DK171501B1 - Paper-like or cardboard-like material and process for its preparation - Google Patents
Paper-like or cardboard-like material and process for its preparation Download PDFInfo
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- DK171501B1 DK171501B1 DK163590A DK163590A DK171501B1 DK 171501 B1 DK171501 B1 DK 171501B1 DK 163590 A DK163590 A DK 163590A DK 163590 A DK163590 A DK 163590A DK 171501 B1 DK171501 B1 DK 171501B1
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
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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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
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- Inorganic Chemistry (AREA)
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Description
i DK 171501 B1in DK 171501 B1
Opfindelsen angår et papir-, karton- eller paplignende materiale med en meget stor andel af uorganiske bestanddele, nemlig uorganiske fibre og uorganiske, partikelformede additiver, d.v.s. af fyldstoffer og pigmenter.The invention relates to a paper, cardboard or cardboard-like material with a very large proportion of inorganic constituents, namely inorganic fibers and inorganic particulate additives, i.e. of fillers and pigments.
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Det er alment kendt, at styrken af papir på basis af uorganiske fibre er betinget af dannelsen af hydrogenbroer mellem de organiske fibre. Det er også kendt, at uorganiske fyldstoffer reducerer de for hydrogenbindingerne 10 til rådighed værende fiberflader ved mekanisk separation af fibrene eller blokerer til binding egnede positioner på fibrene og i stedet tilvejebringer svagere fiber-fyld-stof-fiber-bindinger, hvorved findelte fyldstoffer reducerer styrken særligt meget.It is well known that the strength of paper based on inorganic fibers is contingent upon the formation of hydrogen bridges between the organic fibers. It is also known that inorganic fillers reduce the fiber surfaces available to the hydrogen bonds 10 by mechanically separating the fibers or blocking suitable positions on the fibers and instead provide weaker fiber-filler-fiber bonds, whereby finely divided fillers reduce the strength. very much.
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Hvis man altså ved fremstillingen af papir- eller paplignende materialer kun anvender uorganiske fibre og fyldstoffer, altså stoffer, der ikke udviser nogen hydro-genbrobindingsevne, har de fremkomne aktive stoffer kun 20 ringe styrker.Thus, if only inorganic fibers and fillers are used in the manufacture of paper or cardboard-like materials, ie substances which have no hydrogen bonding ability, the resulting active substances have only 20 low strengths.
Fra EP-A-0 109 782 og EP-A-0 027 705 kender man papirag-tige materialer, der indeholder fibre, såsom glasfibre eller mineraluldsfibre, uorganiske partikelformede fyld-25 stoffer, såsom ler og bentonit, samt hydrolyseret stivelse som organisk bindemiddel. Til forbedring af styrken og til reduktion af sprødheden anvendes dog desuden også organiske fibre.EP-A-0 109 782 and EP-A-0 027 705 disclose paper-like materials containing fibers such as glass fibers or mineral wool fibers, inorganic particulate fillers such as clay and bentonite, and hydrolyzed starch as an organic binder. . However, organic fiber is also used to improve the strength and to reduce the brittleness.
30 Fra DE-A-26 06 487 kender man en fremgangsmåde til kontinuerlig fremstilling af formdele, der indeholder uorganiske fibre, en kiselsol og anionisk stivelse. Disse formdele indeholder dog ikke nogen uorganiske partikelformede fyldstoffer.30 DE-A-26 06 487 discloses a process for the continuous production of mold parts containing inorganic fibers, a silicon sol and anionic starch. However, these mold parts do not contain any inorganic particulate fillers.
Fra EP-B-0 080 986 (AT-E-13777) kender man en fremgangsmåde til fremstilling af papir, i henhold til hvilken der 35 DK 171501 B1 2 fremkonuner et produkt, der indeholder organiske fibre, d.v.s. cellulosefibre, mineralske fyldstoffer, anionisk kolloidal kiselsyre og kationisk guar. Et sådant produkt er brændbart på grund af dets store andel af organiske 5 fibre og er derfor ikke velegnet til mange anvendelser ved høj temperatur.EP-B-0 080 986 (AT-E-13777) discloses a method for making paper according to which a product containing organic fibers is produced, i.e. cellulose fibers, mineral fillers, anionic colloidal silicic acid and cationic guar. Such a product is combustible due to its large proportion of organic fibers and is therefore not suitable for many high temperature applications.
Fra US-A-3 253 978 kender man en fremgangsmåde til fremstilling af et porøst, uorganisk blad, der Indeholder 10 uorganiske fibre og/eller større flokkulater, en anionisk kiselsol og kationiske stivelse. Et sådant blad indeholder dog ingen findelte uorganiske fyldstoffer og udviser en utilstrækkelig styrke.US-A-3,253,978 discloses a process for the preparation of a porous, inorganic leaf containing 10 inorganic fibers and / or larger flocculates, an anionic silica sol and cationic starch. However, such a leaf contains no finely divided inorganic fillers and exhibits insufficient strength.
15 Fra GB-A-21 27 867 kender man et fibermateriale, der har ringe massefylde, og som indeholder uorganiske fibre, uorganiske fyldstoffer og en høj andel af kationisk guar.15 GB-A-21 27 867 discloses a low density fiber material containing inorganic fibers, inorganic fillers and a high proportion of cationic guar.
De uorganiske fyldstoffer er standardfyldstoffer, der anvendes i forholdsvis små mængder. Desuden tilsætter man 20 borax med henblik på udfældning af guaren på de uorganiske fibre.The inorganic fillers are standard fillers used in relatively small quantities. In addition, 20 borax is added to precipitate the guar on the inorganic fibers.
Fra GB-A-2 031 043 kender man et fiberholdigt bladmateriale, der indeholder fibre i en matrix af plastisk ler 25 (ball clay). Materialet kan desuden indeholde bentonit til regulering af afvandingshastigheden. Som bindemiddel anvender man hydrolyserbar stivelse. Materialet indeholder desuden en forholdsvis høj andel af cellulose-fibre.GB-A-2 031 043 discloses a fibrous sheet material containing fibers in a matrix of plastic clay 25 (ball clay). The material may additionally contain bentonite to control the drainage rate. Hydrolyzable starch is used as a binder. The material also contains a relatively high proportion of cellulose fibers.
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Fra US-A-3 702 279 kender man fremstilling af et termisk isolationsmateriale, hvorved uorganiske fibre blandes med et bindemiddel af en uorganisk sol, hvorpå solen geleres.US-A-3 702 279 discloses the preparation of a thermal insulating material, whereby inorganic fibers are mixed with a binder of an inorganic sol and the sun is gelled.
Dette materiale indeholder ingen partikelformede additi-35 ver. Der anvendes ingen organiske bindemidler. Materialet sintres efter tørringen.This material contains no particulate additives. No organic binders are used. The material is sintered after drying.
