EP2365130A1 - Composite de fibres imprégné, sa fabrication et son utilisation - Google Patents

Composite de fibres imprégné, sa fabrication et son utilisation Download PDF

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Publication number
EP2365130A1
EP2365130A1 EP20110155082 EP11155082A EP2365130A1 EP 2365130 A1 EP2365130 A1 EP 2365130A1 EP 20110155082 EP20110155082 EP 20110155082 EP 11155082 A EP11155082 A EP 11155082A EP 2365130 A1 EP2365130 A1 EP 2365130A1
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EP
European Patent Office
Prior art keywords
fiber composite
additive
composite fiber
reactive component
paper
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EP20110155082
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German (de)
English (en)
Inventor
Reinhard Kräuter
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Bene_fit Systems & Co KG GmbH
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Bene_fit Systems & Co KG GmbH
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Publication of EP2365130A1 publication Critical patent/EP2365130A1/fr
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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
    • D21H21/14—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 function or properties in or on the paper
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately

Definitions

  • the invention relates to a fiber composite which comprises at least one additive integrated into the fiber composite which is suitable for improving at least one property of the fiber composite selected from the group consisting of opacity, whiteness, cellulose content, strength, flame retardancy, air permeability, porosity Gloss, smoothness, haptic, printability, hapticity, coatability, dyeability, color rendering, wet strength, tear propagation resistance, bondability, sheet-forming properties, dewaterability, volume index, roughness, drying, coatability, chemical resistance, pick resistance, mottling and others.
  • the additive can be prepared from at least two liquid and / or solid reactive components which can be supplied separately to the fiber composite and which can be reacted with one another during or after the production of the fiber composite by chemical reaction to the additive.
  • the invention relates to a method for producing a fiber composite, which comprises at least one integrated in the fiber composite additive, which is suitable for improving at least one property of the fiber composite, which is selected from a group, which opacity, whiteness, cellulose content, strength, flame retardancy , Air permeability, porosity, gloss, smoothness, haptics, printability, hapticity, coatability, dyeability, color rendering, wet strength, tear propagation resistance, bondability, sheet forming properties, dewaterability, volume index, roughness, drying, coatability, chemical resistance, pick resistance, mottling and others.
  • the additive is prepared from at least two liquid and / or solid reactive components, which are fed to the fiber composite separately and which be reacted with each other during or after the production of the fiber composite to the additive.
  • Paper is a material that is mainly used for writing and printing and consists largely of vegetable fibers.
  • fillers, pigments and additives are used in papermaking.
  • Important applications for such fiber composites are in addition to the use as information carrier packaging (cardboard, cardboard), hygiene papers such as toilet paper and specialty papers such as wallpaper.
  • the main component of paper is usually pulp or mechanical pulp (eg made of groundwood).
  • fillers and / or pigments are added to the stock. Through this one is able to adapt the properties of the paper to a certain extent to the respective requirements.
  • Possible fillers are z. Kaolin, talc, titanium dioxide, ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • Kaolin is mainly used as a pigment in papermaking. Kaolin remains chemically inert over a wide pH range and can therefore be used not only in acidic but also in alkaline production processes.
  • Talc reduces the porosity of paper and is therefore used to improve the printability of uncoated papers.
  • Titanium dioxide With titanium dioxide high opacity, good light scattering and excellent gloss can be achieved. TiO 2 is many times more expensive than calcium carbonate and is therefore not used in standard filling or coating applications. Titanium dioxide is one of the most expensive components compared to the mentioned fillers and pigments for paper.
  • GCC ground
  • PCC precipitated calcium carbonate
  • GCC contains 40-75% particles with a size (particle diameter d 50 ) of less than 2 ⁇ m.
  • PCC is a synthetic industrial mineral made from quicklime or its raw material, limestone. The paper industry is the largest buyer of PCC and uses the material as a filler and as a coating pigment. PCC reduces fiber strength and therefore can not be used in bulk as a filler. The same applies to other fillers used according to the prior art.
  • Further properties of papers can be influenced by further additives.
  • high opacity and high whiteness are crucial goals z. B. in the production of specialty papers.
  • pigments especially TiO 2 can Both the whiteness, but especially the opacity be increased significantly.
  • TiO 2 causes high opacity and a high whiteness, but has no beneficial self-extinguishing properties, or no flame retardant effect, which are in some applications of great interest.
