alka- listabiliserad eller ammoniumstabiliserad kiselsyrasol med kolloid storlek av 1-50 nm. Denna typ av kiselsyra är sedan gammalt känd i litteraturen. R.K. Iler (1) beskriver den som suspenderade polymo- lekylära kiselsyrapartiklar i vatten. För flertalet latexar erhålles de bästa resultaten med kiselsyrasol med partikelstorlek av 3-5 nm eller specifik yta av 400-600 m2/g. Vid högre specifik yta hos kisel- syrakolloiden erhålles ett snabbare agglomereringsförlopp, som kan vara svårt att styra, dvs resultatet av kiselsyratillsatser kan i 7804781-8 olyckliga fall medföra en latex med makroskopiska agglomerat (> 50 pm), vilket ej är önskvärt ur penetreringssynpunkt. Vid låg specifik yta hos kiselsyrakolloiden har densamma en låg aktivitet på grund av färre OH-grupper. Emellertid erhålles även den relaterade agglomere- ringseffekten vid så låg specifik yta hos kiselsyrasolen som 100 m2/g.The silicic acid used in the systems is colloidal silicic acid, ie alkaline list-stabilized or ammonium-stabilized silicic acid sol with colloid size of 1-50 nm. This type of silicic acid has long been known in the literature. R.K. Iler (1) describes it as suspended polymers. lexical silicic acid particles in water. For most latexes are obtained the best results with silica sol with a particle size of 3-5 nm or specific surface area of 400-600 m2 / g. At higher specific surface area of silicon the acid colloid, a faster agglomeration process is obtained, which can be difficult to control, ie the result of silicic acid additives can in 7804781-8 unfortunate cases result in a latex with macroscopic agglomerates (> 50 pm), which is not desirable from a penetration point of view. At low specific surface of the silicic acid colloid, the same has a low activity due to fewer OH groups. However, the related agglomeration is also obtained. the ring effect at as low a specific surface area of the silicic acid sol as 100 m2 / g.
Här krävs av förståeliga skäl högre halt kiselsyrasol i latexsyste- met än då soler med högre speciffliyta användes vid latexmodifieringen.For understandable reasons, higher levels of silicic acid sol are required in latex systems. than sols with a higher specific surface area were used in the latex modification.
Alkaliteten eller molratiot (SiO2/MZO), M = Na, K, Li eller NH4) på kiselsyrasolen är även av betydelse för resultatet av latexmodifierin- genl Vid låg ratio,_ dvs hög alkalitet i latexsystemet, utbildas ej några vätebindningar. Härvid erhålles naturligtvis ingen agglomere- ring av latexen och någon migreringsförhindrande effekt kan därmed V inte noteras vid limning av fibermaterial. För att tillrämiigt låg alkalitet skall fås (pH < 9) bör kiselsyrans ratio ej understiga 20 vid modifiering av flertalet latices. Någon kritisk övre gräns för ration föreligger ej men vid värden större än ca 500 är lagringssta- tbiliteten otillräcklig. Givetvis spelar latexens egen surhet härvid en stor roll.Det är således möjligt att med en ren syra eller latent syra modifiera latexen eller kiselsyran så att en enligt föreliggan- de uppfinning migreringsobenägen latex fås, trots ett ratio så lågt som ca 5 hos kiselsyrasolen. En attraktiv möjlighet som härvid prö- vats med gott resultat är att i närvaro av kiselsyrasol med lågt ra- tio tillföra latexsystemet s.k. latenta surgörare, såsom ammonium- salter, estrar, aminer, etanolamin etc. Då erhålles en stabil agglo- mereringsfri latex med hög alkalitet. Efter limning (bestrykning) av fibermaterialet (pigmentet) och i början av torkprocessen fås en reducering av alkaliteten på grund av sönderfall och/eller avdunst- ning av den latenta surgöraren. Härigenom uppnås ett kritiskt pH un- der 9, varvid latexen kan fås att agglomerera på ovan beskrivet sätt.The alkalinity or molar ratio (SiO2 / MZO), M = Na, K, Li or NH4) of The silicic acid sol is also important for the result of latex modification genl At low ratio, _ ie high alkalinity in the latex system, is not formed some hydrogen bonds. In this case, of course, no agglomeration is obtained. ring of the latex and any anti-migration effect can thus V not noted when gluing fibrous material. To reasonably low alkalinity should be obtained (pH <9) the silicic acid ratio should not be less than 20 when modifying the majority of latices. Some critical upper limit for ration does not exist but at values greater than about 500 the storage tbility insufficient. Of course, the latex's own acidity plays a role here a large role.It is thus possible to with a pure acid or latent acid modify the latex or silicic acid so that a the invention migration-prone latex is obtained, despite a ratio so low as about 5 in the silicic acid sun. An attractive opportunity that is with good results is that in the presence of silica sol with low ten add the latex system so-called latent acidifiers, such as ammonium salts, esters, amines, ethanolamine, etc. A stable agglomerate is then obtained. merceration-free latex with high alkalinity. After gluing (coating) of the fibrous material (pigment) and at the beginning of the drying process a reduction of the alkalinity due to decomposition and / or evaporation of the latent acidifier. This achieves a critical pH 9, wherein the latex can be made to agglomerate in the manner described above.