DK 171501 B1 3DK 171501 B1 3
Det er opfindelsens formål at tilvejebringe et papir-, karton- eller paplignende materiale, der på den ene side er ubrændbart og som på den anden side har en høj styrke og flexibilitet og er godt forarbejdeligt. Disse egen-5 skaber kunne hidtil ikke forenes, d.v.s. man har hidtil antaget, at en forholdsvis høj andel af organiske fibre er nødvendig, hvis man vil fremstille fibermaterialer med høj styrke og flexibilitet samt med god forarbejdelighed, hvorved brændbarheden naturligvis blev forøget.It is an object of the invention to provide a paper, cardboard or cardboard-like material which, on the one hand, is non-combustible and which, on the other hand, has a high strength and flexibility and is easily processable. These properties could not be reconciled so far, i.e. It has hitherto been assumed that a relatively high proportion of organic fibers is necessary if one wants to produce high strength and flexibility fiber materials and good processability, which of course increases the combustibility.
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Materialet ifølge opfindelsen, der er af den i indledningen til krav 1 angivne art, er ejendommelig ved det i den kendetegnende del af krav 1 angivne. Herved opnås opfindelsens formål.The material according to the invention, which is of the kind set forth in the preamble of claim 1, is characterized by that specified in the characterizing part of claim 1. The object of the invention is thereby achieved.
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Materialerne Ifølge opfindelsen er ikke brændbare. De opfylder kravene svarende til DIN 4102 i klasse A. På grund af de gode styrkeegenskaber af materialerne ifølge opfindelsen lader de sig let forarbejde på lignende måde 20 som papir, karton og pap på grundlag af cellulosefibre. Fremstillingen af materialerne kan foretages på de sædvanlige papir-, karton- eller papmaskiner.The materials of the invention are non-combustible. They meet the requirements of DIN 4102 in Class A. Due to the good strength properties of the materials of the invention, they are easily processed in a similar manner to paper, cardboard and cardboard based on cellulose fibers. The materials can be manufactured on the usual paper, cardboard or cardboard machines.
De gode styrkeegenskaber er overraskende af den grund, at 25 man hidtil har været af den opfattelse, at styrkeværdierne blev drastisk reduceret ved store fyldstofindhold og ved voksende partikelfinhed. Styrkeværdierne af materialerne Ifølge opfindelsen forøges derfor Indenfor vide grænser med voksende mængder og voksende partikelfinhed 30 af de partikelformede, uorganiske additiver.The good strength properties are surprising because 25 hitherto it has been believed that the strength values were drastically reduced by high filler contents and by increasing particle fineness. Therefore, the strength values of the materials according to the invention are increased within wide limits with increasing amounts and increasing particle fineness 30 of the particulate inorganic additives.
Ved "partikelformede, uorganiske additiver" forstår man ifølge opfindelsen ikke fiberformede additiver, fordi længden af fibrene i almindelighed ligger i en størrel-35 sesorden svarende til nogle mm. Ved "partikelstørrelse" forstår man den største dimension af en partikel, hvilket f.eks. er vigtigt ved fladtrykte partikler. Partiklerne DK 171501 B1 4 af det anioniske, flokkulatdannende aktive pigment udviser ofte tendens til at danne større agglomerater. Ifølge opfindelsen forstår man derfor ved partikelstørrelse størrelsen af primærpartiklerne.By "particulate, inorganic additives" according to the invention, non-fibrous additives are understood as the length of the fibers is generally in an order of magnitude corresponding to some mm. By "particle size" is understood the largest dimension of a particle, e.g. is important for flattened particles. The particles DK 171501 B1 4 of the anionic flocculating active pigment often show a tendency to form larger agglomerates. According to the invention, therefore, by particle size, the size of the primary particles is understood.
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Forbedringen af styrkeegenskaberne er sandsynligvis betinget af, at det anioniske flokkulatdannende aktive pigment og det kationiske polymer kulhydrat dels tillejrer sig til de uorganiske fibre og at de dels tillejrer sig 10 til de uorganiske, partikelformede basisfyldstoffer. Partiklerne af basisfyldstof sætter sig fast på fiberoverfladerne og forhindrer på denne måde, at de i og for sig glatte, uorganiske fibre glider langs hinanden, hvorved der fremkommer en skubbefast fibervliess. Uorganiske 15 fibre er ikke i stand til, hverken ved hydrogenbrodannel-se eller ved tværbinding i kombination med skrumpning, at tilvejebringe styrker af den størrelse, som forekommer ved vegetabilske fibre. Styrken af et blad af rent uorganiske fibre beror på en "sammenklæbning" af de enkelte 20 fibre med hinanden ved fiberberøringspunkterne ved hjælp af organiske bindemidler. På grund af den ringe flexibi-litet af uorganiske fibre har en sådan fibervliess kun relativt få fiber-fiber-berøringspunkter, og desuden er retentionen af organiske bindemidler ved afvanding i 25 forbindelse med den sædvanlige papirfremstillingsproces yderst ringe. Det færdige produkt har således kun ringe styrke.The enhancement of the strength properties is probably contingent on the fact that the anionic flocculate active pigment and the cationic polymer carbohydrate partly adhere to the inorganic fibers and partly adhere to the inorganic particulate base fillers. The particles of base filler adhere to the fiber surfaces, thus preventing smooth, inorganic fibers from sliding along one another, resulting in a push-resistant fiber web. Inorganic fibers are unable, either by hydrogen bridging or by crosslinking in combination with shrinkage, to provide strengths of the size found in vegetable fibers. The strength of a sheet of pure inorganic fibers depends on a "bonding" of the individual 20 fibers to each other at the fiber touch points by means of organic binders. Due to the poor flexibility of inorganic fibers, such fiber web has relatively few fiber-fiber touch points, and furthermore, the retention of organic binders by dewatering in connection with the usual papermaking process is extremely poor. Thus, the finished product has little strength.
