EP0399010B1 - Papier-, karton- oder pappenartiger werkstoff und verfahren zu dessen herstellung - Google Patents

Papier-, karton- oder pappenartiger werkstoff und verfahren zu dessen herstellung Download PDF

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Publication number
EP0399010B1
EP0399010B1 EP89912436A EP89912436A EP0399010B1 EP 0399010 B1 EP0399010 B1 EP 0399010B1 EP 89912436 A EP89912436 A EP 89912436A EP 89912436 A EP89912436 A EP 89912436A EP 0399010 B1 EP0399010 B1 EP 0399010B1
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EP
European Patent Office
Prior art keywords
cationic
material according
weight
inorganic
carbohydrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89912436A
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German (de)
English (en)
French (fr)
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EP0399010A1 (de
Inventor
Manfred Zeuner
Peter Doblanzki
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Individual
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Individual
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Priority to AT89912436T priority Critical patent/ATE85097T1/de
Publication of EP0399010A1 publication Critical patent/EP0399010A1/de
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Publication of EP0399010B1 publication Critical patent/EP0399010B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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

Definitions

  • the invention relates to an incombustible paper, cardboard or cardboard-like material with a very high proportion of inorganic constituents, namely inorganic fibers and inorganic particulate additives, i.e. of fillers and pigments.
  • Paper-like materials are known from EP-A-0 109 782 and EP-A-0 027 705, which contain inorganic fibers, such as glass fibers or mineral wool fibers, inorganic particulate fillers, such as clay and bentonite, as well as hydrolyzed starch as an organic binder.
  • inorganic fibers such as glass fibers or mineral wool fibers
  • inorganic particulate fillers such as clay and bentonite
  • hydrolyzed starch such as an organic binder.
  • organic fibers are also used to improve strength and reduce brittleness.
  • EP-A-0 109 782 describes the addition of at least 2% by weight of cellulose fibers, but the proportion of the combustible components should not exceed 10% by weight.
  • DE-A-26 06 487 discloses a process for the continuous production of moldings which contain inorganic fibers, a silica sol and anionic starch. However, these molded parts do not contain any inorganic particulate fillers.
  • GB-A-21 27 867 discloses a low-density fiber material which contains inorganic fibers, inorganic fillers and a high proportion of cationic guar.
  • the inorganic fillers are standard fillers that are used in relatively small quantities.
  • Borax is also added to precipitate the guar onto the inorganic fibers.
  • GB-A-2 031 043 discloses a fibrous sheet material which contains inorganic fibers in a matrix of plastic clay (ball clay).
  • the material may also contain bentonite to regulate the rate of drainage.
  • Hydrolyzable starch is used as the binder.
  • the material also contains a relatively high proportion of cellulose fibers.
  • the invention has for its object to provide a paper, cardboard or cardboard-like material which is on the one hand non-flammable and on the other hand has high strength and flexibility and is easy to process. These properties were previously incompatible, i.e. For the production of fiber materials with high strength and flexibility and with good processability, a relatively high proportion of organic fibers was previously considered necessary, which naturally increased the flammability.
  • the materials according to the invention are not flammable. They meet the requirements of DIN 4102, class A. Because of their good strength properties, the materials according to the invention, like paper, cardboard and cardboard, can easily be processed further on the basis of cellulose fibers. The materials can be produced on the usual paper, cardboard or cardboard machines.
  • particle inorganic additives are not fibrous additives, since the length of the fibers is generally of the order of millimeters lies.
  • Particle size means the largest dimension of a particle, which is important, for example, in the case of flattened particles.
  • the particles of the anionic flake-forming active pigment sometimes tend to form larger agglomerates.
  • the particle size is understood to mean the size of the primary particles.
  • the improvement in the strength properties is probably due to the fact that the anionic flake-forming active pigment and the cationic polymeric carbohydrate accumulate on the one hand on the inorganic fibers and on the other hand on the inorganic particulate base fillers.
  • the basic filler particles settle on the fiber surfaces and in this way prevent the inorganic fibers, which are inherently smooth, from sliding against one another, as a result of which a non-slip fiber fleece is obtained.
  • Inorganic fibers are not able to develop strengths either by hydrogen bonding or by crosslinking in combination with shrinkage, as is the case with vegetable fibers.
  • the strength of a sheet of purely inorganic fibers is based on an "adhesion" of the individual fibers to one another at the fiber contact points with the aid of organic binders. Due to the low flexibility of inorganic fibers, such a nonwoven fabric has only relatively few fiber-fiber contact points, and the retention of organic binders during dewatering in the conventional paper-making process is extremely low. The finished product is therefore of low strength.
  • the base fillers used according to the invention can form a flake together with a suitable cationic carbohydrate on account of their surface size and structure and on account of their charge properties.