En enligt uppfinningen modifierad latex har karakteriserats med av- seende på storlek av partikelagglomerat och dess fördelning med en partikelanalysator ("Coulter-Counter" från Coulter Electronic Corp., England). Dessa mätningar visade att en verklig agglomerering fås under de givna betingelserna. En kommersiell SBR-latex (“Dow® d75" från Dow Chemical Co., USA) tjänade härvid som modellsystem. Den giv- na latexen hade en partikelstorlek mindre än 1 pm. Latexen saknade innehåll av kopplingssubstanser av typ nonjoniska tensider med eter- grupper. Latexen modifierades med en kiselsyrasol (10% SiO2 på torr SBR) med en specifik yta av 540 m2/g och ett ratio R = 40. Det modi- 7804781-8 fierade systemets pH blev 8,0. Partikelkarakterisering av latexen visade ingen skillnad jämfört med den omodifierade latexen, dvs en partikelstorlek under 1 Fm förelåg. Tillsattes emellertid en enligt uppfinningen föreslagen kopplingssubstans, erhölls genast en parti- kelförstoring (agglomerat), så att mikroskopiska agglomerat 1-30|pm stora erhölls. Den uppnådda förändringen är illustrerad i bifogade ritningsdiagram.A latex modified according to the invention has been characterized by looking at the size of the particle agglomerate and its distribution by one particle analyzer ("Coulter-Counter" from Coulter Electronic Corp., England). These measurements showed that a real agglomeration is obtained under the given conditions. A commercial SBR latex ("Dow® d75") from Dow Chemical Co., USA) served as a model system. The given The latex had a particle size of less than 1 .mu.m. The latex was missing content of nonionic surfactants with ether groups. The latex was modified with a silica sol (10% SiO 2 on dry) SBR) with a specific surface area of 540 m2 / g and a ratio R = 40. 7804781-8 the pH of the system was 8.0. Particle characterization of the latex showed no difference compared to the unmodified latex, i.e. a particle size below 1 Fm was present. However, one was added according to the proposed coupling substance, a batch was immediately obtained kel magnification (agglomerates), so that microscopic agglomerates 1-30 μm large was obtained. The change achieved is illustrated in the attached drawing diagram.