De ifølge opfindelsen anvendte basisfyldstoffer kan på 30 grund af deres overfladestørrelse og -struktur samt på grund af deres ladningsegenskaber danne flokkulat sammen med et velegnet kationisk kulhydrat. Ved flokkulatdannel-sen i vandigt system bliver de uorganiske fibre indlejret af fyldstof. Ved tilsætning af fyldstoffet forøges så-35 ledes ifølge opfindelsen både antallet af berøringspunkterne (fiber-fiber, fyldstof-fiber, fyldstof-fyldstof) og retentionen af kulhydratet. Der opnås kun en god struk- DK 171501 B1 5 turstyrke, når så vidt muligt alle fiber-fiber-krydspunkter er fuldstændigt indlejret og uden fejlpositioner er indlejret i fyldstof og flokkuleringsmidlet er regelmæssigt fordelt. Dette er kun muligt ved på velegnet måde 5 tilvejebragte flokkuleringer. Styringen af flokkuleringen foregår ifølge opfindelsen ved hjælp af de flokkulerings-dannende aktive pigmenter. Disse kan på grund af deres anioniske ladningspotential forskubbe flokkuleringspunkt-erne og bidrager derudover ved tilvejebringelse af en mi-10 kroflokkulering sammen med det kationiske kulhydrat til en god fordeling deraf. De anioniske flokkulatdannende aktive pigmenter kan derudover lukke fejlsteder i fyldstof-fyldstof- og fiber-fyldstof-kombinationer.The base fillers used according to the invention can flocculate together with a suitable cationic carbohydrate, because of their surface size and structure as well as because of their charge properties. In the aqueous system flocculation, the inorganic fibers become embedded in filler. Thus, by the addition of the filler, the invention increases both the number of touch points (fiber-fiber, filler-fiber, filler-filler) and the retention of the carbohydrate. Only a good structural strength is obtained when, as far as possible, all fiber-fiber junctions are completely embedded and without error positions are embedded in filler and the flocculant is regularly distributed. This is only possible with suitable flocculation provided. The flocculation is controlled according to the invention by means of the flocculation-forming active pigments. These, because of their anionic charge potential, can displace the flocculation points and, moreover, by providing a micro-flocculation together with the cationic carbohydrate for a good distribution thereof. In addition, the anionic flocculate active pigments can close failure sites in filler-filler and fiber-filler combinations.
15 Den beskrevne reaktionsmekanisme tydeliggør, at det i denne forbindelsen drejer sig om et meget komplext system, i hvilket der også kan optræde synergistiske virkninger. De enkelte komponenter i materialerne ifølge opfindelse - altså fibre, basisfyldstof, anionisk, flokku-20 latdannende aktivt pigment og kationisk kulhydrat - må derfor være nøje afstemt efter hinanden hvad angår art og tilsat mængde.The described reaction mechanism makes it clear that in this connection it is a very complex system in which synergistic effects can also occur. Therefore, the individual components of the materials of the invention - ie, fibers, basic filler, anionic, flocculating active pigment and cationic carbohydrate - must be closely aligned in terms of species and amount added.
Hvad angår de uorganiske fibre foreligger der ikke nogen 25 indskrænkninger. Et formål med opfindelsen er dog at tilvejebringe fiberholdige materialer, hvori de potentielt cancerogene asbestfibre er erstattet med i sundhedsmæssig henseende acceptable fiber. Hertil hører blandt andre glasfibre, mineralfibre, kiselsyrefibre, basaltfibre 30 og/eller aluminiumoxidfibre. Tykkelsen og længden af de uorganiske fibre kan variere indenfor brede områder. Fortrinsvis har mindst 80% af de uorganiske firbre en længde i området fra ca. 1-6 mm. Man kan også anvende blandinger af uorganiske fibre, der adskiller sig fra hinanden hvad 35 angår sammensætning, længde og tykkelse.As for the inorganic fibers, there are no 25 restrictions. It is, however, an object of the invention to provide fibrous materials in which the potentially carcinogenic asbestos fibers have been replaced with acceptable fiber for health reasons. These include glass fibers, mineral fibers, silicic fibers, basalt fibers 30 and / or alumina fibers. The thickness and length of the inorganic fibers may vary within wide ranges. Preferably, at least 80% of the inorganic lizards have a length in the range of from 1-6 mm. Mixtures of inorganic fibers which differ in composition, length and thickness may also be used.
DK 171501 B1 6DK 171501 B1 6
Heller Ikke hvad angår de partikelformede uorganiske basisfyldstoffer foreligger der nogen begrænsninger. Velegnet er f.eks. S102, kaolin, aluminiumoxid, blegejord, gips, calciumcarbonat, titandioxid, perliter, vermicu-5 liter og/eller andre i og for sig kendte papirfyldstoffer eller fyldstoffer til formstofmasser og farver.Nor are there any limitations to the particulate inorganic basic fillers. Suitable is e.g. S102, kaolin, alumina, bleach, gypsum, calcium carbonate, titanium dioxide, perliter, vermiculite, and / or other per se known paper or filler compositions and dyes.
Nogle af disse basisfyldstoffer, såsom gips og blegejord, afgiver ved opvarmning krystalvand eller adsorptionsvand 10 og virker på denne måde brandhæmmende. En dermed samme-lignelig virkning har calciumcarbonat, der ved højere temperaturer afgiver carbondioxid.Some of these basic fillers, such as gypsum and bleaching soil, emit crystal water or adsorption water 10 upon heating and thus act as flame retardant. A similar effect thus has calcium carbonate, which emits carbon dioxide at higher temperatures.
Indholdet af uorganiske basisfyldstoffer andrager i al-15 mindelighed 35-75 vægt-%, fortrinsvis 55-70 vægt-%, beregnet i forhold til den tørre masse.The content of basic inorganic fillers is generally 35-75% by weight, preferably 55-70% by weight, calculated in relation to the dry mass.
Det uorganiske basisfyldstof har fortrinsvis for mellem 35 og 99 vægtprocents vedkommende en partikelstørrelse 20 < 2 am og en partikelstørrelse på > 20 wm for ikke mere end 10 vægtprocents vedkommende.Preferably, the inorganic base filler has between 35 and 99% by weight a particle size of 20 <2 am and a particle size of> 20 wm for no more than 10% by weight.
Det anioniske, flokkulatdannende aktive pigment er fortrinsvis aluminiumhydroxid, bentonlt eller kolloidalt 25 amorft Si02· Indholdet af aktivt pigment andrager i almindelighed ca. 1-15 vægt-%, fortrinsvis 2-10 vægt-%, beregnet i forhold til materialets tørre masse.The anionic flocculant-forming active pigment is preferably aluminum hydroxide, bentonic or colloidal amorphous SiO2. The content of active pigment is generally approx. 1-15% by weight, preferably 2-10% by weight, calculated in relation to the dry mass of the material.
Hvis man anvender et anionisk, kolloidalt, amorft Si02, 30 anvendes dette fortrinsvis i form af en 30-40% vandig dispersion. Fortrinsvis anvender man anioniske kiselsoler, der er fremkommet ved kontakt mellem en fortyndet vandglasopløsning og en sur kationbytter og ældning af den fremkomne sol. De er dispergeret 1 alkalisk medium, 35 der reagerer med siliciumoxid-overfladen og der danner en negativ ladning. På grund af den negative ladning frastøder partiklerne gensidigt hinanden og tilvejebringer DK 171501 B1 7 derved en stabilisering af produktet. Velegnede handelsprodukter kan f.eks. rekvireret under betegnelsen Ludox (varemærke fra firmaet Du Pont), selv om man også kan anvende andre produkter.If an anionic, colloidal, amorphous SiO2 is used, this is preferably used in the form of a 30-40% aqueous dispersion. Preferably, anionic silica sols obtained by contact between a dilute water glass solution and an acidic cation exchanger and aging of the resulting sun are used. They are dispersed in an alkaline medium which reacts with the silica surface and forms a negative charge. Due to the negative charge, the particles mutually repel each other and thereby provide a stabilization of the product. Suitable trading products can e.g. obtained under the designation Ludox (trademark of the company Du Pont), although other products can also be used.