  • the very expensive TiO 2 does not contribute to the reinforcement of the paper.
  • a high tensile strength is z. B. desired in the manufacture of kraft paper or decorative paper. The strength of the tensile strength is usually measured as breaking load in. The force necessary to tear a paper sample is given in Newton.
  • the tensile strength mainly depends on the basis weight
  • the tensile strength is often referred back to the basis weight and given as the tensile index with the unit of measure Nm / g (or kNm / g).
  • the strength is reduced.
  • the paper industry has an interest in having innovative processes and formulations which make it possible to provide a paper product with high opacity and high filler content at a favorable price. These should have the properties and functionalities known or improved from the state of the art, in particular with regard to strength and self-extinguishing properties.
  • Possibilities for this purpose include, for example, the fibers by physical, chemical or mechanical methods or a combination of these methods z. B. in combination with other methods or materials, eg. As fillers or pigments to change so that they give the paper higher strength at the same time lesser amount of fiber. A positive side effect here is that the optical properties and processing properties of papers thus produced could also be improved due to the higher filler content.
  • the above-mentioned fillers and pigments in the indicated mineralogical or chemical or morphological form are added to the process of papermaking or, as in DE 10 2006 029 642 B3 described, precipitated in the pulp suspension.
  • a method for loading a pulp suspension with fillers, in particular calcium carbonate wherein calcium hydroxide is introduced in liquid or dry form into the fiber suspension and precipitated by a chemical reaction of the fillers in the pulp suspension.
  • the PCC precipitates rhombohedral, scalenohedral or spherical and the crystals have dimensions of 0.05 - 5 ⁇ m.
  • DE 10 2005 015 196 A1 describes a process for flame retardant finishing of fiber products using polyethyleneimine and a phosphoric acid.
  • EP 112 903 3 B1 discloses a process in which a particularly highly concentrated slurry with up to 70% solids of satin white is obtained. This is z. B. used for high quality art papers with a high gloss and a high degree of whiteness as an additive. These papers receive their excellent print appearance and exceptional feel, as requested and expected by customers for high quality art paper, through a special satin-lay process.
  • the object of the invention is therefore to provide a fiber composite which comprises at least one additive integrated in the fiber composite, which is suitable for improving at least one property of the fiber composite, wherein the additive of at least two reactive components can be produced, which the fiber composite fed separately are and which during or after the production of the fiber composite with each other by chemical reaction to the additive can be implemented.
  • Another aim is that a high opacity and a high degree of whiteness in the fiber composite can be achieved with a reduced proportion of TiO 2 or without the addition of TiO 2 .
  • the relative proportion of fibers in the production or coating of a fiber composite should be reduced to reduce the manufacturing costs and at the same time the strength of the fiber composite should be kept almost constant or increased.
  • An essential aspect of the invention is a fiber composite which comprises at least one additive integrated in the fiber composite, which is suitable for improving at least one property of the fiber composite which is selected from a group which opacity, whiteness, cellulose content, strength, flame retardancy, air permeability , Porosity, gloss, smoothness, feel, printability, hapticity, flatability, dyeability, color rendering, wet strength, tear propagation resistance, bondability, sheet forming properties, dewaterability, bulk index, roughness, drying, coatability, chemical resistance, pick resistance, mottling and others, the additive consisting of at least two reactive components can be produced, which can be supplied to the fiber composite separately and which can be reacted with each other during or after the production of the fiber composite by chemical reaction to the additive.
  • the additive consisting of at least two reactive components can be produced, which can be supplied to the fiber composite separately and which can be reacted with each other during or after the production of the fiber composite by chemical reaction to the additive.
  • the chemical reaction of the at least two liquid and / or solid reactive components to form an additive during or after the production of the fiber composite offers the possibility of being able to use cavities in the fiber composite particularly efficiently.
  • at least one of the reactive components preferably all reactive components, are liquid and / or solid and / or gaseous components.
  • a fiber composite in which at least one of the reactive components is selected from a group which comprises Ca compounds, Mg compounds, Ba compounds, Sr compounds, Al compounds, ammonium compounds, borates, silicates, phosphates, sulfates , Salts of organic acids, silica and others, which components may be present as a solid, suspension, emulsion and / or solution in aqueous and / or organic solvent.
