AU620470B2 - Paper-like or cardboard-like raw material and process for making it - Google Patents

Description

"6O 4p 0: ANNOUNCEMENT OF THE LATER PUBUCA TION U' OF INTERNA TICWAL SEARCH REPORTS INTERNA[TONALE AN MELDUNG YEROFFE3NTLICHT NACH DEM VERTRAG OBER DIE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (PCT) (51) Internationale Patentkclassiflkation 5 (11) Internationale Verbffentlichungsnummer: WO 90/05211 D21H 21/52, 13/36 A3 (43) Internationales Veroft'entlichungsdatum: 17. Mai 1990 (17.05.90) (21) Internationales Aktenzeiv,-hen: PCT/EP89/0 1287 Vergffentlicht M11 intemiationalem. Recherchenbericht.

(22) InternationrIes Annmeidedatumn: 28. Oktober 1989 (28.10.89) VorAbiauf derffirAnderungen der Ansprichezuge,',;ssen Frisi. Veroffentfichung wird wiederhol fialls Anderungen Prioritlitsdaten:enrfe.

P38774.2 Nvemer 988(0711.8)8E Verbohtlichunsdatu des internationalen Recherchenbe- Anmelder und Erfinder: ZEIJNER, Manfred [DE/DE]; 28. Juni 1990 (28.06.90 DOBLAxNZKsI, Peter [DE/DE]1; Frauenfeld 7, D-8359 Orten )urg (DE).

(74) Anwiilte SPLANEMANN, R. usw. ;Tat 13, D-8000 MOnchen 2 (DE).

(81) Besti3mmungsshiate~n: AT (europdisches Patent), AU, BE (euiropfiisches Patent), BR, CH- (europflisches Patent), DE (europflisches Patent, DK, Fl, FR (europaisches Patent), GB (europiisches3 Patent), IT (europiiisches Patent), JP, KP, LU (Curopfiisches Patent), NL (europtiisches Patent), NO, SE (europtiisches Patent), US.

(54)Title: PAPER-LIKE OR CARDBOARD-LIKE RAW MATERIAL AND PROCESS FOR MAKING IT

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STELLUNG

(57) Abstract A paper-like or cardboard-like raw material containing inorganic fibres, particulate inorganic additives and organic biniders or flocculents is characterized in that the particulate inorganic additives comprise 40-80 wvt. of the dry mass of the -caw material; the particulate inorganic additives contain 1) a basic filler of which at least 20 wt, has a particle size 2 l.1m and not more than 20 wt. has a particle size 20 lim and 0.5 and an anionic flocculating active pigment of which at least 50 wt. has a primary particle size 2 lim; 1) the organic flocculant is a cationic polymeric carbohydrate with a mean molecular we-ght between 100 000 and 2 000 000 and a degree of substitution between 0.01 and 0.3 and amounts to 0.5 to 6 wt. of the dry mass of the raw mateu ial; 1000 g of basic filler may bind, with Hloc formation, not more than 0, 1 mmol of cationic carbohydrate and 1000 g of anionic flocculating active pigment binds, with Hoc formation, at east 0, 1 nmmol of cationic carbohydrate.

(57) Zusammenfassung Emn papier-, karton- oder pappenartiger Werkstoff enthaltencl anorganische Fasern, anorganische teilchenfd5rmige Zustltze und organische Binde- oder Flockungsmittel ist dadurch gekennzeichnet, dali die teil,nenf6rmigen anorganischen ZwuItze 40-80 Gew.-% der Trockenmasse des Werkstoffs ausmachen; dali die anorganischen teilchonf~rmigen Zusitze aus 1) einemn Basisftillstoff, von dem mindestens 20 Gew.-% eine Teilchengr5le von 2 ltm und nicht mwhr als 20 Gev eine Teilchengrblie von 20 jini einerseits und von 0,5 lim andererseits haben, und einemn anionischer llockenibildenden Aktivpigment, von dem mindestens 50 Gew.-% eine Primilrteilchengr~lie von 2 [tun Itioben, zusammengesetzt sind; dali das organische Flokkungsmittel ein kationiscbes polymeres Kohlenhydrat mit einemn mittleren Molekulargewicht von 100 000 bis 2 000 000 und elnem Substitutionsgrad von 0,01 bis 0,3 darstellt und, in einer Menge von 0,5 bis 6 bezogen auf die Trockenmasse des Werkstoffs, vorliegt und dali 1000 g Basisfillistoff nicht mehr als 0,1 mMoI und 1000 g anionisches flockenbilderdes Aktivpigment mindestens 0,1 mMoI kationisches Koblenhydrat unter Flockenibildung zu binden

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4 Paper, cardboard or paperboard-like material and a process for its production The present invention relates to paper, cardboard-or paperboard-like material with a very high portion of inorganic constituents, namely inorganic fibres and inorganic particulate additives, i.e. fillers and pigments.

It is generally known that the strength of paper based on organic fibres is dependent on the formation of hydrogen bonds between the organic fibres. It is also known that by mechanically parating the fibres from one another the inorganic fillers re- *9 duce the fibre surfaces available for binding with hydrogen bonds Sor block the spots on the fibre capable of binding and replace them with weaker fibre-filler-fibre bonds, whereby fine fillers reduce the strength considerably.

Thus, if only inorganic fibres and fillers are used during the manufacture of paper or paperboard-like materials, i.e.

substances that are not capable of binding with hydrogen bonds, then the strength of the materials obtained is low.