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Hvis man som aktivt pigment anvender aluminiumhydroxid, kan dette fremstilles in statu nascendi ud fra et alkali-aluminat og en syre, fortrinsvis ud fra natriumaluminat og svovlsyre, eller ud fra et aluminiumsalt og alkali, 10 fortrinsvis ud fra aluminiumsulfat og natronlud.If aluminum pigment is used as an active pigment, this can be prepared in statu nascendi from an alkali aluminate and an acid, preferably from sodium aluminate and sulfuric acid, or from an aluminum salt and alkali, preferably from aluminum sulphate and sodium hydroxide.
Hvis man som aktivt pigment anvender bentonit, foretrækkes kvældedygtigt alkalibentonit.If bentonite is used as active pigment, swellable alkali bentonite is preferred.
15 Forholdet mellem de uorganiske partikelformede additiver og det kationiske polymer kulhydrat vælges fortrinsvis på en sådan måde, at der ikke foreligger noget ladningsoverskud, således at der dannes et optimalt flokkulat.Preferably, the ratio of the inorganic particulate additives to the cationic polymer carbohydrate is chosen in such a way that there is no charge excess to form an optimum flocculate.
20 Foretrukne polymer kulhydrater er kationiske stivelser, kationisk amylopectin, kationiske galatomannaner (f.eks. guar eller cassia) og/eller kationisk carboxymethylcellu-lose. Kulhydraterne kan på i og for sig kendt måde kationiseres, ved at de eventuelt hydrolyserede udgangsku1-25 hydrater kvaterniseres med kvaternære ammoniumforbindelser. Men kulhydratet kan også kationiseres i henhold til tørkationiseringsmetoden. Til de kationiske kulhydrater kan man også tilsætte kationiske polyvinylalkoholer.Preferred polymer carbohydrates are cationic starches, cationic amylopectin, cationic galatomannans (e.g., guar or cassia) and / or cationic carboxymethyl cellulose. The carbohydrates can be cationized in a manner known per se by quaternizing the optionally hydrolyzed starting carbonates with quaternary ammonium compounds. But the carbohydrate can also be cationized according to the dry cation method. Cationic polyvinyl alcohols can also be added to the cationic carbohydrates.
30 Indholdet af polymert, kationisk kulhydrat andrager i regelen 1-5 vægt-%, fortrinsvis 1-3 vægt-%, beregnet i forhold til materialets tørre masse. Dette afhænger i det væsentlige af det ønskede anvendelsesområde. Hvis man vil fremstille materialer med høj temperaturbestandighed, 35 anvender man det polymere, kationiske kulhydrat i ringe mængder. Materialer til anvendelse ved høje temperaturer er f.eks. tætningsmaterialer i den kemiske industri og i DK 171501 B1 8 motorindustrien samt temperaturbestandige filtermaterialer til varme gasser og væsker. Desuden kan materialerne Ifølge opfindelsen også anvendes ved højere kulhydratkoncentrationer som isolationsmaterialer i byggeindustrien, 5 især ved tørre byggearbejder, f.eks. som kabelspor og brandbeskyttelsesisolationer, til brandbeskyttelsesdøre, væg- og loftpaneler, bærelag til varmeisolerende materialer samt til Ildfaste displays til salgsformål (i varehuse). Et yderligere vigtigt anvendelsesområde ligger på 10 det område, der omfatter bygning af fartøjer, fordi materialerne ifølge opfindelsen ved siden af deres temperaturbestandighed har en lav massefylde. Heller ikke ved et højere indhold af kationisk kulhydrat forekommer der nogen antændelse af materialet, idet det kationiske 15 kulhydrat kun forkulles.The polymeric cationic carbohydrate content is generally 1-5% by weight, preferably 1-3% by weight, calculated in relation to the dry mass of the material. This essentially depends on the desired scope. To produce materials with high temperature resistance, the polymeric cationic carbohydrate is used in small amounts. Materials for use at high temperatures are e.g. sealing materials in the chemical industry and in the DK 171501 B1 8 engine industry as well as temperature resistant filter materials for hot gases and liquids. In addition, the materials of the invention can also be used at higher carbohydrate concentrations as insulating materials in the construction industry, especially in dry construction work, e.g. such as cable tracks and fire protection insulation, for fire protection doors, wall and ceiling panels, support layers for heat insulating materials and for refractory displays for sale purposes (in warehouses). A further important area of application lies in the area comprising building vessels, because the materials of the invention, in addition to their temperature resistance, have a low density. Also, at a higher content of cationic carbohydrate, no ignition of the material occurs, the cationic carbohydrate being charred only.
Det kationiske polymere kulhydrat har i almindelighed en gennemsnitlig molekylevægt på fra 200000 til 1000000, fortrinsvis mellem 300000 og 800000, og en substitutions-20 grad mellem 0,15 og 0,02.The cationic polymeric carbohydrate generally has an average molecular weight of from 200000 to 1000000, preferably between 300000 and 800000, and a degree of substitution between 0.15 and 0.02.
Materialerne ifølge opfindelsen kan desuden indeholde kationiske, anioniske eller ikke-ionogene retentionshjælpemidler. Det drejer sig herved i reglen om de i papirindu- 25 strien sædvanlige retentionshjælpemidler, der fortrinsvis tilsættes i mængder mellem ca. 0,02 og 0,2 vægt-%, beregnet i forhold til materialets tørre masse.The materials of the invention may additionally contain cationic, anionic or nonionic retention aids. As a rule, these are the usual retention aids used in the paper industry, which are preferably added in amounts between about 10%. 0.02 and 0.2% by weight, calculated relative to the dry mass of the material.
Som retentionshjælpemiddel kan man f.eks. anvende et 30 kationisk polyacrylamid med en molekylevægt på fra ca. Ι-ΙΟ millioner eller en polyethylenimin med en molekylevægt på ca. 80000 til 300000.As a retention aid, for example, use a cationic polyacrylamide having a molecular weight of from ca. Ι-ΙΟ million or a polyethyleneimine having a molecular weight of approx. 80000 to 300000.
Materialerne ifølge opfindelsen kan desuden indeholde 35 midler til forøgelse af den våde styrke, fortrinsvis i en mængde af ca. 0,2-5 vægt-%, beregnet på materialets tørre masse. Velegnede midler til forøgelse af den våde styrke DK 171501 B1 9 er f.eks. urinstof- eller melamin-formaldehydharpikser, polyamidamin-epichlorhydrinharpikser og lignende.The materials of the invention may additionally contain 35 agents for increasing the wet strength, preferably in an amount of approx. 0.2-5% by weight, based on the dry mass of the material. Suitable means for increasing the wet strength DK 171501 B1 9 are e.g. urea or melamine formaldehyde resins, polyamidamine epichlorohydrin resins and the like.