Den tillsatta kopplingssubstansen var i ovannämnda fall en nonjonten- sid av fettalkoholtyp med 80 etylenoxidgrupper. Vid impregnering av non-wovenmaterial, alt. pappersbestrykning, erhölls en klart lägre migrering (bindemedelsvandring) med en enligt uppfinningen modifierad latex. Detta kan förklaras med att stora bindemedelsaggregat (parti- kelagglomerat) har mindre benägenhet att vandra i fibermaterialets tvärsnitt vid torkningen. Detta innebär en likformig bindemedelsför- delning i ett flortyg eller ett pigmentskikt. Genom den fördelaktiga bindemedelsfördelningen fås ett starkare material. Denna styrkeökning är mest påtaglig i materialets z-riktning (delamineringsstyrkan). I gynnsamma fall erhölls en tiofaldig ökning av z-styrkan jämfört med omodifierad latex.The added coupling substance was in the above-mentioned case a nonionic side of fatty alcohol type with 80 ethylene oxide groups. When impregnating non-woven material, alt. paper coating, a clearly lower one was obtained migration (binder migration) with a modified according to the invention latex. This can be explained by the fact that large binder assemblies ( kelagglomerate) have less tendency to migrate in the fibrous material cross section during drying. This means a uniform binder division in a fleece fabric or a pigment layer. Through the advantageous the binder distribution is given a stronger material. This increase in strength is most noticeable in the z-direction of the material (delamination strength). IN favorable cases, a ten-fold increase in the z-strength was obtained compared with unmodified latex.
Kopplingssubstansen kan tillsättas latexen antingen före eller efter soltillsatsen men kan också sättas till solen före dennas inbland- ning i latexen.The coupling substance can be added to the latex either before or after the additive but can also be added to the sun before its involvement. in the latex.
Genom att surgöra den modifierade latexen till pH 2-4 uppnås en spe- ciellt hög stabilitet, dvs någon ytterligare agglomerering eller flockulering efter modifikationen kan ej noteras på flera veckor, medan den normala användningstiden i industriella sammanhang endast är några dygn.By acidifying the modified latex to pH 2-4, a specific particularly high stability, ie no further agglomeration or flocculation after the modification can not be noted for several weeks, while the normal service life in industrial contexts only is a few days.
Med föreliggande uppfinning uppnås en optimering av det organiska bindemedlets fördelning i fibermaterial, såsom cellulosa, rayon, po- lyester, polyakrylnitril, polypropen, glasfiber etc. eller i pigment- skikt, såsom kaolin vid pappersbestrykning eller titandioxid i latex- färger. Att det modifierade bindemedlet fördelar sig jämfört med omo- difierat bindemedel på ett överlägset sätt i fibermaterial pâvisades på följande sätt. Det limmade floret (50% rayonfiber - 50% cellulosa- fiber) doppades i en lösning av 1% sudanrött. Sudanrött är ett färg- ämne som enbart färgar det organiska bindemedlet, som i detta fall var ett polyakrylat. Floret delaminerades därefter, varvid florets 7sø47s1-s innerytor frilades. Med en ljushetsmätare och ett rödkänsligt filter kunde-färgintensiteten och därmed bindemedelshalten bestämmas i flo- rets ytter- och innerskikt. Förhållandet (Iy/Ii) mellan rödljusinten- si/teten hos ytterytan (Iy) och innerytan (Ii) är ett mått på migre- ringsbenägenheten hos bindemedlet. För latex modifierad under givna betingelser var Iy/Ii = 1,05 medan för omodifierad latex eller latex som kiselsyramodifierats under andra betingelser än som här angetts Iy/Ii = 1,30 - 1,40. Ett klart samband pâvisades också mellan binde- medlets fördelning i flortyget och flortygets delamineringsstyrka (z-styrka). Den modifierade latexen gav vid impregnering av flortyg en 5-10-faldig ökning av z-styrkan. Dessutom ökade den vanliga drag- styrkan (i x-y-riktning) med 50-100% jämfört med omodifierad latex under i övrigt lika betingelser. Liknande styrkeökningar erhölls också om bindemedlet applicerades med valsar (print-bonding) eller om det sprayades på flortyget.With the present invention an optimization of the organic is achieved distribution of the binder in fibrous materials, such as cellulose, rayon, lyester, polyacrylonitrile, polypropylene, glass fiber, etc. or in pigment layers, such as kaolin for paper coating or titanium dioxide in latex colors. That the modified binder is distributed in comparison with differentiated binder in a superior manner in fibrous material was detected in the following way. The glued web (50% rayon fiber - 50% cellulose fiber) was dipped in a solution of 1% sudan red. Sudan red is a colorful substance which only dyes the organic binder, as in this case was a polyacrylate. The floret was then delaminated, leaving the floret 7sø47s1-s inner surfaces were exposed. With a brightness meter and a red-sensitive filter customer color intensity and thus the binder content is determined in outer and inner layers of the year. The ratio (Iy / Ii) between the red light intensity The density of the outer surface (Iy) and the inner surface (Ii) is a measure of propensity of the binder. For latex modified under given conditions were Iy / Ii = 1.05 while for unmodified latex or latex silicic acid modified under conditions other than those specified herein Iy / Ii = 1.30 - 1.40. A clear link was also demonstrated between the distribution of the agent in the fleece and the delamination strength of the fleece (z-strength). The modified latex gave on impregnation of nonwovens a 5-10-fold increase in z-strength. In addition, the usual traction the strength (in the x-y direction) by 50-100% compared to unmodified latex under otherwise equal conditions. Similar strength increases were obtained also if the adhesive was applied with rollers (print-bonding) or if it was sprayed on the fleece fabric.