Paper-like materials containing inorganic fibres such as glass fibres or mineral wool fibres, inorganic particulate fillers such as clay and bentonite, and hydrolyzed starch as the .organic binder are known from EP-A-0 109 782 and EP-A-0 027 705.

However, organic fibres are also used to improve strength and reduce brittleness.

A process for the continuous manufacture of formed parts containing inorganic fibres, a silica sol and anionic starch is known from DE-A-26 06 487. However, these formed parts do not contain any inorganic particulate fillers.

EP-B-0 080 986 (AT-E-13777) discloses a process for manufacturing paper according to which a product containing organic p. 41j

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Ki 2 fibres, i.e. cellulose fibres, mineral fillers, anionic colloidal silicic acid and cationic guar is cbtained. On account of the high portion of organic fibres, such a product is combustible and therefore not suitable for high temperature applications.

A process for producing a porous inorganic sheet containing inorganic fibres and/or larger flocs, an anionic silica sol and cationic starch is known from US-A-3 253 978. Howe er, such a sheet does not contain any fine inorganic fillers and its strength is inadequate.

A fibrous material with low density which contains inorganic fibres, inorganic fillers and a high portion of cationic guar is known from 3B-A-21 27 867. The inorganic fillers are standard fillers that are used in relatively small quantities.

Furthermore, borax is added to precipitate guar on the inorganic fibres.

A fibrous sheet material which contains inorganic fibres in a matrix of ball clay is known from GB-A-2 031 043. To control the speed of dewatering, the material can also contain bentonite.

Hydrolyzable starch is used as the binder. Furthermore, the material contains a relatively high portion of cellulose fibres.

Production of a thermal insulating material is known from US-A-3 702 279, whereby inorganic fibres are mixed with a binder of an inorganic sol, whereupon the sol gels. This material does not contain any particle-like inorganic additives. No organic binders are used. The material is sintered following drying.

The object of the invention is to produce a paper, cardboard or paperboard-like material which is on the one hand noncombustible and on the other hand has a high strength and .ii -3 3 i flexibility and can be processed easily. Until now these properties were incompatible, i.e. until now it was considered necessary to use a relatively high portion of organic fibres to manufacture fibrous materials of high strength and flexibility as well as good processibility, which of course increased the combustibility.

To solve this object, the present invention proposes using paper, cardboard or paperboard-like materials containing inorganic fibres, inorganic particulate additives and organic binders or flocculating agents, which are characterised in that the particulate inorganic additives constitute S40-80% by weight of the drymatter of the material.

S(2) the inorganic particulate additives are composed of a base filler of which at least 20% by weight has a particle size of 2 /m and not more than 20% by weight has a particle size of >20. m on the one hand and <0.5 Am on the other hand, and S(2.2) an anionic flocculating active pigment of which f at least 50% by weight has a primary particle size of 2 pm, the organic flocculating agent is a cationic polymeric carbohydrate with an average molecular weight of 100,000 to 2,000,000 and a degree of substitution of 0.01 to 0.3 and is present in a quantity of 0.5 to 6% by weight, based on the dry matter of the material, and 1000 g of bise filler is unable to bind more than 0.1 mMol and 1000 g of anionic flocculating active pigment is able to bind at least 0.1 mMol cationic carbohydrate under flocculation.

y 4 The materials according to the present invention are not combustible. They meet the requirements of DIN 4102, Class A. On account of their good strength properties the materials according to the invention can be easily processed further on the basis of cellulose fibres similar to paper, cardboard and paperboard. The materials can be manufactured on the usual paper, cardboard or paperboard machines.

The good strength properties are surprising since the view was hitherto held that the strength values decrease drastically with high filler contents and increasing particle fineness.

By comparison, the strength values of the materials according to the present invention increase within wide limits with increasing quantities and increasing particle fineness of the particulate inorganic compounds.

According to the invention no fibrous additives are .in- 'cluded under oarticulate inorganic additives" since the length of the fibres generally lies in the order of millimeters. "Par- 9 tide size" is understood as the largest dimension of a particle, which is important, for example, with flattened particles. The .particles of the anionic flocculating active pigment sometimes tend to form larger agglomerates. According to the invention, Sparticle size is therefore understood as the size of the primary particle.

The improvement in the strength properties presumably depends on the fact that the anionic flocculating active pigment and the cationic polymeric carbohydrate settle down on the one hand by the inorganic fibres and on the other hand on the inorgan- 7 ic particulate base fillers. The base filler particles settle firmly

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M16-,on the surfaces of the fibres and in this way prevent the smooth inorganic fibres from sliding on one another, whereby a nonslip nonwoven fabric is obtained. Inorganic fibres are incapable of developing strength either by binding with hydrogen bonds or through cross linkage in combination with shrinkage as is the case with plant fibres. The strength of a sheet made from purely inorganic fibres is based on "gluing" the individual fibres together at the contact points of the fibres with the aid of organic binders. Such nonwoven fabric has relatively few fibre-fibre points of contact on account of the low flexibility of the inorganic fibres and in addition the retention of organic binder during dewatering in the conventional paper-making process is extremely low. The strength of the finished product is thus low.

On account of their surface size and structure as well as on account of their charge properties the base fill.ers used according to the invention can form flocs together with a suitable cationic carbohydrate. The inorganic fibres are embedded by the filler during flocculation in the aqueous system. Consequently, according to the invention the number of contact points (fibrefibre; filler-fibre; filler-filler) as well as the retention of the carbohydrate is increased by the addition of the filler. Good structural strength is achieved only if all fibre-fibre intersection points possible are embedded by the filler completely and without defects and if the flocculating agent is evenly distributed. This is only possible with suitably formed flocs. According to the invention, flocculation is controlled with the aid of the flocculating active pigments. They can displace the point of flocculation on account of their anionic charge potential and, SWA L/ o

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7 -i 6moreover, through formation of a microfloc together with the cationic carbohydrate contribute, to a good distribution thereof. The anionic flocculating active pigments cant in additionclose defects in the filler-filler and fibre-filler compound.