  • the reactive components is selected from a group which comprises Ca compounds, Mg compounds, Ba compounds, Sr compounds, Al compounds, ammonium compounds, borates, silicates, phosphates, sulfates , Salts of organic acids, silica and others, which components may be present as a solid, suspension, emulsion and / or solution in aqueous and / or organic solvent.
  • the described components offer by reaction with other substances, which may also be selected from the group of these components, the ability to produce a variety of additives directly in the fiber composite can.
  • the positive effect of some of the additives that can be produced thereby is already known, but this is often significantly enhanced by the chemical reaction directly in the fiber composite. It is thus possible, for example, to produce fiber composites with a very high degree of whiteness or L * value in the L * a * b * color space even without the use of TiO 2 .
  • a fiber composite for. As a paper to equip flame retardant in a simple and cost-effective manner. Other chemical and / or physical properties of the fiber composite (eg paper, cardboard, cardboard), such.
  • the additive is present in the fiber composite as a solid.
  • it is also possible that it is present as a gel, liquid film, sol or other forms in the fiber composite.
  • a possible additive in high-grade paper grades with a high gloss and a high degree of whiteness is satin white of the empirical formula Ca 6 Al 2 (SO 4 ) 3 (OH) 12 ⁇ 26H 2 O, which occasionally also contains Ca 6 Al 2 [(OH) 12
  • particularly highly concentrated suspensions are used for coating papers Additive containing up to 70% solids used. Thanks to a special calendering process, these paper grades receive their excellent print appearance and an extraordinary feel.
  • the suspensions are characterized by a disadvantageously high viscosity, which makes handling very difficult. Both the materials used for the preparation of this suspension and the difficult handling make paper containing satin-white more expensive.
  • the additive in the fiber composite is satin white and / or has the empirical formula Ca 6 Al 2 [ (OH) 12
  • a Ca component may first be added as filler to a fiber composite before, during or after its production. Subsequently, the fiber composite is coated by a customary in the paper industry application unit according to the prior art (eg, film press, size press, blade) with an Al-containing component, for example Al 2 (SO 4 ) 3 . This penetrates the paper and forms with the contained Ca-component in the fiber composite satin white.
  • the reaction conditions such as a possibly necessary pH adjustment or others are adapted to the respective requirements.
  • the fiber composite initially contains an Al-containing component and is then coated in a subsequent step with a Ca-containing component.
  • the use of highly viscous suspensions can be dispensed with.
  • the additive comprises a carbonate group and / or a silicate group and / or a sulfate group and an alkaline earth metal, preferably Ca and / or Mg, this additive having a structure by which the fiber composite is additionally crosslinkable.
  • Such additives are particularly preferred in order to be able to maintain or even increase the strength of the fiber composite even in the case of possibly reduced cellulose content.
  • Such carbonates or silicates or sulfates form net-like structures which reinforce the fiber composite in addition to the net-like composite of the cellulose fibers. This can be done, for example, in that in the reaction of the reactive components used, these crystallize in the form of fine needles or rods and are present in this form in the fiber composite. The individual needles and / or rods interlock and thus form an additional network.
  • the additive crystals can be firmly bonded to the individual cellulose fibers, which not only two separate networks, namely one made of cellulose fibers and another of additive crystals, which penetrate each other, but a single network, which includes both cellulose fibers and additive crystals and so has a special strength. Also other crystal forms, e.g. Tufts are suitable for such network structure enhancing crosslinks.
  • the invention is therefore not limited to additives which crystallize in needle and / or rod form.
  • other additives with similar crosslinking properties is possible, even if they have no carbonate group and / or silicate group.
  • these are phosphates.
  • the fiber composite is particularly preferably a cardboard and / or a paper or a paperboard and / or paper precursor. Since particular requirements are placed on the material properties in the case of boards and / or papers, particular demands are placed on the additives for these applications.
  • the formation of the additives during or after the production of the fiber composite makes it possible to influence a wide range of properties of a paper or a cardboard. In some cases it is possible to increase the proportion of additives and / or to improve the effectiveness of the additives in the fiber composite.
  • Such a fiber composite preferably takes place as a storage medium for information, as hygiene articles and / or for applications in the construction industry, packaging industry and / or as a decorative element. Especially in these applications, high demands are made in particular with regard to strength, feel, opacity, gloss, smoothness, printability, color rendering, volume index, roughness, chemical resistance, mottling and others.