Genom tillsats av 5-10% av nämnda kiselsyra till latexar använda som bindemedel i pigmentslammor för pappersbestrykning erhölls en 50-100%- ig ökning av tryckfärgsadsorptionen (K & N-värde enligt metod utar- betad av K & N Laboratories,Evanston, Ill., USA) på det bestrukna papperet. Ytstyrkan på papperet, dvs delamineringsstyrkan i själva bestrykningsskiktet (pick resistance) var i allmänhet oförändrad el- ler minskade något men ökade för vissa latexar med upp till 30%. Den mängd SiO2 som tillfördes (5-10% räknat på torr latex) motsvarade 0,6-1,2% av kaolinmängden. Om i stället kaolinmängden ökades med 0,6-1,2% erhölls ingen mätbar effekt på vare sig K & N-värdet eller I ytstyrkan. Om latexmängden ökas i en smet, ökar ytstyrkan och sjunker K & N-värdet.och om latexmängden minskar, stiger K & N-värdet, medan ytstyrkan avtar. Detta samband mellan K & N~värdet och ytstyrkan ändras väsentligt genom tillsats av nämnda kiselsyra, så att en kraf- tig ökning av K & N-värdet endast ger en liten minskning av ytstyr- kan (ex. 4) eller att en mindre ökning av K & N-värdet faktiskt ger en ökning också av ytstyrkan (ex. 5).By adding 5-10% of said silicic acid to latexes used as binder in pigment sludges for paper coating a 50-100% - increase in ink adsorption (K&N value according to method grazed by K & N Laboratories, Evanston, Ill., USA) on the coated the paper. The surface strength of the paper, ie the delamination strength itself the pick resistance layer was generally unchanged. clay decreased slightly but increased for some latexes by up to 30%. The amount of SiO2 added (5-10% based on dry latex) corresponded 0.6-1.2% of the amount of kaolin. If instead the amount of kaolin was increased by 0.6-1.2%, no measurable effect was obtained on either the K&N value or In surface strength. If the amount of latex is increased in a batter, the surface strength increases and decreases The K&N value.and if the amount of latex decreases, the K&N value increases, while surface strength decreases. This relationship between the K & N value and the surface strength substantially altered by the addition of said silicic acid, so that a increase in the K&N value only gives a small reduction in surface can (ex. 4) or that a small increase in the K&N value actually gives an increase also in surface strength (ex. 5).