The reaction mechanism described makes it clear that this is a very complex system in which synergistic effects can also occur. The individual components of the material according to the invention, i.e. fibres, base filler, anionic flocculating active pigment and cationic carbohydrate, must therefore be matched exactly to one another with respect to type and quantity added.

There are no limitations with respect to the inorganic fibres. It is the aim of the present invention, however, to provide fibrous materials in which the potentially carcinogenic asbestos fibres are replaced by fibres unharmful to health. These include, among others, glass fibres, mineral fibres, silicic acid fibres, basalt fibres and/or aluminium oxide fibres. The thickness and length of the inorganic fibres can fluctuate within a wide range. Preferably at least 80% of the inorganic fibres have a length in the range of approximately 1 to 6 mm. A mixture of inorganic fibres which differ from one another with respect to composition, length and thickness can also be used.

There are also no limitations with respect to the 'pa-r *tile-like inorganic base fillers. For example, SiO 2 kaolin, aluminium oxide, fuller's earth, gypsum, calcium carbonate, titanium dioxide, zinc oxide, perlite, vermiculite and/or other known paper fillers or fillers for synthetic substana, and paints are suitable.

i 7 Some of these base fillers, such a gypsum and fuller's earth, give off water of crystallization or adsorption water during heating and are in this way fire-retardant. Calcium carbonate, which gives off carbon dioxide at higher temperatures, has a comparable effect.

The content of inorganic basefillers generally amounts to 35 to 75% by weight, preferably 55 to 70% by weight, based on the dry matter of,the material.

Preferably 35 to 99% by weight of the inorganic base filler has a particle size of <2 p~m and not more than 10% by weight has a particle size of >20 1 im.

The anionic flocculating active pigment is preferably aluminium hydroxide, bentonite or colloidal amorphous SiO 2 The content of active pigments generally amounts to approximately 1 to preferably 2 to 10% by weight, based on the dry matter of the material.

If an anionic colloidal amorphous Si02 is used, then it is preferably used in the form of a 30-40% aqueous dispersion.

Preferably anionic silica scls, which were obtained through contact of a diluted water glass solution with an acidic cation exchanger and ageing of the sol obtained, are used. They are dispersed in an alkaline medium which reacts with the silicon dioxide surface and there generates a negative charge. The particles repel one another on account of the negative charge and thus bring about stabilization of the product. Suitable comr 1 ercal products are available, for example, under the name Ludox (Tride Mark for the firm Du Pont), although other products can also be used.

1* 1- 1 8 If aluminium hydroxide is used as the active pigment, then it can be produced in status nascendi from an alkali aluminate and an acid, preferably sodium aluminate and sulphuric acid, or from an aluminium salt and alkali, preferably aluminium sulphate and caustic soda.

If bentonite is used as the active pigment, then alkali bentonite capable of swelling is preferred.

The ratio between inorganic partic -liko additives and cationic polymeric carbohydrate is preferably selected so, that an optimum floc forms.

Preferred polymeric carbohydrates include cationic starch, cationic amylopectin, cationic galactomannan (for example, guar or cassia) aud/or cationic carboxymethylcellulose. The carbohydrates can be cationized in such known manner in that the possibly hydrolyzed initial carbohydrates are quaternized with quaternary ammonium compounds. The carbohydrates can, however, according to also be cationized the dry cationizatipn process. Polyvinyl alcohols can also be added to the cationic carbohydrates.

The content of polymeric cationic carbohydrate as a rule amounts to 1 to 5, preferably 1 to 3% by weight, based on the dry matter of the material. This depends essentially on the desired field of application. If materials with a high temperature stability are to be produced, then small quantities of polymeric cationic carbohydrate are used. Materials for use at high temperatures include, for example, packing materials used in the chemical industry and motor construction as well as temperaturestable filter materials for hot gases and liquids. Furthermore, with higher carbohydrate concentrations the materials according to P ^~S M 9 9 the present invention can also be used as insulating material in buildings, particularly in dry construction, for example as cable routes and fire protection insulations, for fire doors, wall and ceiling paneling, support layers for heat insulating materials as well as fireproof displays for advertising purposes (in department stores). The construction of motor vehicles is another important field of application since in addition to temperature stability the materials according to the present invention have a low specific weight. Even with a higher content of cationic carbohydrate the material does not ignite since the cationic carbohydrate merely carbonizes.

The cationic polymeric carbohydrate generally has an average molecular weight of 200,000 to 1,000,000, preferably 300,000 to 800,000 and a degree of substitution of 0.15 to 0.02.

The materials according to the present invention can also contain cationic, anionic or nonioniQ retention aids. As a rule, these retention aids are common in the paper industry and are preferably added in quantities of approximately 0.02 to 0.2% by weight, based on the dry matter of the material.

A cationic polyacrylamide with a molecular weight of approximately 1 to 10 million or a polyethylene imine with a molecular weight of approximately 80,000 to 300,000 can be used as the retention aid.

The materials according to the present invention can also contain wet strength agents, preferably in a quantity of approximately 0.2 to 5% by weight, based on the dry matter of the material. Suitable wet strength agents are, for example urea formaldehyde or melamine formaldehyde resins, polyamide amine 'Taeppichlorohydrin resins and the like.