  • Another essential aspect of the invention is a method for producing a fiber composite which comprises at least one additive integrated in the fiber composite, which is suitable for improving at least one property of the fiber composite which is selected from a group which opacity, whiteness, cellulose content, strength , flame retardancy, air permeability, porosity, gloss, smoothness, haptics, printability, creasability, coatability, dyeability, color rendering, wet strength, tear propagation resistance, bondability, sheet forming properties, dewaterability, volume index, roughness, drying, coatability, chemical resistance, pick resistance, mottling and others wherein the additive is prepared from at least two reactive components which are supplied separately to the fiber composite and which are reacted with each other during or after the production of the fiber composite to the additive.
  • the additive is prepared from at least two reactive components which are supplied separately to the fiber composite and which are reacted with each other during or after the production of the fiber composite to the additive.
  • the handling can be facilitated, since many times soluble reactive components are used and not a suspension of the additive must be handled.
  • the distribution of the additive in the fiber composite can also be improved, since - especially in the case of homogeneous solutions of the reactive components - the reaction to the additive can be very homogeneously distributed over the entire fiber composite. This leads to improved properties, in particular with regard to mottling.
  • the formation of the additive in terms of the strength of the fiber composite is advantageous because in the formation of the additive this can also get into the finest gaps in the fiber composite. As a result, for example, an additional crosslinking of cellulose fibers via the additive in these areas is possible.
  • liquid and / or solid reactive components are used.
  • the reaction of the reactive components to the additive is possible during various process steps.
  • at least one first reactive component is added to a fiber before and / or during formation of a fiber composite
  • at least one further second reactive component is added to the fiber composite in a second step during and / or after its formation this second reactive component, preferably brought about by an adjustment of defined reaction conditions and optionally by addition of further reactants, with the first reactive component for the reaction to the additive.
  • the addition of the second reactive component may be independent of the reaction to the additive. It is likewise possible for the addition of the second additive and / or the reaction to take place in a time- and / or place-offset manner. Optionally, this can also be done before or after the production of the paper or the (possibly partial) drying.
  • At least one first reactive component is introduced onto the fiber composite and / or into the fiber composite, and in a second subsequent step at least one further, second reactive component is applied to the fiber composite and / or introduced into the fiber composite and this second reactive component, preferably by an adjustment of defined reaction conditions and optionally by adding further reactants, with the first reactive component for the reaction to the additive brought.
  • the production of the fiber composite takes place, for example. of the paper sheet and only in a subsequent step, the first reactive component is applied to the fiber composite. It is e.g. by diffusion possible that the first reactive component also penetrates into the interior of the fiber composite. The penetration depth can be controlled via a selection of process parameters.
  • a plurality of additives are formed by such a method.
  • at least one third reactive component is introduced onto the fiber composite and / or into the fiber composite
  • at least one further, fourth reactive component is applied to the fiber composite and / or introduced into the fiber composite and this fourth reactive component, preferably by setting defined reaction conditions and optionally by adding further reactants, brought to the reaction with the third reactive component to the additive.
  • the example of papermaking can therefore be any material.
  • the reactive components are applied at the same time to a fiber composite or introduced into this.
  • a first and a second reactive component is introduced onto the fiber composite and / or fiber composite and this second reactive component, preferably by setting defined reaction conditions and optionally by adding further reactants, with the first reactive Component brought to the reaction for the additive.
  • the time and place of addition of the respective reactive components to one another and, in particular, the time and place of initiation of the reaction of these components with one another are independent.
  • Particularly preferred is a method in which the first and second reactive components are added to the fiber composite, which react to satin white with the empirical formula Ca 6 Al 2 (SO 4 ) 3 (OH) 12 ⁇ 26H 2 O.
  • the highly viscous suspension of satin white must be handled procedurally in order to introduce the satin white into the fiber composite.
  • the fiber composite is admixed with first and second reactive components which react to form an additive comprising a carbonate group and / or a silicate group and / or a sulfate group and an alkaline earth metal, preferably Ca and Mg, and preferably has a structure , which additionally crosslinks the fiber composite.
  • Example (natural or synthetic) prefers Shape, example Ca sources Ca (OH) 2 , CaO, CaSO 4 , CaCl 2 , Ca (NO 3 ) 2 , Ca 2+ CaO, Ca (OH) 2 , Ca 2+ Powder / suspension, solution Mg sources Mg (OH) 2, MgO, MgSO4, MgCl2, Mg (NO 3).