Vid tillsats av 5-10% av nämnda kiselsyra till pigmenterade latex- färger ökades vattenângpermeabiliteten 2-4 gånger. Vattenângpermea- biliteten mäts som viktminskning av en burk innehållande vatten, som förseglats med en 0,1 mm tjock film av den pigmenterade latexfärgen uttryckt i mg/cm2, h). 7894781-8 Exempel 1 Fyra latexprover (A, B, C, D) framställdes enligt följande: Till 50 g akrylnitril-butadienlatex ("Hycar®H-36" från B.F. Goodrich Chemical Company, 41% torrhalt) sattes 33,5 g jonbytt vatten. I prov B och D satsades därefter 1,0 g av en 10-procentig lösning av "Berol®-08", en fettalkoholpolyglykoleter med 18 kolatomer i kolkedjan och ca 80 etenoxidgrupper i glykoleterkedjan. Under omröring tillsattes 16,0 g 13,0-procentig kiselsyrasol. Den i prov A och B satsade solen hade molratio (SiO2:Na20) 57 och specifik yta 500 m2/g, medan solen som satsades i C och D hade ratio 100 och specifik yta 250 m2/g. Latexens pn efter moaifieringen blev 8,5 (A øch s) resp. 8,0 (c och n). Late- xens pH justerades därefter till pH 4,0 med 10-procentig oxalsyra.When adding 5-10% of said silicic acid to pigmented latex colors, the water vapor permeability was increased 2-4 times. Water vapor permea- mobility is measured as weight loss of a can containing water, which sealed with a 0.1 mm thick film of the pigmented latex paint expressed in mg / cm2, h). 7894781-8 Example 1 Four latex samples (A, B, C, D) were prepared as follows: To 50 g acrylonitrile-butadiene latex ("Hycar® H-36" from B.F. Goodrich Chemical Company, 41% dry content) was added 33.5 g of ion-exchanged water. In samples B and D then 1.0 g of a 10% solution of "Berol®-08" was charged, a fatty alcohol polyglycol ether having 18 carbon atoms in the carbon chain and about 80 ethylene oxide groups in the glycol ether chain. While stirring, 16.0 g was added 13.0% silica sol. The sun invested in samples A and B had molar ratio (SiO2: Na2O) 57 and specific surface area 500 m2 / g, while the sun as was invested in C and D had a ratio of 100 and a specific surface area of 250 m2 / g. Latexens pn after the moaification was 8.5 (A and s) resp. 8.0 (c and n). Late- The pH of the xen was then adjusted to pH 4.0 with 10% oxalic acid.
De modifierade latices hade en torrhalt av 20% och SiO2-halten var 10,0% räknat på torr latex. Ett obundet flortyg av blandfiber (50% cellulosa ~ 50% rayon) med ytvikt 60 g/m2 impregnerades därefter med latexsuspensionerna (A-D) efter utspädning till 8% torrhalt.The modified latices had a dry content of 20% and the SiO2 content was 10.0% calculated on dry latex. An unbound nonwoven fabric of mixed fiber (50% cellulose ~ 50% rayon) with a basis weight of 60 g / m2 was then impregnated with the latex suspensions (A-D) after dilution to 8% dry matter.
Ett referensprov impregnerades med ren latex ("Hycar®H-36") spådd till 8% torrhalt. De impregnerade proverna torkades 4 min. vid 155°C, varefter torr dragstyrka (F) och delamineringsstyrka (Z) bestämdes vid 20% bindemedelshalt i floret: Prov F Z kg/1,5 cm g/1,5 cm A 2,05 4 B 3,09 115 C 1,90 4 D 2,75 31 Referens 1,89 4 Exempel 2 Till 100 g "Hycar®H-36" sattes en lösning av 0,1 g “Berol®-08" och 2,0 g citronsyra i 5 g jonbytt vatten. Under kraftig omröring satsades därefter 68 g 6%-ig kiselsyrasol med ratio 10,2 och specifik yta 990 m2/g. Torrhalten i den modifierade latexen blev 20%, pH 3,1 och Si02-halten 10,0% räknat på torr latex. Den modifierade latexen späd- des till 8% torrhalt och en polyestervadd av ytvikt ca 60 g/m2 impreg- nerades.Ett referensprov impregnerades med ren “Hycar®H-36" spådd till 8% torrhalt. Efter torkning 6 min. vid 125°C bestämdes torr dragstyrka (F) och delamineringsstyrka (Z) vid 25% bindemedelshalt i polyestervadden: 7804781-8 8 F. kg/1,5 cm Z. g/1,5 cm Modifierad latex 3,10 _ 237 Referens-latex 2,38 