Opfindelsen omfatter tillige omdannelsen af materialerne 5 ifølge opfindelsen til tredimensionale formlegemer. Hertil hører bl.a. rør, skaller, filterlegemer, isolationsvægge , tætningselementer o.s.v.The invention also includes the conversion of the materials 5 of the invention into three-dimensional mold bodies. These include: pipes, shells, filter bodies, insulation walls, sealing elements, etc.
Materialerne Ifølge opfindelsen fremstilles fortrinsvis 10 ved, at man blander en vandig dispersion af de uorganiske fibre og de partikelformede, uorganiske basisfyldstoffer med en vandig suspension af det aktive pigment, og at man til denne blanding kort før formgivningen tilsætter det kationiske polymere kulhydrat. Formgivningen kan f.eks.The materials of the invention are preferably prepared by mixing an aqueous dispersion of the inorganic fibers and the particulate, inorganic base fillers with an aqueous suspension of the active pigment and adding to the mixture shortly before shaping the cationic polymeric carbohydrate. The design can e.g.
15 gennemføres på en papir- eller papmaskine. 1 dette tilfælde taler man om en bladdannelse. Fremstillingen af de tredimensionale formlegemer foregår fortrinsvis i henhold til fiberstøbemetoden. Men det er også muligt at henlægge det endnu fugtige ark i en tredimensional form og at 20 tørre den.15 is carried out on a paper or cardboard machine. In this case, one is talking about leaf formation. The preparation of the three-dimensional mold bodies is preferably carried out according to the fiber molding method. But it is also possible to lay the still moist sheet in a three-dimensional form and to dry it.
Formgivningen gennemføres fortrinsvis efter, at der har dannet sig et flokkulat i den vandige blanding efter tilsætningen af det kationiske polymere kulhydrat.The shaping is preferably carried out after a flocculate has formed in the aqueous mixture after the addition of the cationic polymeric carbohydrate.
2525
Formgivningen gennemføres fortrinsvis efter at der er forløbet mindst 10 sekunder efter tilsætningen af det kationiske polymere kulhydrat. Retentionshjælpemidlet tilsættes fortrinsvis efter tilsætningen af det kationiske 30 polymere kulhydrat.The shaping is preferably carried out after at least 10 seconds have elapsed after the addition of the cationic polymeric carbohydrate. The retention aid is preferably added after the addition of the cationic polymeric carbohydrate.
For at opnå homogene produkter fremstiller man fortrinsvis separate våde dispergeringer af de uorganiske fibre og de uorganiske basisfyldstoffer før tilvejbringeisen af 35 dispersionen, hvorpå man sammenblander de separte disper sioner med hinanden. På denne måde sikrer man sig, at hver bestanddel bliver optimalt dispergeret ved udvælgel- DK 171501 B1 10 se a£ en velegnet omrøringshastighed, omrøringsvarighed o.s.v. F.eks. afhænger dlspergerlngsparametrene af beskaffenheden, partikelstørrelsen og massefylden af basisfyldstof partiklerne .In order to obtain homogeneous products, separate wet dispersions of the inorganic fibers and the basic inorganic fillers are preferably prepared prior to the formation of the dispersion, whereupon the separate dispersions are mixed together. In this way, it is ensured that each component is optimally dispersed by selecting a suitable agitation rate, agitation duration, etc. For example. the interlock parameters depend on the nature, particle size and density of the base filler particles.
55
Til den blandede dispersion af uorganiske fibre og uorganiske baslsfyldstofpartikler tilsætter man derpå den vandige dispersion af de aktive pigmenter, hvorpå det katlo-niske kulhydrat tilsættes kort før bladdannelsen (ca. 10-10 30 sekunder) tilsættes. Derpå tilsættes retentionsmidlet.To the mixed dispersion of inorganic fibers and inorganic bases filler particles is then added the aqueous dispersion of the active pigments, to which the catholic carbohydrate is added shortly before leaf formation (about 10-10 30 seconds). Then the retention agent is added.
Opfindelsen forklares nærmere ved hjælp af de følgende eksempler.The invention is further explained by the following examples.
15 EKSEMPEL 1-6EXAMPLES 1-6
Man fordispergerer langfibrede glasfibre (2-6 mm) i vand. Derpå fremstiller man en separat fordispersion af mineralfibre med en fiberlængde på indtil ca. 3 mm. Som mine-20 ralfiber anvendes handelsproduktet "Inorphil" (varemærke fra firmaet Laxå, Sverige). Vægtandelene mellem glasfibre og mineralfibre er angivet i tabel 1. Derpå fremstiller man en dispersion af kaolin (basisfyldstof). Partikelstørrelserne og vægtandelene af de anvendte kaolinsorter 25 er også angivet i tabel I.Long-fiber glass fibers (2-6 mm) are dispersed in water. Then a separate redispersion of mineral fibers having a fiber length of up to approx. 3 mm. The mineral product "Inorphil" (trademark of the company Laxå, Sweden) is used as mineral fiber. The weight ratios between glass fibers and mineral fibers are given in Table 1. Then a dispersion of kaolin (base filler) is prepared. The particle sizes and weight percentages of the kaolin species 25 are also listed in Table I.
De tre fordispersioner bliver grundigt blandet med en dispersion af kollidalt, amorft Si02· Dispersionens vandindhold andrager ca. 60-70 vægt-%.The three dispersions are thoroughly mixed with a dispersion of collidally amorphous SiO 2 · The water content of the dispersion is approx. 60-70% by weight.
3030
Derpå tilsætter man en opløsning af kationisk stivelse (handelsprodukt Amijel, Q-Tak 210 fra firmaet Cerestar) (tørstofindhold af opløsningen = 1 vægt-%). Vægtandelen af kolloidalt Si02 og kationisk stivelse er også angivet 35 i tabel I.Then a solution of cationic starch (commercial product Amijel, Q-Tak 210 from Cerestar company) is added (solids content of the solution = 1% by weight). The weight ratio of colloidal SiO 2 and cationic starch is also given in Table I.
DK 171501 B1 11DK 171501 B1 11
Efter tilsætning af den kationiske stivelse danner der sig et flokkulat. I eks. 6 tilsætter man desuden et kati-onisk polyacrylamid som retentionsmiddel (Nalco 47-32; varemærke fra firmaet Nalco Chemical Co.) i den i tabel I 5 angivne mængde.After addition of the cationic starch, a flocculate forms. In Example 6, a cationic polyacrylamide as a retention agent (Nalco 47-32; trademark of the company Nalco Chemical Co.) is also added in the amount given in Table I 5.
Ca. 20 sekunder efter tilsætningen af den kationiske stivelse indføres den vandige masse i et bladdannelsesanlæg af laboratorietypen i henhold til Rapid-KOthen, hvor-10 på den vandige fase frasuges. Man opnår et blad, som efter tørringen har en tykkelse af ca. 0,3 mm. Trækstyrkerne af forsøgsbladene er angivet i tabel I.Ca. Twenty seconds after the addition of the cationic starch, the aqueous mass is introduced into a Rapid-KOthen laboratory-type leaf formation plant in which 10 of the aqueous phase is aspirated. A leaf is obtained which after drying has a thickness of approx. 0.3 mm. The tensile strengths of the test blades are given in Table I.