  • the ion form is optional for all NH 4 (OH), NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 , polyammonium phosphate
  • the ion form is also optional for all Solution, gaseous, powder, suspension Ca sources Ca (OH) 2, CaO, C 3 SO 4, CaCl 2, Ca (NO 3) 2, Ca 2+ CaO, Ca (OH) 2 , Ca 2+ Powder 1 suspension, solution Mg sources Mg (OH) 2, MgO, MgSO4, MgCl2, Mg (NO 3) 2, Mg 2+ MgO, Mg (OH) 2 , Mg 2+ Powder 1 suspension Combined Ca and Mg sources Dolomit
  • the following table shows an overview of chemical-physical parameters for further description of the first or further components.
  • the degree of purity of the reactive components used can be comparatively low, since an additional purification can take place by the reaction to the additive. For example, this is possible if the contaminant can not react with the second or another reactive component and therefore, for. B. remains in solution and can be washed out with remaining solvent from the fiber composite.
  • Table 2 parameter unit Area P refers Mostly preferred Purity****) ma% 1-100 5-100 10-100 Heavy metals ***) ma% ⁇ 10 ⁇ 5 ⁇ 1 ***) Sum of: Cu, Pb, Hg, Zn, Ni, Cd, Cr ****) purity as a single substance or as a mixture of these individual substances analogous to Table 1 or similar
  • Table 3 parameter unit Area P refers Mostly preferred Purity****) ma% 1-100 5-100 10-100 Heavy metals ***) ma% ⁇ 10 ⁇ 5 ⁇ 1 ***) Sum of: Cu, Pb, Hg, Zn, Ni, Cd, Cr ****) purity as a single substance or as a mixture of these individual substances analogous to Table 1 or similar
  • a paper according to the prior art is first used and this coated by means of a laboratory film press with a second component.
  • the fiber composite used as base paper was a office paper, 80 g / m 2 , DIN A4, CaCO 3 30% by mass, to which an H 2 SO 4 solution, 10% by mass, was applied.
  • the conditions of the laboratory film press in producing the fiber composite according to Example 1 are shown in Table 4.
  • the subsequent drying took place over 30 s with 100% IR and hot air capacity (1000 watts total device output).
  • Table 4 doctor squeegee pressure rolling pressure speed Wet application [g] [bar] [bar] [M / min] - - 600 11 0.36 0.24 0.27
  • Table 5 A selection of chemical and physical data of a so produced fiber composite according to Example 1 are shown in Table 5.
  • Table 5 parameter blank Pattern with reactive components 2 Whiteness, R 457, Elrepho 90 92 Inorganic paper components, X-ray diffraction CaCO 3 CaCO 3 and CaSO 4 To clarify this is For clarity, this graphic is enlarged after the description as Fig. 1 shown. Graphic following the description enlarged as Fig. 2 shown. REM irregular particle structure For clarity, this illustration is enlarged as follows Fig. 3 shown. Fiber and Stem Particle Structure For clarity, this illustration is enlarged as follows Fig. 4 shown.
  • Table 7 The results of investigations into the fire behavior of such treated fiber composites are shown in Table 7. It can be seen that a reaction has taken place which makes the paper self-extinguishing. The coating impregnated the paper in such a way that a flame-retardant property was achieved. The other paper parameters could be kept the same, improved or only insignificantly deteriorated.
  • Table 7 Blank office paper Blank sample of printing paper Office paper with order c Printing paper with order c Office paper with order d Printing paper with order d fire behavior Not self-extinguishing Not self-extinguishing self-extinguishing self-extinguishing self-extinguishing self-extinguishing self-extinguishing self-extinguishing self-extinguishing.
  • a paper with a reactive component 1 was prepared and then coated with a second reactive component 2 by means of a laboratory film press.
  • a Rapid Köthen sheet former was used to prepare a paper having a first reactive component.
  • the conditions for making paper analogous to Example 3 are shown in Table 8.
  • Table 8 raw materials unit concentration Pulp suspension ma% 4.0 1.
  • reactive component comprising CaCO 3 and MgO as suspension ma% 20 Paper, Targets value sheet weight G 2.3 Fibrous material in the leaf ma% 70 Salary, 1st reactive component, should ma% 30 *)
  • d 90 10 ⁇ m
  • d 50 3 ⁇ m and high purity of CaCO 3 and MgO.