87 Exempel 3 Till 1000 g av en akrylatlatex ("Primal®HA 8" från Rohm and Haas, 45% torrhalt) sattes under omröring 203 g jonbytt vatten och 30,3 g av en kiselsyrasol med 15,0% Si02, molratio (Si02:Na2O) = 50 och speci- fik yta = 550 m2/g. Härvid erhölls en Si02-halt av 10,0% på akrylat- polymeren och en torrhalt av 15% i systemet, vilket är lämpligt för impregnering av non-woven (flortyg) i industriell skala. Efter 15 mi- nuter sänktes pH till 3,0 med 0,1 N oxalsyra. (Någon särskild kopp- lingssubstans behöver i detta fall ej tillsättas, då denna latex re- dan är-försatt med nonjonisk tensid med vätebindande grupper). Även ett referensprov på ren "Primal®Ha-8" vid 15% torrhalt impregnerades.A reference sample was impregnated with pure latex ("Hycar®H-36") predicted to 8% dry matter. The impregnated samples were dried for 4 minutes. at 155 ° C, after which dry tensile strength (F) and delamination strength (Z) were determined at 20% binder content in the floret: Sample F Z kg / 1.5 cm g / 1.5 cm A 2.05 4 B 3.09 115 C 1.90 4 D 2.75 31 Reference 1.89 4 Example 2 To 100 g of "Hycar® H-36" was added a solution of 0.1 g of "Berol®-08" and 2.0 g of citric acid in 5 g of ion-exchanged water. With vigorous stirring was charged then 68 g of 6% silica sol with a ratio of 10.2 and specific surface area 990 m2 / g. The dry content of the modified latex was 20%, pH 3.1 and SiO2 content 10.0% calculated on dry latex. The modified latex diluted to a dry matter content of 8% and a polyester wad of a basis weight of about 60 g / m2 impregnated A reference sample was impregnated with pure "Hycar®H-36" predicted to 8% dry matter. After drying 6 min. at 125 ° C was determined dry tensile strength (F) and delamination strength (Z) at 25% binder content in polyester wadding: 7804781-8 8 F. kg / 1.5 cm Z. g / 1.5 cm Modified latex 3.10 _ 237 Reference latex 2.38 87 Example 3 To 1000 g of an acrylate latex ("Primal®HA 8" from Rohm and Haas, 45% dry matter) was added with stirring 203 g of ion-exchanged water and 30.3 g of a silicic acid sol with 15.0% SiO 2, molar ratio (SiO 2: Na 2 O) = 50 and specific fixed area = 550 m2 / g. This gave a SiO 2 content of 10.0% on acrylate. the polymer and a dry matter content of 15% in the system, which is suitable for impregnation of non-woven (woven fabric) on an industrial scale. After 15 mi- The pH was lowered to 3.0 with 0.1 N oxalic acid. (Any special cup- in this case does not need to be added, as this latex dan is-provided with nonionic surfactant with hydrogen bonding groups). Also a reference sample of pure "Primal®Ha-8" at 15% dry content was impregnated.
Flortygen torkades vid 120°C samt upphettades 2 min. vid 150°C för att akrylatet skall härda och ge maximal våtstyrka. Båda floren hade samma mängd upptaget bindemedel eller 20%. Styrkedata framgår av ta- bellenlnedan: Dragstyrka maskinriktning Z-styrka kg/1,5 cm ltorr, torr våt g/1,5 cm Modifierad latex 3,46 1,81 114 Referensprov 2,50 1,29 15 Exempel 4 En modifierad kiselsyrasol (I) framställdes sålunda: Till 20,0 g alkalistabiliserad kiselsyrasol med ratio 40, specifik yta 580 m2/g och S102-halt 15,0% sattes 2,4 g av en 10-procentig lösning av "Berol®-08".The fluoride fabrics were dried at 120 ° C and heated for 2 minutes. at 150 ° C for that the acrylate should harden and give maximum wet strength. Both flora had the same amount of binder taken up or 20%. Strength data can be found in bellenlnedan: Tensile strength machine direction Z-strength kg / 1.5 cm ltorr, dry wet g / 1.5 cm Modified latex 3.46 1.81 114 Reference test 2.50 1.29 15 Example 4 A modified silicic acid sol (I) was prepared as follows: To 20.0 g alkali-stabilized silicic acid sol with ratio 40, specific surface area 580 m2 / g and S102 content 15.0% was added 2.4 g of a 10% solution of "Berol®-08".