Som det fremgår af eksemplerne 1 til 6 tiltager styrken 15 kraftigt, hvilket er overraskende og i modsætning til, hvad man ved i papirindustrien i dag, med voksende ind hold af basisfyldstof og voksende partikelfinhed under samtidig bibeholdelse af udmærkede værdier for retentionen.As can be seen from Examples 1 to 6, Strength 15 increases sharply, which is surprising and contrary to what is known in the paper industry today, with increasing content of base filler and growing particle fineness while maintaining excellent values for retention.
2020
Allerede sammenligningseksemplerne 1 og 3 viser indflydelse af partikelfinheden, mens sammenligningseksemplerne 3 og 4 viser indflydelsen af fyldstofindholdet på den mekaniske styrke.Already Comparative Examples 1 and 3 show the influence of particle fineness, while Comparative Examples 3 and 4 show the influence of filler content on mechanical strength.
2525
Eksemplerne 2, 5 og 6 ifølge opfindelsen viser de fra tilsætningen af det anioniske flokkulatdannende aktive pigment betingede stigninger i styrken, idet den i henhold til eks. 5 i sammenligning med eks. 2 tilvejebragte 30 forøgede styrke også er betinget af den større andel og den højere partikelfinhed af basisfyldstoffet.Examples 2, 5 and 6 of the invention show the increases in the strength conditional on the addition of the anionic flocculant-forming active pigment, since the increased strength according to Example 5 compared to Example 2 is also dependent on the greater proportion and the higher particle fineness of the base filler.
Eks. 6 viser, at styrken i forhold til materialet i det nærmest sammenlignelige eksempel 5 kan forøges yderligere 35 ved anvendelse af et retentionshjælpemiddel.Ex. 6 shows that the strength relative to the material of the nearly comparable Example 5 can be further increased by using a retention aid.
EKSEMPEL 7-10 DK 171501 B1 12EXAMPLES 7-10 DK 171501 B1 12
Fremstillingen af fiber- og fyldstof-fordispersionen foretages i henhold til eksemplerne 1 til 6, hvorved man 5 anvender de i tabel II angivne stoffer og vægtforhold. Blandingen af fordispersionen med de andre bestanddele samt bladdannelsen gennemføres ligeledes som angivet i eksemplerne 1 til 6.The preparation of the fiber and filler dispersion is carried out according to Examples 1 to 6, using the substances and weight ratios listed in Table II. The mixing of the dispersion with the other components as well as the leaf formation is also carried out as indicated in Examples 1 to 6.
10 1 eks. 7 anvender man som aktivt pigment i stedet for den kolloidale, amorfe kiselsyre en aluminiumhydroxid-disper-sion, der blev fremstillet in situ af aluminiumsulfat og natriumhydroxid.In Example 7, as active pigment, instead of the colloidal, amorphous silicic acid, an aluminum hydroxide dispersion made in situ of aluminum sulfate and sodium hydroxide is used.
15 1 eks. 8 anvender man bentonit som aktivt pigment. Eks. 9 blev optaget som sammenligningseksempel (uden aktivt pigment ).In Example 8, bentonite is used as active pigment. Ex. 9 was included as a comparative example (without active pigment).
Eksemplerne 7 til 10 skal vise indfyldelsen af de for-20 skellige, flokkulatdannende aktive pigmenter på styrkeegenskaberne af de ikke brændbare, uorganiske materialer ifølge opfindelsen. Udvalget og mængden af det flokkulatdannende atkive pigment er i vidt omfang afhængigt af egenskaberne af basisfyldstoffet. Den anvendte mængde 25 af organiske hjælpemidler, såsom kulhydrater, er i høj grad begrænset ved kravene til ikke-brændbarhed. På grund af tilsætningen af aktive pigmenter til basisfyldstoffet bliver suspensionen "forskudt" i retning af det i hvert tilfælde gunstige flokkuleringsområde, og først 30 herved opnår man en acceptabel, mekanisk styrke.Examples 7 to 10 show the filling of the various flocculating active pigments on the strength properties of the non-combustible inorganic materials of the invention. The range and amount of flocculating pigment is largely dependent on the properties of the base filler. The amount of organic aids used, such as carbohydrates, is greatly limited by the non-flammability requirements. Due to the addition of active pigments to the base filler, the suspension is "staggered" towards the favorable flocculation area in each case, and only 30 to obtain an acceptable mechanical strength.
Dette dokumenteres ved en sammenligning af styrkerne af materialerne i henhold til eks. 1, 3 (tabel I) og 9, ved hvilke der ikke anvendtes noget aktivt pigment, med 35 de i hvert tilfælde tilsvarende værdier i de øvrige eksempler.This is documented by a comparison of the strengths of the materials according to Examples 1, 3 (Table I) and 9, in which no active pigment was used, with the corresponding values in each case in the other examples.
EKSEMPEL 11-15 DK 171501 B1 13EXAMPLES 11-15 DK 171501 B1 13
Fremstillingen af fordispersionerne, sammenblandingen af dispersionerne samt bladdannelsen gennemføres som angivet 5 i eks. 1 til 6. De enkelte stoffer samt deres vægtandele er angivet i tabel III. De i denne tabel angivne eksempler viser, at man kan anvende forskellige kationiske kulhydrater, når de udviser en velegnet substitutionsgrad (DS) og en velegnet molekylvægt.The preparation of the dispersion dispersions, the mixing of the dispersions and the leaf formation are carried out as indicated 5 in Examples 1 to 6. The individual substances and their weight proportions are given in Table III. The examples given in this table show that various cationic carbohydrates can be used when exhibiting a suitable degree of substitution (DS) and a suitable molecular weight.
10 I eks. 15 anvendte man en kombination af to forskellige kulhydrater, som ligeledes giver brugbare styrkeværdier.In Example 15, a combination of two different carbohydrates was used which also gives usable strength values.
Tilsvarende blade kan fremstilles på egnede papir-15 eller papmaskier (lang- eller rundsi) i enhver passende tykkelse. Den totale retention udgør i afhængighed af recept og maskintype mellem 85 og 95%. Afhængigt af arten og mængden af de anvendte fibermaterialer og fyldstoffer 3 kan massefylden variere mellem 500 og 1000 kg/m . Isola-20 tionsevnen og dermed anvendelsesmuligheden afhænger hovedsageligt af massefylden af det tilvejebragte materiale, mens temperaturbestandigheden først og fremmest afhænger af fibrenes smeltepunkt. I de angivne eksempler på recepter vil erstatning af glasfibrene med andre fibre 25 med en større temperaturbestandighed være problemløs og uden negative virkninger på de mekaniske egenskaber.Corresponding blades can be made on suitable paper or cardboard (long or circular sieve) of any suitable thickness. Total retention, depending on prescription and machine type, amounts to between 85 and 95%. Depending on the nature and amount of the fiber materials and fillers used 3, the density may vary between 500 and 1000 kg / m. The insulation capacity and thus the applicability depends mainly on the density of the material provided, while the temperature resistance depends primarily on the melting point of the fibers. In the examples given above, replacing the glass fibers with other fibers 25 having a greater temperature resistance will be problem-free and without adverse effects on the mechanical properties.