  • Part 2 Coating of a fiber composite obtained by the method described in Part 1 with a second reactive component
  • Table 11 parameter base paper Base paper after order opacity 85 90 fire behavior Not self-extinguishing self-extinguishing REM irregular Contains mineral fiber approaches X-ray diffraction CaCO 3 , MgO, Mg (OH) 2 CaCO 3 , MgO, Mg (OH) 2 , MgNH 4 PO 4 .H 2 O
  • a reactive material is added to the pulp prior to paper sheet formation and, after sheet formation, is located in the sheet and thereafter reacted with a second component.
  • pulp used in this example is pulp.
  • the first reactive component used in this example is an aqueous suspension of a mixture of Ca (OH) 2 and Mg (OH) 2 prepared by hydration of fully calcined dolomite.
  • a laboratory sheet former Rost-Köthen
  • a fiber composite is produced from an aqueous suspension of the pulp with the addition of the first reactive component, which is then fumigated in the moist state with CO 2 as an example of the second component.
  • the conditions are varied.
  • the reaction takes place a) at low temperature and b) at elevated temperature.
  • Table 12 shows the chemical and physical data of a fiber composite that can be produced according to Example 4. As the table shows, both whiteness and opacity could be increased over the control.
  • a fiber composite according to the prior art is prepared and applied near the surface of a first reactive material by brushing and this immediately reacted with a second component to the reaction.
  • a fiber composite according to the prior art filter paper is used as a fiber composite according to the prior art filter paper.
  • This is coated by means of semiautomatic film applicator with a suspension of the reactive component 1 (6 microns squeegee, 140 mm / sec squeegee speed).
  • Reactive component 1 used here is an aqueous suspension of a mixture of Ca (OH) 2 and Mg (OH) 2 , for example prepared by hydration of fully calcined dolomite.
  • the coated fiber composite is then gassed in the wet state with CO 2 as an example of the second component. The conditions are varied here.
  • a base paper according to the prior art is coated with a suitable and known application method, eg Curtaincoating in parallel with a Ca-containing aqueous component and an Al-containing aqueous component, wherein the reaction product forms directly on the paper surface.
  • the Ca component is a suspension of Ca (OH) 2 (10% by mass) and the Al component is an Al 2 (SO 4 ) 3 solution (5% by mass). With water, these components react after the reaction Ca 3 Al 2 (OH) 12 + 3 CaSO 4 .2H 2 O ⁇ Ca 6 Al 2 (SO 4 ) 3 (OH) 12 .226H 2 O to satin white. It comes directly to the surface of the base paper to form a layer of satin white, associated with an increase in whiteness, opacity and smoothness.
  • the fiber composites thus obtained may e.g. used as paper and are brought there in the known and due to the technical, economic and environmental benefits in new applications used.
  • inventive storage and / or application of a first or further and / or second or further component in the paper or on the paper surface leads to the chemical formation of new mineral modifications and / or a physical phase change of materials.
  • new paper properties are also formed, eg. Example, caused by structural change of materials increase the strength, opacity, whiteness or self-extinguishing properties.
  • the products of the invention are suitable for use z.
  • FIG. 1 shows a spectrum of the X-ray diffraction analysis of the blank of Example 1.
  • especially calcite CaCO 3 provides a clear signal.
  • a signal for gypsum CaSO 4 -2H 2 O can not be recognized, or does not stand out from the background noise.
  • FIG. 3 shows a scanning electron micrograph of the particle structure of the blank of Example 1. It can be seen predominantly platelet-shaped particles, which have largely attached to agglomerates together. However, a large number of individual particles can also be recognized.
  • FIG. 4 shows a scanning electron micrograph of the particle structure of the coated paper of Example 1. Here it can be seen that predominantly rod-shaped particles have formed. Partly they are stacked to clumps. Some of the rod-shaped crystals have also attached to the cellulose fiber, which extends from the right edge of the image obliquely to the left to the upper edge of the picture.
  • FIG. 5 shows a scanning electron micrograph of the particle structure of the resulting additives of Example 4 at low temperature reaction control. It can be seen a variety of rod-shaped crystals, which are distributed seemingly disordered over the entire image section. They do not seem to have a preference orientation. Many of the rod-shaped crystals have lateral extensions, which allow the individual crystals to interlock with one another and thus form a composite in the form of a chaotically appearing network.