10 The forming of materials as three-dimensional moulded bodies is also subject .of this invention. These include tubes, casting shells, filter ,?Oies, insulating walls, packing elements, etc.

The materia.3 according to the present invention are preferably manufactured by mixing an aqueous dispersion of inorganic fibres and the particle like inorganic base fillers with an aqueous suspension of the active pigment and adding cationic polymeric carbohydrate to this mixture shortly before shaping. Shaping can be carried out, for example, on a paper or cardboard machine. This is referred to as sheet-making. The three-dimensional moulded bodies are preferably produced according to the fibrous casting process. It is also possible, however, to deposit the still damp sheet in a three-dimensional shape and dry it.

Shaping is preferably carried out after flocs have formed in the aqueous mixture following the addition of cationic polymeric carbohydrate.

Shaping is preferably carried out after 10 seconds have expired following the addition of cationic polymer carbohydrate. The retention aid is preferably added following the addition of the cationic polymeric carbohydrate.

To obtain homogeneous products, the inorganic fibres and the inorganic base fillers are preEerabiy subjected separately to wet dispersing prior to production of the dispersion, whereupon the separate dispersions are mixed with one another. Selection of a suitable stirring speed, duration of stirring, etc. guarantees that each constituent is optimally dispersed. The dispersing parameters depend, for example, on the nature, length and thickness 4 V I 11 of the inorganic fibres or on the nature, particle size an4 specific weight of the base filler particles.

The aqueous dispersion of active pigments is then added to the mixed dispersion of inorganic fibres and inorganic base filler particles, whereupon the cationic carbohydrate is added shortly (approximately 10 to 30 seconds) before sheet-making. The retention agent is subsequently added.

The present invention will be explained on the basis of the following examples.

Examples 1 to 6 Glass fibre with long fibres (2-6 mm) is pre-dispersed in water. A separate pre-dispersion is then produced from mineral fibres with a fibre length of up to approximately 3 min. The commercial product "Inorphil" (Trade Mark for the firm Laxa, Sweden) is used as the mineral fibre. The percentages by weight between glass fibres and mineral fibres are given in Table I. A dispersion of kaolin (base filler) is subsequently produced. The particle sizes and the percentages by weight of the types of kaolin used are likewise given in Table I.

The three pre-dispersions are thoroughly mixed with a dispersion of colloidal amorphous SiO 2 The water content of J the dispersion amounts to approximately 60-70% by weight.

A solution of cationic starch (commercial product Amijel, Q-Tak 210 of the firm Cerestar) is then added (solids content of the solution 1% by weight). The percentages by weight of colloidal SiO 2 and cationic starch are likewise given in Table I.

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-12 Flocs form following the addition of cationic starch.

According to Example 6, a cationic polyacrylamide is also added as retention agent (N~alco 47-32; Trade Mark of the firm Nalco Chemical Co.) in the quantity given in Table I.

Approximately 20 63conds after the cationic starch is added, the aqueous substance is brought to a Rapid-KMthen laboratory sheet-making plant wb~reupon the aqueous phase is sucked off.

A sheet having a thickness of approximately 0.3 mm after drying is obtained. The tensile strengths of the test sheets are given in Table I.

Examples 1 to 6 show that surprisingly and contrary to the level of knowledge in the paper industry today the strength increases sharply with the increasing base filler content and the greater particle fieness with simultaneously very good retention values.4 The pomparative examples 1 and 3 a~!ready show the influence of the particig fineness, whereas comparative examples 3 and 4 show the influence of the filler content on the mechanical ;*ength.

Examples 2, S and 6 according to the invention show the increases in strength caused by the addition of the anionic flocculating active pigment, whereby the increased strength according to Examp',e 5 over Example 2 is also caused by the higher portion and the gi~eater particle fineness of the base filler.

Example 6 shows that the strength can be increased even further compared with the material of the next comparable Example by using a retention aid.

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'4 I, 13 Examples 7 to The fibre and filler pre-dispersior are produced according to Examples 1 to 6, whereby the substances and weight ratios given in Table II are used. Mixture of the pre-dispersions with the other constituents as well as sheet-making are likewise carried out according to Examples 1 to 6.

In Example 7 an aluminium hydroxide dispersion, which was produced in situ as aluminium sulphate and sodium hydroxide, is used as the active pigment instead of the colloidal amorphous silicic acid.

Bentonite is used as the active pigment in Example 8.

Example 9 was included as a comparative example (without active pigment).

Examples 7 to 10 should illustrate the influence of the various flocculating active pigments on the strength properties of the non-combustible, inorganic materials according to the present invention. The selection and quantity of flocculating active pigment depends to a large es'c't on the properties of the base filler. The requirements for non-combustibility sharply limit the quantity of organic auxiliary agents, such as carbohydrates, used.

By adding active pigments to the base filler, the suspension is "pushed" into the most favourable flocculation range and an acceptable mechanical strength is achieved only through this.

This is demonstrated by comparing the strengths of the materials according to Examples 1, 3 (Table I) and 9, to which no active pigment was added, with the respective values of the remaining examples.

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I j i P 1 dem mindestens 50 Gew. eine Primiirteilchengr6e von 2 ini haben, zusammengesetzt sind; da as organiscne Kkungsmittel ein kationisches polymeres Kohlenhydrat mit einem mittleren Molekulargewicht von 100 000 bis 2 000 000 und einem Substitutionsgrad von 0,01 bis 0,3 darstellt und in einer Menge von 0,5 bis 6 bezogen auf die Trockenmasse des Werkstoffs, vorliegt und da( 1000 g Basisfillstoff nicht mehr als 0,1 mMol und 1000 g anionisches flockenbildendes Aktivpigment mindestens 0,1 mMol kationisches Kohlenhydrat unter Flockenbildung zu binden verma6gen.