30 35 14 DK 171501 B130 35 14 DK 171501 B1
Tabel ITable I
Eks. nr. 123456 5 vægt-%Ex. No. 123456 5% by weight
Mineralfiber (- 3 ram) 32,5 26,5 32,5 18,5 18,5 18,5 10 Glasfiber (2-6 mm) 15,0 11,0 15,0 9,0 9,0 9,0Mineral fiber (- 3 frame) 32.5 26.5 32.5 18.5 18.5 18.5 10 Fiberglass (2-6 mm) 15.0 11.0 15.0 9.0 9.0 9.0
Kaolin nr. 1 struktur af de 15 små plader (46% <2 vm) 50,0 54,5 --- --- --- ---Kaolin # 1 structure of the 15 small plates (46% <2 sqm) 50.0 54.5 --- --- --- ---
Kaolin nr. 2 struktur af de 20 små plader (71% <2 urn) — —- 50,0 70,0 64,5 64,5Kaolin # 2 structure of the 20 small plates (71% <2 µm) - 50.0 70.0 64.5 64.5
Kolloidalt amorft Si02 25 (partikelstør- else 15 - 20 nm) --- 5,5 --- --- 5,5 5,5Colloidal Amorphous SiO2 (Particle Size 15-20 nm) --- 5.5 --- --- 5.5 5.5
Kat. stivelse Molvægt 800000 30 - 1 mio.Cat. starch Molar weight 800000 30 - 1 ml.
DS: 0,05 2,5 2,5 2,5 2,5 2,5 2,45DS: 0.05 2.5 2.5 2.5 2.5 2.5 2.45
Kat. polyacryl- amid (Nalco 47-32)--- --- --- --- --- 0,05Cat. polyacrylamide (Nalco 47-32) --- --- --- --- --- 0.05
Trækstyrke (MPa) 0,9 3,8 2,3 4,0 5,3 5,6 35 15 DK 171501 B1Tensile strength (MPa) 0.9 3.8 2.3 4.0 5.3 5.6 35 DK 171501 B1
Tabel IITable II
Eks. nr._7_8_9_10 vægt-% 5 Mineralfiber (- 3 mm) 26,5 26,5 26,5 26,5Ex. No. 7_8_9_10% by weight 5 Mineral fiber (- 3 mm) 26.5 26.5 26.5 26.5
Glasfiber (2-6 mm) 11,0 11,0 11,0 11,0 10Fiberglass (2-6 mm) 11.0 11.0 11.0 11.0 10
Kaolin nr. 2 struktur af de små plader (71% <2 um) 56,6 58,0 15Kaolin # 2 structure of the small plates (71% <2 µm) 56.6 58.0 15
Kaolin nr. 3 struktur af de små plader (45% <2 um) --- --- 60,0 54,5 20Kaolin # 3 structure of the small plates (45% <2 µm) --- --- 60.0 54.5 20
Aluminiumsulfat 2,0 --- --- ---Aluminum sulphate 2.0 --- --- ---
Natriumhydroxid 1,4 --- --- --- 25 Bentonit --- 2,0 --- ---Sodium Hydroxide 1.4 --- --- --- Bentonite --- 2.0 --- ---
Kolloidalet amorft Si02 (partikelstørrelse 30 15 - 20 nm) --- --- --- 5,5Colloidal amorphous SiO 2 (particle size 30 - 20 nm) --- --- --- 5.5
Kat. stivelse Molvægt 800000 - 1 mio. DS 0,05 2,5 2,5 2,5 2,5Cat. starch Molar weight 800000 - 1 million DS 0.05 2.5 2.5 2.5 2.5
Trækstyrke (MPa) 4,2 4,4 1,3 4,2 35Tensile strength (MPa) 4.2 4.4 1.3 4.2 35
Tabel IIITable III
DK 171501 B1 16DK 171501 B1 16
Eks. nr. 11 12 13 14 15 5 vægt-%Ex. No. 11 12 13 14 15 5% by weight
Mineralfiber (- 3 nun) 19.0 27,0 27,0 18,5 27,0Mineral fiber (- 3 nun) 19.0 27.0 27.0 18.5 27.0
Glasfiber (2-6 nun) 9,5 11,5 11,5 9,0 11,0 10 Kaolin nr. 2 struktur af de små plader (71% <2 um) --- 54,5 54,5 --- 54,0Fiberglass (2-6 nun) 9.5 11.5 11.5 9.0 11.0 10 Kaolin No. 2 structure of the small sheets (71% <2 µm) --- 54.5 54.5 - - 54.0
Calciumcarbonat 15 (99% <2 um) 68,0 --- --- 64,5 ---Calcium carbonate (99% <2 µm) 68.0 --- 64.5 ---
Alkalisk aktiveret bentonit 2,0 --- --- --- ---Alkaline activated bentonite 2.0 --- --- --- ---
Kolloidalt amorft Si02 (partikelstør- 20 relse 15 - 20 nm) --- 5,5 5,5 5,5 5,5Colloidal amorphous SiO 2 (particle size 15-20 nm) --- 5.5 5.5 5.5 5.5
Kat. guar nr. 1 DS: 0,11 1,5 --- --- --- ---Cat. Guar No. 1 DS: 0.11 1.5 --- --- --- ---
Kat. guar nr. 2 DS: 0,02 --- 1,5 --- --- --- 25 Kat. guar nr. 3 DS: 0,1 --- — 1,5 --- 1,0Cat. Guar No. 2 DS: 0.02 --- 1.5 --- --- --- 25 Cat. Guar No. 3 DS: 0.1 --- - 1.5 --- 1.0
Kat. cassiaCat. cassia
Molvægt 400000 --- --- --- 2,5 ---Molecular weight 400000 --- --- --- 2.5 ---
Kat. stivelse 30 molvægt 800000 - 1 mio.Cat. starch 30 mole weight 800000 - 1 million
DS: 0,05 --- --- --- --- 1,0DS: 0.05 --- --- --- --- 1.0
Trækstyrke (MPa) 4,0 4,1 4,0 4,7 4,2 35Tensile strength (MPa) 4.0 4.1 4.0 4.7 4.2 35
Claims (25)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3837746A DE3837746C1 (en) | 1988-11-07 | 1988-11-07 | |
| DE3837746 | 1988-11-07 | ||
| PCT/EP1989/001287 WO1990005211A2 (en) | 1988-11-07 | 1989-10-28 | Paper-like or cardboard-like raw material and process for making it |
| EP8901287 | 1989-10-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK163590A DK163590A (en) | 1990-07-06 |
| DK163590D0 DK163590D0 (en) | 1990-07-06 |
| DK171501B1 true DK171501B1 (en) | 1996-12-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| DK163590A DK171501B1 (en) | 1988-11-07 | 1990-07-06 | Paper-like or cardboard-like material and process for its preparation |
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|---|---|
| EP (1) | EP0399010B1 (en) |
| JP (1) | JPH03502219A (en) |
| AU (1) | AU620470B2 (en) |
| BR (1) | BR8907153A (en) |
| CA (1) | CA2001784A1 (en) |
| DE (2) | DE3837746C1 (en) |