  • FIG. 6 a scanning electron micrograph of the particle structure of the resulting additives of Example 4 is shown, but in reaction at elevated temperature.
  • the rod-shaped crystals obtained also in this experimental procedure appear slightly larger than those in Fig. 5 and to be slightly more irregular. This results in a variety of interaction options through which the individual crystals can interact with each other.
  • the network structure seems out compared to that Fig. 5 however, to be less dense.
  • FIG. 7 shows a scanning electron micrograph of the particle structure of the resulting additives from Example 5 at low temperature reaction control.
  • rod-shaped crystals can be clearly seen. Some of these are covered with the smaller crystals, so that forms a rough surface, through which the individual rods can get caught with each other. It seems to have formed a comparatively wide-meshed network structure, since almost every rod-shaped particles is in contact with at least two other of these particles.
  • FIG. 8 shows a scanning electron micrograph of the particle structure of the resulting additives from Example 5 in reaction at elevated temperature. Again, a variety of rod-shaped crystals can be seen, on which have accumulated smaller, particles of undetermined geometry. The network-like compound forming by interaction of the rods seems to be opposite to the one in FIG Fig. 7 shown to be denser.

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WO2017152217A1 (fr) * 2016-03-10 2017-09-14 Monash University Composition de matériau et procédé de production d'une composition de matériau présentant des propriétés barrière améliorées
EP2948591B1 (fr) 2013-01-22 2017-10-18 Emin Leydier Matériaux fibreux en feuille à propriétés de résistance mécanique améliorées, procédé, utilisation et compositions aqueuses associés

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US5275699A (en) * 1992-10-07 1994-01-04 University Of Washington Compositions and methods for filling dried cellulosic fibers with an inorganic filler
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EP1129033B1 (fr) 1998-11-10 2005-02-02 Rethmann Lippewerk GmbH Procede de production de liaisons de calcium contenant de l'eau de cristallisation
DE102005015196A1 (de) 2005-04-02 2006-10-05 Ciba Spezialitätenchemie Pfersee GmbH Verfahren zur flammhemmenden Ausrüstung von Faserprodukten
DE102006029642B3 (de) 2006-06-28 2008-02-28 Voith Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension mit Füllstoff
DE102007019794A1 (de) * 2007-04-26 2008-10-30 Voith Patent Gmbh Verfahren zum Beladen von Fasern einer Faserstoffsuspension mit CaCO3 gebildet aus CaCI2 und Ca(HCO3)2, (NH4)2CO3 und/oder NH4HCO3

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US2935437A (en) * 1953-11-20 1960-05-03 Columbia Southern Chem Corp Method of making a pigment-filled paper
DE1546234A1 (de) * 1963-12-16 1970-05-21 Wildbad Papier Verfahren zur Herstellung von alterungsbestaendigen Papieren
US5824364A (en) * 1992-04-07 1998-10-20 International Paper Company Methods of manufacture for highly loaded fiber-based composite material
US5275699A (en) * 1992-10-07 1994-01-04 University Of Washington Compositions and methods for filling dried cellulosic fibers with an inorganic filler
US6387212B1 (en) * 1998-02-20 2002-05-14 L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for obtaining fibers integral with calcium carbonate particles
EP1129033B1 (fr) 1998-11-10 2005-02-02 Rethmann Lippewerk GmbH Procede de production de liaisons de calcium contenant de l'eau de cristallisation
DE102005015196A1 (de) 2005-04-02 2006-10-05 Ciba Spezialitätenchemie Pfersee GmbH Verfahren zur flammhemmenden Ausrüstung von Faserprodukten
DE102006029642B3 (de) 2006-06-28 2008-02-28 Voith Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension mit Füllstoff
DE102007019794A1 (de) * 2007-04-26 2008-10-30 Voith Patent Gmbh Verfahren zum Beladen von Fasern einer Faserstoffsuspension mit CaCO3 gebildet aus CaCI2 und Ca(HCO3)2, (NH4)2CO3 und/oder NH4HCO3

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2948591B1 (fr) 2013-01-22 2017-10-18 Emin Leydier Matériaux fibreux en feuille à propriétés de résistance mécanique améliorées, procédé, utilisation et compositions aqueuses associés
WO2017152217A1 (fr) * 2016-03-10 2017-09-14 Monash University Composition de matériau et procédé de production d'une composition de matériau présentant des propriétés barrière améliorées

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