Till 100 g SBR-latex (“Dow®675" från Dow Chemical, 50% torrhalt) sat- tes under omröring hela mängden modifierad sol (I), varvid erhölls en kiselsyramodifierad latex (II) innehållande 6,0% Si02 räknat på torr plast. En bestrykningsslamma (III) bereddes genom att 50 g jon- bytt vatten vägdes upp och 0,18 g dispergeringsmedel (Na-polyakrylat “Polysalz CA" från BASF) och 3 droppar 50-procent Na0H löstes däri. 100 g kaolin ("Dinkie A" från English China Clay) inblandades och det hela omrördes med propelleromrörare 30 min. vid 1700 rpm. Däref- 7804781-8 ter silades slamman och pH-justerades till 8,5. Torrhalten blev 67%.To 100 g of SBR latex ("Dow®675" from Dow Chemical, 50% dry matter) while stirring, the entire amount of modified sol (I) was obtained to give a silicic acid modified latex (II) containing 6.0% SiO 2 calculated on dry plastic. A coating slurry (III) was prepared by adding 50 g of ionic changed water was weighed and 0.18 g of dispersant (Na polyacrylate) "Polysalz CA" from BASF) and 3 drops of 50% NaOH were dissolved therein. 100 g of kaolin ("Dinkie A" from English China Clay) was mixed and the whole was stirred with propeller stirrer for 30 min. at 1700 rpm. Therefore 7804781-8 The sludge was filtered and adjusted to pH 8.5. The dry content was 67%.
En bestrykningssmet (IV) tillverkades genom att till hela lerslamman (III) sätta 27,6 g av den modifierade latexen (II) under försiktig omröring. Smeten (IV) kom att ha en torrhalt av 63% och innehålla 12 delar modifierad eller 11,3 delar ren SBR på 100 delar kaolin.A coating batter (IV) was made by adding to the entire clay sludge (III) carefully place 27.6 g of the modified latex (II) stirring. The batter (IV) came to have a dry content of 63% and contain 12 parts modified or 11.3 parts pure SBR on 100 parts kaolin.
Ett ytlimmat papper beströks med bestrykningssmeten (IV) med hjälp av trådlindade stavar på vanligt sätt. Det bestrukna papperet torkades omedelbart i värmeskåp med luftcirkulation vid 80°C under 3 min. och fick därefter ligga i klimatrum 1 dygn vid 22°C 65% RH. Papperen väg- des sedan och beläggningen beräknades. Därefter provades glans, tryck- färgsadsorption (K&N-värde) och ytstyrka (IGT-värde metod utarbetad av Institut voor Grafische Techniek, Amsterdam) enligt gängse meto- der inom pappersindustrin.A surface-glued paper is coated with the coating paste (IV) using wire-wound rods in the usual way. The coated paper was dried immediately in an oven with air circulation at 80 ° C for 3 minutes. and then allowed to lie in a climate room for 1 day at 22 ° C 65% RH. The paper weighs was then calculated and the occupancy was calculated. Thereafter, gloss, pressure color adsorption (K&N value) and surface strength (IGT value method developed by the Institute of Graphic Technology, Amsterdam) according to standard in the paper industry.