1 1- 14 Examples 11 to Production of the pre-dispersions, mixture of the dispersions as well as sheet-making are carried out according to Examples 1 to 6. The individual substances and"their percentages by weight are given in Table III. The Examples given in this Table sl ow that various cationic carbohydrates can be used if they have a suitable degree of substitution (DS) and a suitable molecular weight.

In Example 15 a combination of two different carbohy- 6rates is used which likewise results in suitable strength values.

Corresponding sheets in any thickness can also be manufactured on suitable paper or paperboard machines (endless wire or board machine). Depending on the recipe and the type of machine the total retention amounts to between 85 and 95%. The specific weight can vary in the range of 500 to 1000 kg/m 3 depending on the type and quantity of fibrous materials and fillers used. The insulating capability and thus the range of applications depends primarily on the specific weight of the material produced, whereas the temperature stability depends.first of all from the melting point of the fibres. In the recipes examples given, the glass fibres could be replaced by other fibres with a higher temperature stability without any difficulty and without detrimental effects on the mechanical properties.

t ill; \I i contain any inorganic particulate fillers.

EP-B-0 080 986 (AT-E-13777) discloses a process for manufacturing paper according to which a product containing organic i: Fi I- -r r -i rl L 1I I 1 r 15 TABLE I Example No. 1 2 by weight Mineral fibre 3 mm) Glass fibre (2-6 mm) Kaolin No. 1 Sheet structure (46% <2 /m) Kaolin No. 2 Sheet structure (71% <2 m) Colloidal amorphous SiO 2 (particle size 20 nm) Cationic starch Molecular weight 800,000 1 million DS: 0.05 Cationic polyacrylamide (Nalco 47-32) Tensile strength (MPa) 32.5 26.5 32.5 18.5 18.5 18.5 15.0 11.0 15.0 9.0 9.0 50.0 54.5 50.0 70.0 64.5 64.5 5.5 5.5 2.5 2.5 2.5 2.5 2.45 0.05 0.9 3.8 2.3 4.0 5.3 5.6 Rt.

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i; il Li The object of-. the invention is to produce a paper, cardboard or paperboard-like material which is on the one hand noncombustible and on the other hand has a high strength and 16 TABLE II Example No.

by 26.5 26.5 weight 26.5 Mineral fibre 3 mm) Glass fibre (2-6 mm) Kaolin No. 2 Sheet structure (71% 2 /im) Kaolin No. 3 Sheet structure <2 /m) Aluminium sulphate Sodium hydroxide Bentonite Colloidal amorphous Si0 2 (particle size 20 nm) Cationic starch Molecular weight 800,000 1 million DS: 0.05 Tensile strength (MPa) 26.5 I1.0 11.0 11.0 11.0 136.6 58.0 60.0 54.5 2 .0 1 .4 2.0 5 2.5 4.2 2.5 2.5 4.4 1.3 4.2

K~

~i Aj~ 4 pp, 0.1 mMol and 1000 g of anionic flocculating active pigment is able to bind at least 0.1 mMol cationic carbohydrate under flocculation.

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11 12 13 14 by weight Mineral fibre 3 mm) 19.0 27.0 27.0 18.5 27.0 Glass fibre (2-6 mm) Kaolin No. 2 Sheet structure (71% 2 pm) Calcium carbonate (99% <2 tm) Alkali activated bentonite Colloidal amorphous Si0 2 (particle size 20 nm) Cationic guar No. 1 DS: 0.11 Cationic guar No. 2 DS: 0.02 Cationic gua' No. 3 DS: 0.1 Cationic cassia Molecular weight 400,000 Cationic starch Molecular weight 800,000 1 million DS! 0.05 Tensile strength (MPa) 9.5 11.5 11.5 S 54.5 54.5 68.0 5.5 5.5 9.0 11.0 54.0 64.5 5.5 1.5 S 1.5 4.0 4.1 4.0 4.7 4.2

Claims (3)

1. Paper, cardboard- or paperboard-like material containing inorganic fibres, inorganic particulate additives and organic binder or flocculating agents, characterized in that the particulate inorganic additives constitute