  • a suitable cationic carbohydrate on account of their surface size and structure and on account of their charge properties.
  • the inorganic fibers are embedded in the filler.
  • the number of points of contact fiber-fiber; Filler fiber; Filler-filler
  • Good structural strength is only achieved if all fiber-fiber crossing points are completely embedded without filler defects and the flocculant is evenly distributed. This is only possible with a suitably designed flake.
  • the flocculation is controlled according to the invention with the aid of the flake-forming active pigments.
  • anionic flake-forming active pigments Due to their anionic charge potential, these can shift the flocculation point and, in addition, contribute to a good distribution of the latter by forming a microfloc together with the cationic carbohydrate.
  • the anionic flake-forming active pigments can: also close defects in the filler-filler and fiber-filler composite.
  • reaction mechanism described illustrates that this is a very complex system in which synergistic effects can also occur.
  • the individual components of the materials according to the invention - that is to say fibers, base filler, anionic flake-forming active pigment and cationic carbohydrate - must therefore be precisely coordinated with one another with regard to the type and amount added.
  • An object of the invention is to provide fiber-containing materials in which the potentially carcinogenic asbestos fibers are replaced by fibers which are harmless to health. These include glass fibers, mineral fibers, silica fibers, basalt fibers and / or aluminum oxide fibers.
  • the thickness and length of the inorganic fibers can vary within wide ranges. Preferably at least 80% of the inorganic fibers have a length in the range of about 1 to 6 mm. Mixtures of inorganic fibers which differ from one another in terms of composition, length and thickness can also be used.
  • Ge are, for example SiO2, kaolin, aluminum oxide, bleaching earth, gypsum, calcium carbonate, titanium dioxide, zinc oxide, perlite, vermiculite and / or other known paper fillers or fillers for plastic materials and paints.
  • Some of these basic fillers such as gypsum and bleaching earth, release water of crystallization or adsorption water when heated and thus have a fire-retardant effect.
  • Calcium carbonate which emits carbon dioxide at higher temperatures, has a comparable effect.
  • the content of inorganic base fillers is generally 35 to 75% by weight, preferably 55 to 70% by weight, based on the dry matter of the material.
  • the inorganic base filler preferably has a particle size of ⁇ 2 ⁇ m to 35 to 99% by weight and a particle size of> 20 ⁇ m to no more than 10% by weight.
  • the anionic flake-forming active pigment is preferably aluminum hydroxide, bentonite or colloidal amorphous SiO2.
  • the content of active pigments is generally about 1 to 15, preferably 2 to 10% by weight, based on the dry matter of the material.
  • an anionic colloidal amorphous SiO2 is used, this is preferably used in the form of a 30-40% aqueous dispersion.
  • Anionic silica sols which are obtained by contacting a dilute water glass solution with an acidic cation exchanger and aging the sol obtained are preferably used. They are dispersed in an alkaline medium that reacts with the silicon dioxide surface and creates a negative charge there. Bump because of the negative charge the particles mutually from one another thus stabilize the product.
  • Suitable commercial products are available, for example, under the name Ludox (trademark of the Du Pont company), although other products can also be used.
  • aluminum hydroxide is used as the active pigment, this can be prepared 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 sulfate and sodium hydroxide solution.
  • bentonite is used as the active pigment, swellable alkali bentonite is preferred.
  • the ratio between the inorganic particulate additives and the cationic polymeric carbohydrate is preferably chosen so that there is no excess charge so that an optimal floc forms.
  • Preferred polymeric carbohydrates are cationic starch, cationic amylopectin, cationic galactomannans (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 carbohydrates with quaternary ammonium compounds. However, the carbohydrates can also be cationized using the dry cationization method. Cationic polyvinyl alcohols can also be added to the cationic carbohydrates.
  • the polymeric cationic carbohydrate content is generally 1 to 5, preferably 1 to 3,% by weight, based on the dry mass of the material. This essentially depends on the desired field of application. if you want to manufacture materials with high temperature resistance, this becomes polymer cationic carbohydrate used in smaller amounts.
  • Materials for use at high temperatures include sealing materials in chemical and engine construction as well as temperature-resistant filter materials for hot gases and liquids.
  • the materials according to the invention can also be used at higher carbohydrate concentrations as insulating materials in the building industry, in particular in drywall construction, for example as cable routes and fire protection insulation, for fire doors, wall and ceiling panels, carrier layers for heat-insulating materials and as fire-resistant displays for advertising purposes (in department stores).
  • 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 invention can also contain cationic, anionic or nonionic retention aids. These are generally the retention aids customary in the paper industry, which are preferably added in amounts of about 0.02 to 0.2% by weight, based on the dry matter of the material.
  • a cationic polyacrylamide with a molecular weight of about 1 to 10 million or a polyethyleneimine with a molecular weight of about 80,000 to 300,000 can be used as a retention aid.