| DK (1) | DK171501B1 (en) |
| ES (1) | ES2017306A6 (en) |
| FI (1) | FI93757C (en) |
| GR (1) | GR1000750B (en) |
| IE (1) | IE61832B1 (en) |
| NO (1) | NO176028C (en) |
| PT (1) | PT92183B (en) |
| WO (1) | WO1990005211A2 (en) |
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| US5145811A (en) * | 1991-07-10 | 1992-09-08 | The Carborundum Company | Inorganic ceramic papers |
| JPH0995044A (en) * | 1995-04-10 | 1997-04-08 | Canon Inc | Recording paper and ink jet recording using recording paper |
| ES2675222T3 (en) * | 2003-12-22 | 2018-07-09 | Akzo Nobel Chemicals International B.V. | Loading material for a papermaking process |
| EP1697587B1 (en) * | 2003-12-22 | 2009-04-22 | Akzo Nobel N.V. | Paper comprising quaternary nitrogen containing cellulose ether |
| EP2466004B1 (en) * | 2007-02-19 | 2016-06-22 | 3M Innovative Properties Company | Flexible fibrous material, pollution control device, and methods of making the same |
| JP5855348B2 (en) * | 2011-03-29 | 2016-02-09 | アイカ工業株式会社 | Non-flammable substrate |
| JP5876743B2 (en) * | 2012-02-09 | 2016-03-02 | 大王製紙株式会社 | Method for producing composite particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3253978A (en) * | 1961-07-19 | 1966-05-31 | C H Dexter & Sons Inc | Method of forming an inorganic waterlaid sheet containing colloidal silica and cationic starch |
| GB1604908A (en) * | 1977-08-08 | 1981-12-16 | Minnesota Mining & Mfg | Flexible intumescent sheet material with fired strength |
| GB2047297A (en) * | 1979-04-04 | 1980-11-26 | Ici Ltd | Mineral-fibre boards |
| AU546999B2 (en) * | 1980-05-28 | 1985-10-03 | Eka A.B. | Adding binder to paper making stock |
| SE8107078L (en) * | 1981-11-27 | 1983-05-28 | Eka Ab | PAPER MANUFACTURING PROCEDURE |
| US4578150A (en) * | 1982-07-23 | 1986-03-25 | Amf Inc. | Fibrous media containing millimicron-sized particulates |
| US4443262A (en) * | 1982-09-30 | 1984-04-17 | Armstrong World Industries, Inc. | Low density fibrous sheet material |
| DE3306528A1 (en) * | 1982-12-30 | 1984-07-05 | Lüchtrath, Bern, 8700 Würzburg | PAPER, CARDBOARD AND PAPER-LIKE MATERIAL |
| DE3306478A1 (en) * | 1982-12-30 | 1984-07-12 | Bern 8700 Würzburg Lüchtrath | FILLER FOR A PAPER, CARDBOARD OR PAPER-LIKE MATERIAL AND METHOD FOR PRODUCING SUCH MATERIAL |
| GB8621680D0 (en) * | 1986-09-09 | 1986-10-15 | Du Pont | Filler compositions |
-
1988
- 1988-11-07 DE DE3837746A patent/DE3837746C1/de not_active Expired - Lifetime
-
1989
- 1989-10-02 GR GR890100627A patent/GR1000750B/en unknown
- 1989-10-28 EP EP89912436A patent/EP0399010B1/en not_active Expired - Lifetime
- 1989-10-28 WO PCT/EP1989/001287 patent/WO1990005211A2/en active IP Right Grant
- 1989-10-28 DE DE8989912436T patent/DE58903410D1/en not_active Expired - Fee Related
- 1989-10-28 BR BR898907153A patent/BR8907153A/en not_active IP Right Cessation
- 1989-10-28 AU AU45140/89A patent/AU620470B2/en not_active Ceased
- 1989-10-28 JP JP1511642A patent/JPH03502219A/en active Pending
- 1989-10-30 CA CA002001784A patent/CA2001784A1/en not_active Abandoned
- 1989-11-03 ES ES8903724A patent/ES2017306A6/en not_active Expired - Lifetime
- 1989-11-03 PT PT92183A patent/PT92183B/en not_active IP Right Cessation
- 1989-11-06 IE IE355989A patent/IE61832B1/en not_active IP Right Cessation
-
1990
- 1990-07-06 DK DK163590A patent/DK171501B1/en not_active IP Right Cessation
- 1990-07-06 NO NO903041A patent/NO176028C/en unknown
- 1990-07-06 FI FI903434A patent/FI93757C/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| CA2001784A1 (en) | 1990-05-07 |
| FI93757C (en) | 1995-05-26 |
| FI903434A0 (en) | 1990-07-06 |
| GR1000750B (en) | 1992-12-30 |
| JPH03502219A (en) | 1991-05-23 |
| DK163590A (en) | 1990-07-06 |
| IE61832B1 (en) | 1994-11-30 |
| BR8907153A (en) | 1991-02-26 |
| EP0399010B1 (en) | 1993-01-27 |
| DK163590D0 (en) | 1990-07-06 |
| NO176028C (en) | 1995-01-18 |
| ES2017306A6 (en) | 1991-01-16 |
| EP0399010A1 (en) | 1990-11-28 |
| NO176028B (en) | 1994-10-10 |
| DE3837746C1 (en) | 1990-03-29 |
| AU620470B2 (en) | 1992-02-20 |
| NO903041D0 (en) | 1990-07-06 |
| IE893559L (en) | 1990-05-07 |
| NO903041L (en) | 1990-07-06 |
| AU4514089A (en) | 1990-05-28 |
| WO1990005211A2 (en) | 1990-05-17 |
| DE58903410D1 (en) | 1993-03-11 |
| PT92183B (en) | 1995-08-09 |
| PT92183A (en) | 1990-05-31 |
| FI93757B (en) | 1995-02-15 |
| GR890100627A (en) | 1990-12-31 |
| WO1990005211A3 (en) | 1990-06-28 |
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| B1 | Patent granted (law 1993) | ||
| PBP | Patent lapsed | ||
| PBP | Patent lapsed |