40-80% by weight of the dry matter of the material; the inorganic particulate additives are composed of a base filler of which at least 20% by weight F has a particle size of <2 ym and not more than by weight has a particle size of >20 im on the one .hand and <0.5 pm on the other hand, and an anionic flocculating active pigment of which at least 50% by weight has a primary particle si:e of <2 pm, the organic flocculating agent is a cationic polymeric carbohydrate with an average molecular weight of 100,000 to 2,000,000 and a degree of :substitution, of 0.01 to 0.3 and is present in a quantity of 0.5 to 6% by weight, based on the dry matter of the material, and 1000 q of base filler is unable to bind more than 0.1 inMol, and 1000 g of anionic flocculating active pigment is able to bind at least 0.1 mMol cationic carbohydrate under flocculation. 2. A material according to Claim 1, characterized in that the quantity of particulate inorganic additives (1) amounts to approximately 50 to 75% by weight, based on the dry matter of the material. 3. A material according to Claim 1 or Claim 2, characterized in that the quantity of particulate inorganic additives amounts to approximately 60 to 75% by weight, based on the dry matter of the material. 39 4. A material according to any one of Claims 1 to 3, 1 4°NOB i A I known paper fillers or fillers for synthetic substan, and paints are suitable. -19- characterized in that the inorganic fibres are glass fibres, mineral fibres, silicic acid fibres, basalt fibres and/or aluminium oxide fibres. 5. A material according to any one of Claims 1 to 4, characterized in that at least 80% of the inorganic fibres have a length in the range of 1 to 6 mm. 6. A material according to any one of Claims 1 to characterized in that the particulate inorganic base fillers are SiO 2 kaolin, aluminium oxide, fuller's earth, e gypsum, calcium carbonate, titanium dioxide, zinc oxide, perlite, vermiculite. 9.'i 7. A material according to any one of Claims 1 to 6, characterized in that the content of inorganic base fillers amounts to 35 to 75% based on the dry matter of the material. 8. A material according to any one of Claims 1 to 7, S characterized in that the content of inorganic base fillers amounts to 55 to 70% by weight based on the dry matter of the material. 9. A material according to any one of Claims 1 to 8, characterized in that 35 to 99% by weight of the inorganic base filler has a particle size of <2 pm and not more Sthan 10% by weight has a particle size of >20 pm. 10. A material according to any one of Claims 1 to 9, characterized in that the anionic flocculating active pigment is aluminium hydroxide, bentonite or colloidal amorphous SiO. 2 11. A material according to Claim 10, characterized in that the aluminium hydroxide was obtained in status nascendi from an alkali aluminate and an acid, preferably from sodium aluminat' and sulphuric acid, or from an aluminium salt and 39 alkali, preferably from aluminium sulphate and caustic soda. NOB J 1_L 12. A material according to any one of Claims 1 to 11, characterized in that the ratio between the inorganic particulate additives if they have an anionic surface charge, and the cationic polymeric carbohydrate is selected so that there is no excess charge. 13. A material according to any one of Claims 1 to 12, characterized in that the cationic polymeric carbohydrate (3) is cationic starch, cationic amylopectin, a cationic galactomannan and/or cationic carboxymethylcellulose. 14. A material according to any one of Claims 1 to 13, ee characterized in that the content of cationic polymeric i carbohydrate amounts to 1 to 5% based on the dry matter of the material. e A material according to any one of Claims 1 to 14, characterized in that the content of cationic polymeric carbohydrate amounts to 1 to 3% based on the dry matter of the material. 16. A material according to any one of Claims 1 to 14, characterized in that the cationic polymeric carbohydrate (3) is obtained by reacting the initial carbohydrate with a quaternary ammonium compound. 17. A material according to any one of Claims 1 to 16, characterized in that the cationic polymeric carbohydrate (3) has an average molecular weight of 200,000 to 1,000,000 and a Sdegree of substitution of 0.15 to 0.02. 18. A material according to any one of Claims 1 to 17, characterized in that the cationic polymeric carbohydrate (3) has an average molecular weight of 300,000 to 800,000 and a degree of substitution of 0.15 to 0.02. 19. A material according to any one of Claims 1 to 18, 39 characterized in that in addition it contains cationic, p A S 1 1 L 2 M^OB cal industry and motor construction as well as temperature- stable filter materials for hot gas8es and liquids. Furthermore, with higher arbohydrate concentrations the materials according to W-0- .4 -21- anionic or nonionic retention aids. A material according to any one of Claims 1 to 19, characterized in that the retention aid is present in a quantity of approximately 0.02 to 0.2% by weight, based on the dry matter of the material. 21. A material according to Claim 19 or Claim characterized in that the retention aid is a ca..Aonic polyacrylamide with a molecular weight of approximately 1 to million or a cationic polyethylene imine with a molecular weight of approximately 80,000 to 300,000. to: 22. A material according to any one of Claims 1 to 21, characterized in that in addition it contains wet strength *~.agents, feet 0 23. A material according to any one of Claims 1 to 22 as a three-dimensional moulded body. 24. A process for the manufacture of a material according t00~ o any one of Claims 1 to 23, characterized in that ani aqueous Sdispersion of inorganic fibres and particulate inorganic base fillers is mixed with an aqueous suspension of the :active pigment and that cationic polymeric carbohydrate is added to this mixture shortly before shaping. 