  • the materials according to the invention can also contain wet strength agents, preferably in an amount of about 0.2 to 5% by weight, based on the dry matter of the material.
  • Suitable wet strength agents are, for example, urea or melamine-formaldehyde resins, polyamidamine-epichlorohydrin resins and the like. the like
  • the invention also relates to the design of the materials according to the invention as three-dimensional shaped bodies. These include Pipes, shells, filter bodies, insulating walls, sealing elements, etc.
  • the materials according to the invention are preferably produced 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 the cationic polymeric carbohydrate to this mixture shortly before shaping.
  • the shape can e.g. be carried out on a paper or cardboard machine. In this case one speaks of a sheet formation.
  • the three-dimensional moldings are preferably produced by the fiber casting process. However, it is also possible to lay down and dry the still wet sheet in a three-dimensional form.
  • the shaping is preferably carried out after flakes have formed in the aqueous mixture after the addition of the cationic polymeric carbohydrate.
  • the shaping is preferably carried out after at least 10 seconds after the addition of the cationic polymeric carbohydrate.
  • the retention aid is preferably added after the addition of the cationic polymeric carbohydrate.
  • the inorganic fibers and the inorganic base fillers are used before production the dispersion is preferably subjected to wet dispersion separately, whereupon the separate dispersions are mixed with one another. This ensures that each component is optimally dispersed by selecting a suitable stirring speed, stirring time, etc.
  • the dispersion parameters depend on the nature, length and thickness of the inorganic fibers or on the nature, particle size and the specific weight of the base filler particles.
  • the aqueous dispersion of the active pigments is then added to the mixed dispersion of inorganic fibers and inorganic base filler particles, whereupon the cationic carbohydrate is added shortly (about 10 to 30 seconds) before the sheet formation.
  • the retention aid is then added.
  • the three predispersions are thoroughly mixed with a dispersion of colloidal, amorphous SiO2.
  • the water content of the dispersion is about 60-70% by weight.
  • the proportions by weight of colloidal SiO2 and cationic starch are also given in Table I.
  • Example 6 a cationic polyacrylamide is added as a retention agent (Nalco 47-32; trademark of Nalco Chemical Co.) in the amount shown in Table I.
  • the aqueous mass is transferred to a Rapid-Koethen laboratory sheet formation system, whereupon the aqueous phase is suctioned off.
  • a sheet is obtained which, after drying, has a thickness of approximately 0.3 mm.
  • the tensile strengths of the test sheets are given in Table I.
  • Comparative Examples 1 and 3 already show the influence of the particle fineness, while Comparative Examples 3 and 4 show the influence of the filler content on the mechanical strength.
  • Examples 2, 5 and 6 according to the invention show the strength increases caused by the addition of the anionic floc-forming active pigment, the strength increased according to Example 5 compared to Example 2 also being due to the higher proportion and the higher particle fineness of the base filler.
  • Example 6 shows that by using a retention aid, the strength compared to the material of the next comparable example 5 can be increased even further.
  • the fiber and filler predispersions are prepared as in Examples 1 to 6, the substances and weight ratios given in Table II being used.
  • the mixing of the predispersions with the other constituents and the sheet formation are likewise carried out as in Examples 1 to 6.
  • Example 7 an aluminum hydroxide dispersion which was prepared in situ from aluminum sulfate and sodium hydroxide is used as the active pigment instead of the colloidal, amorphous silica
  • Example 8 bentonite is used as the active pigment.
  • Example 9 was included as a comparative example (without active pigment).
  • Examples 7 to 10 are intended to show the influence of the various flake-forming active pigments on the strength properties of the non-combustible inorganic materials according to the invention.
  • the selection and the amount of the flake-forming active pigment largely depends on the properties of the basic filler.
  • the amount of organic auxiliaries, such as carbohydrates, is greatly limited by the non-combustibility requirements.
  • Example 15 a combination of two different carbohydrates was used, which also gives usable strength values.
  • Corresponding sheets can also be produced on suitable paper or cardboard machines (wire or circular screen) in any thickness.
  • the total retention is between 85 and 95% depending on the recipe and machine type.
  • the specific weight can be varied in the range from 500 to 1000 kg / m3.
  • the insulating ability and thus the possible application depends mainly on the specific weight of the material produced, while the temperature resistance depends primarily on the melting point of the fibers. In the recipe examples given, the replacement of the glass fiber with other fibers with a higher temperature resistance would be problem-free and without an adverse effect on the mechanical property.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Magnetic Treatment Devices (AREA)
EP89912436A 1988-11-07 1989-10-28 Papier-, karton- oder pappenartiger werkstoff und verfahren zu dessen herstellung Expired - Lifetime EP0399010B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89912436T ATE85097T1 (de) 1988-11-07 1989-10-28 Papier-, karton- oder pappenartiger werkstoff und verfahren zu dessen herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3837746A DE3837746C1 (enrdf_load_stackoverflow) 1988-11-07 1988-11-07
DE3837746 1988-11-07