En andra bestrykningssmet (V) gjordes genom att tillsätta 24,0 g ren latex ("Dcw®675") till hela lerslamman (III). Smeten, som fick en torrhalt av 64% och innehöll 12,0 delar SBR, beströks, torkades och provades enligt ovan. Följande resultat erhölls: Pappersegenskaper IGT-värde, cm/s hast. A, färg 6, Gl K N- :ns värde tryck 50 kg Modifierad smet 73,7 26,4 75 Referenssmet 71,4 13,5 95 Exempel 5 En modifierad kiselsyrasol framställdes sålunda: Till 20,0 g alkali- serad kiselsyrasol med ratio 52, specifik yta 400 m2/g och torrhalt 15,0% sattes 1,5 g av en 20-procentig lösning av nonylfenolpolygly- koleter (30 etenoxidgrupper). Till 100 g vinylacetat-akrylatlatex ("Acronal®500 D" från BASF) sattes under omröring hela mängden modi- fierad sol, varvid erhölls en kiselsyramodifierad latex innehållande 6,0% SiO2, räknat på mur plast. En bestrykningsslamma bereddes som i exempel 4. En bestrykningssmet tillverkades genom att till hela slamman sätta 29,1 g av den modifierade latexen under försiktig om- röring. smeten kom att ha en torrhalt av 63% och innehöll 12,8 delar modifierad latex eller 12,0 delar ren vinylacetat-akrylat på 100 de- lar kaolin. En andra bestrykningssmet bereddes genom tillsats av 24,0 g ren latex ("Acronal®500 D") till hela lerslamman enligt ovan. Sme- ten fick en torrhalt av 64% och innehöll 12,0 delar vinylacetat-akry- 7804781-8 10 kat. De båda smetarna applicerades på papper, torkades och provades som i exempel 4. Följande resultat erhölls: Pappersegenskaper IGT_värde, Cm/S Glans _ K&N- hast. A, färg 3, % värde tryck 50 kg modifierad smet 66,4 28,5 í 195 Referenssmet 66,0_ 27,0 145A second coating batter (V) was made by adding 24.0 g of pure latex ("Dcw®675") to the entire clay sludge (III). The batter, who got one dry content of 64% and contained 12.0 parts of SBR, coated, dried and tested as above. The following results were obtained: Paper properties IGT value, cm / s hurry. A, color 6, Gl K N- value of pressure 50 kg Modified batter 73.7 26.4 75 Reference batter 71.4 13.5 95 Example 5 A modified silicic acid sol was prepared as follows: To 20.0 g of alkali silicic acid sol with ratio 52, specific surface area 400 m2 / g and dry matter content 15.0% was added 1.5 g of a 20% solution of nonylphenol polyglyceride. carbonates (30 ethylene oxide groups). To 100 g of vinyl acetate-acrylate latex ("Acronal®500 D" from BASF) was added with stirring the entire amount of sol, to obtain a silicic acid modified latex containing 6.0% SiO2, calculated on wall plastic. A coating sludge was prepared as in Example 4. A coating batter was made by adding whole sludge put 29.1 g of the modified latex under gentle stirring. the batter came to have a dry content of 63% and contained 12.8 parts modified latex or 12.0 parts of pure vinyl acetate acrylate in 100 parts lar kaolin. A second coating batter was prepared by adding 24.0 g pure latex ("Acronal®500 D") to the entire clay sludge as above. Sme- The dry matter was 64% and contained 12.0 parts of vinyl acetate-acrylic 7804781-8 10 cat. The two batter were applied to paper, dried and tested as in Example 4. The following results were obtained: Paper properties IGT_value, Cm / S Gloss _ K & N- hast. A, color 3, % value pressure 50 kg modified batter 66.4 28.5 in 195 Reference batter 66.0_ 27.0 145
Claims (3)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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SE7804781A SE429658B (en) | 1978-04-26 | 1978-04-26 | MIGRATION OBJECTED LATEX MATERIAL USED AS A FIBER BINDING PIGMENT PARTICLE M.M. ALSO WAY TO MAKE THE SAME |
DE19792916316 DE2916316A1 (en) | 1978-04-26 | 1979-04-23 | Non-migrating latex binders for fibres and pigments - contg. alkali-stabilised silica sol and coupling agent |
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Application Number | Priority Date | Filing Date | Title |
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SE7804781A SE429658B (en) | 1978-04-26 | 1978-04-26 | MIGRATION OBJECTED LATEX MATERIAL USED AS A FIBER BINDING PIGMENT PARTICLE M.M. ALSO WAY TO MAKE THE SAME |
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DE3920379A1 (en) * | 1989-06-22 | 1991-01-03 | Heinr Aug Schoeller Soehne Gmb | METHOD FOR TREATING THE SURFACE OF A NATURAL PAPER |
DE4402187A1 (en) * | 1994-01-26 | 1995-07-27 | Bayer Ag | Backing nonwovens made of synthetic fibers and their manufacture |
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- 1978-04-26 SE SE7804781A patent/SE429658B/en not_active IP Right Cessation
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