25. A process according to Claim 24, characterized in thait shaping is carried out after flocs have formed in the aqueous mixture following the addition of cationic polymeric carbohydrate 26. A process according to Claim 24 or Claim characterized in that shaping is carried out after 10 seconds have expired following the addition of cationic polymeric carbohydrate 27. A process according to any one of Claims 24 to Claim 39 26, characterized in that the retention aid is added following OS ~1 I K I9 I I -22- the addition of the cationic polymeric carbohydrate 28. A process according to any one of Claims 24 to 27, characterized in that the inorganic fibres and the inorganic base fillers and active pigments are subjected separately to wet dispersing prior to production of the dispersion. 29. A process according to any one of Claims 24 to 28, characterized in that the material is manufactured on a known paper, cardboard or paperboard machine or, if this concerns a three-dimensional moulded body, is manufactured according to the fibrous casting process or through deformation of a still o. damp fibrous web. 30. A material according to Claim 1 substantially as hereinbefore described with reference to any one of the examples. 31. A process according to Claim 24 substantially as hereinbefore described with reference to any one of the examples. 25 DATED: 22 NOVEMBER 1991 .5.505 S *r S 5 S S. S SO PHILLIPS ORMONDE FITZPATRICK Attorneys for: MANFRED ZEUNER and PETER DOBLANZKI VE NOB t p i i i: 9 1 i STranslation of POT/EP89/01287 Paper, cardboard or paperboard-like material and a process for its production Abstract Paper, cardboard or paperboard-like material containing inorganic fibres, inorganic particle-like additives and organic binders and flocculating agents characterized in that the particle-like inorganic additives constitute 40-80% by weight of the dry matter of the material; the inorganic particle-like additives are compos- ed of a base filler of which at least 20% by weight has a particle size of 2 pm and not more than 20% by weight has a particle size of >20 p.m on the one hand and <0.5 pm on the other hand, and an anionic flocculating active pigment of which at least 50% by weight has a primary particle size of 2 Am, the organic flocculating agent is a cationic polymeric carbohydrate with an average molecular weight of 100,000 to 2,000,000 and a degree of substitution of 0.01 to 0.3 and is present in a quantity of 0.5 to 6% by weight, based on the dry matter of the material, and 1 tent of the solution 1% by weight). The percentages by weight of colloidal SiO 2 and cationic starch are likewise given in Table I. -2- 1000 g of base filler is unable to bind more than 0.1 mMol) and 1000 g of anionic flocculating active pigment is able to bind at least 0.1 mMol cationic carbohydrate under floccula- tion. 1 i' i -i INTERNATIONAL SEARCH REPORT Intertational Application No P CT /EP 89 /0 1287 1. CLASIIiCATION OF SUBJECT MATTER (it several Classification symbols apply. indicate all) According to International Patent Classification (IPC) or to both National Cieificatatn and IPC Int.Ci. 5: 0 21 H 21/52, 0 21 H 13/36 I1. FIELDS SEARCNIED Minimum Documentation Fearched Classification system Classification Symbols Int.Cl. 51 21 H ocumentation Searched other than Minimum Documentation to the Extent that such Documnents are included In the Fields Searched' gja ~CumENiTs CONSIDERED TO MR RELEVANT' Category Citation 01 Document,"I with Indication, Where aporooriate. ot the relevant passages Is Relevant to Claim No 13 Y EP, A, 0099586 (AMF INC.) 01 February 1984 1-25 r see claims 1-46 Y US, A, 4443262 PIERSOL ET AL) 1-25 17 April 193~4, see the whole document (cited the application) A GB, A, 2047297 LTD) 26 November 1980 see the whole document A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 51, No. 11, May 1981, APPLETON US page 1235 t. mihara et al: "inorganic fiberboard for heat insulation, A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 57, No. 9, March 1987, APPLETON US page 1351 k. noshiro et al.: "inea f iberboard" A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 58, No. 4, October 1987, APPLETON US page 564 s. toyoshira et al.: 0Special categories of chted documents! 8 T" )!star document Published ailer the International filing data document defining the general state ot the art which is not or oririy date and not in conflict with the application but Cosdee tob fParticular rftevanc@ cited to understand the Principle, w theory underlying the Consiered o beinvention arler ocuentbutpubishd o oraft~r he nteatinal X" document Of particular reevaliea the claimed invention cannot be considered novel fir cannot a oe(nS dared to document whiC May throw doubte on priority Claimts) or involve an inventive stop which is cited to establish the publication date Of another document at particular relevance:- the claimed Invention Citation of other special reason ta specified) cannot be considered to Involve an inventive star, when the docu; ent referting to an oral disclosure, us, exhibition or document ao Com-bined wih one Or MOre other auch docu- other means merits, such combination being~ Obvious to porson skilled 1101 document oubilahed prior to the international filing date but the art later than the priority date claimed document member ol the soMe Niltent family IV, CERTIFICATION Date of the Actual Completion of the international Search Date Of Mail111ing of this InternatIonal Search Report 02 May 1990 (02.05-90) 09 May 1990 (09,05.90) Interriational Searching Authority Signature of Authorized (oofier European Patent Office__ Form PCT/ISAij10 lascond itheet) 4January 19IS) .1. b' dv- I,, 9- I ~f, kfthsftl~na AicAtionNoPC T/EP 8 9/ 0128 7 Ill. r2CUMENTS CONSIDERED TO SE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category I CRUMn Of OOLWMinn Wit Iumutc. wnm aWrkmU. of im fem omAw j Paieam to Cilm No i norgan ic f iberboard Form PCTIISAI2O Ioa sheet) WJwwY IMS) I I ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8901287 SA 32220 This alinex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The m.em~bers are as contained in the European Patent Office EDP ile on The European Patent Office is in no way liable for these particulars wvhich are merely given for the purpose of information. 02/05/90 Patent document Publication Patent family Publication cited in search report 7date member(s) Tdate EP-A-0099586 01-02-84 US-A- 4578150 25-03-86 AU-A- 1887483 23-02-84 CA-A- 1221080 28-04-87 WO-A- 8400569 16-02-84