Publications (2)

Publication Number Publication Date
EP0399010A1 EP0399010A1 (de) 1990-11-28
EP0399010B1 true EP0399010B1 (de) 1993-01-27

Family

ID=6366655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89912436A Expired - Lifetime EP0399010B1 (de) 1988-11-07 1989-10-28 Papier-, karton- oder pappenartiger werkstoff und verfahren zu dessen herstellung

Country Status (14)

Country Link
EP (1) EP0399010B1 (enrdf_load_stackoverflow)
JP (1) JPH03502219A (enrdf_load_stackoverflow)
AU (1) AU620470B2 (enrdf_load_stackoverflow)
BR (1) BR8907153A (enrdf_load_stackoverflow)
CA (1) CA2001784A1 (enrdf_load_stackoverflow)
DE (2) DE3837746C1 (enrdf_load_stackoverflow)
DK (1) DK171501B1 (enrdf_load_stackoverflow)
ES (1) ES2017306A6 (enrdf_load_stackoverflow)
FI (1) FI93757C (enrdf_load_stackoverflow)
GR (1) GR1000750B (enrdf_load_stackoverflow)
IE (1) IE61832B1 (enrdf_load_stackoverflow)
NO (1) NO176028C (enrdf_load_stackoverflow)
PT (1) PT92183B (enrdf_load_stackoverflow)
WO (1) WO1990005211A2 (enrdf_load_stackoverflow)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145811A (en) * 1991-07-10 1992-09-08 The Carborundum Company Inorganic ceramic papers
JPH0995044A (ja) * 1995-04-10 1997-04-08 Canon Inc 記録紙及びこれを用いたインクジェット記録方法
RU2345189C2 (ru) * 2003-12-22 2009-01-27 Эка Кемикалс Аб Наполнитель для изготовления бумаги
WO2005061792A1 (en) * 2003-12-22 2005-07-07 Akzo Nobel N.V. Paper comprising quaternary nitrogen containing cellulose ether
CN101617082B (zh) * 2007-02-19 2012-12-12 3M创新有限公司 柔性纤维质材料、污染控制装置及其制造方法
JP5855348B2 (ja) * 2011-03-29 2016-02-09 アイカ工業株式会社 不燃性基材
JP5876743B2 (ja) * 2012-02-09 2016-03-02 大王製紙株式会社 複合粒子の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080986B1 (en) * 1981-11-27 1985-06-12 Eka Ab A process for papermaking

Family Cites Families (9)

* Cited by examiner, † Cited by third party
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
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 (de) * 1982-12-30 1984-07-05 Lüchtrath, Bern, 8700 Würzburg Papier-, karton- und pappenartiger werkstoff
DE3306478A1 (de) * 1982-12-30 1984-07-12 Bern 8700 Würzburg Lüchtrath Fuellstoff fuer einen papier-, karton oder pappenartigen werkstoff und verfahren zur herstellung solcher werkstoffe
GB8621680D0 (en) * 1986-09-09 1986-10-15 Du Pont Filler compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080986B1 (en) * 1981-11-27 1985-06-12 Eka Ab A process for papermaking

Also Published As

Publication number Publication date
PT92183B (pt) 1995-08-09
WO1990005211A2 (de) 1990-05-17
IE893559L (en) 1990-05-07
FI903434A0 (fi) 1990-07-06
NO903041D0 (no) 1990-07-06
FI93757B (fi) 1995-02-15
AU620470B2 (en) 1992-02-20
PT92183A (pt) 1990-05-31
AU4514089A (en) 1990-05-28
DK163590D0 (da) 1990-07-06
NO903041L (no) 1990-07-06
IE61832B1 (en) 1994-11-30
DK171501B1 (da) 1996-12-02
GR1000750B (el) 1992-12-30
NO176028B (no) 1994-10-10
CA2001784A1 (en) 1990-05-07
DE58903410D1 (de) 1993-03-11
GR890100627A (en) 1990-12-31
DK163590A (da) 1990-07-06
ES2017306A6 (es) 1991-01-16
DE3837746C1 (enrdf_load_stackoverflow) 1990-03-29
FI93757C (fi) 1995-05-26
NO176028C (no) 1995-01-18
BR8907153A (pt) 1991-02-26
EP0399010A1 (de) 1990-11-28
WO1990005211A3 (de) 1990-06-28
JPH03502219A (ja) 1991-05-23

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