115-A- 4596660 24-06-86 US-A-4443262 17-04-84 CA-A- 1189255 25-06-85 DE>-A,C 3324395 05-04-84 FR,-A,B 2533948 06-04-84 GB--A,B 2127867 18-04-84 GG-A-2047297 26-11-80 JP-A- 55136159 23-10-80 AM 1ir more details about this annex :see Official Jounal of the European Patent Office, No. 12182 4: A f t C IERNTIONLERRECHERC ENBERICA' intornationales Aktenzechefl rul/tr !KIASSIFIKATIOIN DES ANNMELDULNGSC.EGF.NSTANDS (l nielreren Klassilikationssymbolen sind aile anzttgeben) 6 Nach der inie,'nationalen Patentkiassifikatinn (IPC) oder lnch der nationalen Kiassifikalion und der IPC Int.Kl. 5 0211121/52 21H13/36 RECHERCIJERTE SACIIGEBIETE Recherchierter Nlindestprofstoff Recherchierie nichi zum NlindesiPrilfstoff Rehitrende Verdffentlichungen, so'selt diese tinter die recherchierten Sachgebiete fallen Ill. EINSCI II.ACGIGE VEROFFENTLICHUNGEN 9 Art. 0 Kennzeichnung der Verdffentlichungl, soweit erfnrderlicli tnter Angahe d's maflgeblichen Teile1 B eir. Anspruch Nr.1 3 Y EP,A,0099586 (AMF INC.) 01 Februar 1984 1-25 siehe Anspr~che 1-46 Y US,A,4443262 (J.L.PIERSOL ET AL) 17 April 1984 1-25 siehe das ganze Oqkument (in der Anmeldung erwghnt) A GB,A,2047297 LTD) 26 November 1980 siehe das ganze Ookument A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 51, no. 11, Mai 1981, APPLETON US Seite 1235 t.niihara et al: "inorganic fiberboard for heat insulation" A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 57, no. 9, M~rz 1987, APPLETON US Seite 1351 k.noshiro et al.: I "mineral fiberboard" 0 lesnndere Kategorien von angegebenen VertiffentIlchttngen2: 'Al Vertlffentlicho 0g. die den ailgentelnen Stand der Technik T'S &ie Verttffentiichung, die nach dem Internationalen An- definlert, alter n1 cht ais bestnders bedeutsans anttiselen ist meidedatun, oder dens Priorllthtsdalum veritffentiicht snorden IF' ititeres Dokument, das jedoch ersl amn oder nacit dent intern*- 1st und mit der AnmeldunR nicht kolildiert, sondern our zun tionsien Antueldedatum verlffntlicht wnrdren 1st Verstitodnis des der Erfindung zugrundeliegenden Prinzips Vcriffentlichung, die geelgnet lot, elnen Priorititsanspruch oder der lhr zugrundeliegenden Theorie angegehen in? zweifeihaff erscheinen sti hassen, oder dutcht die das Verlif- W Verbffentlichung von besonderer fledeuiung-, die iteantpruch- fentiichungsdatum einer anderen Im Rechcrchenhericht go- to Erfindung kann nicht als neu oder auf erfinderischer Tgtig- n annten Verfiffentlichung beiegt werden soil oder die aus elnent keit beruihcnd betrachtet 'serden anderen besonderen Grund angcegben Ist ('sic ausgefuhes) 'V Veritffentllchung von besonderer Bedeutung-, die bean ~uch- Q Veitffnthlhun, di sid sa mitdlice OfenbrttnlI Erflndting~kann nlchl ala auf erfinderisce r T~tlgtt be elne Benut7.unR, cine Aussteliog uder andere Ntafloahoten ruhend hetrachtet werden, wenn die Verliffentlchung mit bezieht elnet oder mereren anderen Vertiffentlichungen dieser Kate- gorie In Verbindung gebracht "ind und diese Verbindung fUr 'P Verliffentlichung, die vor dens internationalen Anmoidoda. einen Finebmann naheilloend lot turn, alter nach dem heansprutelten l'riorittsdattn verOffent- W Verfiffentlichung, die Mitglied derseiben Patentfansulle ist licht wnrden is? IV. NIESCIIEINIGING Datum des Abschlusses dei Internatlonaico Recherche Absendedatum des Internalionnien Rechcrchenberichts 02.MAI 1990 J6 Vj 19G Internationale Recherchctthehlnde Onterschnift des hevolimtlchtigten Nedlensteten EUROPA ISCFS PATENTAw SONGY O.M-L.A. K PCT/EP 89/01287 Internationales Aktenzeichen Illi. EINSCIIIAGIGE VEROFFFNTLICIUNC.EN (Fontsetzung von Blatt 2) KennzeichnunR der VerOffentlichunR, soWeil erforderlich unter Angabe der maBgcblichen Teile J etr. Anspruci Nr A BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol 58, no. 4, Oktober 1987, APPLETON US Seite 564 s.toyoshima et al.: "inorganic fiberboard' 'I K IF.71811i kvT/SA/M1 f7mislzbogrnt fJuiuv 1985) 4 ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT OBER DIE INTERN. ATiONALE PATENTANMELDUNG NR. EP 8901287 SA 32220 In diesem Anhang sind die Mitglieder der Patentlamilien der im obcngcnannten internationalen Recherchenhericht angefiurten Patentdokumente angegehen. Die Angahen uiher die Familienmitglieder ents-prechen dem Stand der Datei des FEuropliischen Patentamts am fliese Angaben dienen nur zur Unterrnchtung tend erfolgen ohne Gewaihr. 02/05/90 rwRehechnhrihtDtum der Mitglied(er) der Datum der ange hte Paetoumn erentlichung Platentfamilie Verbffentlichung EP-A-0099586 01-02-84 US-A- 4578150 25-03-86 AU-A- 1887483 23-02-84 CA-A- 1221080 28-04-87 WO-A- 8400569 16-02-84 US-A- 4596660 24-06-86 US-A-4443262 17'-04-84 CA-A- 1189255 25-06-85 DE-A,C 3324395 05-04-84 FR-A,B 2533948 06-04-84 GB-A,B 212786/ 18-04-84 GB-A-2047297 26-11-80 JP-A- 55136159 23-10-80 F~r n~hcre Einizelheiten zu diesem Anhang :siehe Anitshlalt des Europhischen P'tntnts, Nr. 12/82