FI64675C - DRYGT FYLLMEDEL INNEHAOLLANDE FIBERBANOR OCH FOERFARANDE FOER FRAMSTAELLNING DAERAV - Google Patents

Description

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Patent- OCh registerst / relsen Ansöktn utlegd och utl.skrlften published 31U0.CSj (32) (33) (31) Privilege claimed —Beg »r <J prtorltet 02.02.78 USA (US) 874458 (71) Dow Chemical Europe SA, Leland I, Doan-Strasse 3 »8810 Horgen,

Switzerland-Schwei z (CH) (72) Kent Bruce MeReynolds, Midland, Michigan, USA (US) (74) Oy Kolster Ab (54) Filler-rich fibrous webs and method for their production - Drygt fyllmedel innehällande fiber-banor och förfarande för framställning thereof

The invention relates to pigmented, felted fibrous webs, in particular to high-filler webs with a low fiber content, and to a process for their production.

Paper is described as a thin sheet-like product composed of a number of interconnected, small discrete fibers (usually pulp fibers). Small amounts of latex have been used in the papermaking process. Fillers have also been used to improve certain properties of the paper, despite the fact that the strength of the web decreases as a result. The amount of fillers heretofore used in papermaking processes with conventional equipment, such as a flat wire machine, has generally not been greater than 30-35% of the total dry weight of the web, although up to 40% has been shown to be feasible. Retention of fillers during web formation has been perceived as a significant problem.

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The use of asbestos in the manufacture of other types of fibrous webs has been tried for many years. Such fibrous webs have preferably been used in the manufacture of various products, such as floor coverings and damped spaper. However, there is evidence that asbestos fibers are harmful to human health. In some countries, the use of asbestos is banned and the United States is considering fairly severe restrictions on its use. Thus, there is a great need to find new systems that do not use asbestos. Such new asbestos-free systems can reach the state of the art, although their total properties do not exceed those of asbestos-containing materials. When properties or manufacturing methods improve, such systems are very useful.

It would be particularly advantageous if a new method for producing high-filler papers, and in particular asbestos-free products, could be implemented with existing equipment, without the need for large, new capital investments.

The water-felted self-supporting web of the invention consists essentially of a combination of (A) water-dispersible fibers, (B), a film-forming, water-insoluble organic polymer, and (C) a water-insoluble, non-fibrous, inorganic filler for which the web is characterized in that it contains 1-30% fibers, 2-30% organic polymer and 60-95% filler.

A preferred method of making this web also uses a flocculant.

A fiber is a water-insoluble, water-dispersible natural or man-made fiber or a mixture of such fibers. Usually, water dispersibility is provided by a small amount of ionic or hydrophilic groups or charges that are insufficient in size to provide water solubility. Both long and short fibers or mixtures thereof are useful, but short fibers are preferred. Many fibers obtained from natural materials are anionic, e.g. wood pulp. Some of the active ingredients are treated 64675 to make them slightly ionic, i.e., anionic or cationic. Glass fibers, crushed glass, blown glass, waste paper pulp, cotton and linen pulp, mineral wool, artificial wood such as polyethylene, straw, ceramic cake fibers, nylon fibers, polyester fibers, etc. are useful. Particularly useful fibers are cellulose and ligno-cellulose fibers, commonly known as various softwood and hardwood pulps, such as stone-ground wood pulp, hot-milled mechanical pulp, chemimechanical pulp, semi-chemical pulp, and chemical pulp. Specific examples are unbleached sulphite pulp, bleached sulphite pulp, unbleached sulphate pulp and bleached sulphate pulp.

The film-forming, water-insoluble organic polymer useful in the practice of this invention is natural or synthetic and may be a homopolymer, a copolymer of two or more ethylenically unsaturated monomers, or a mixture of such polymers. In particular, for ease of handling to prepare the product and to limit the loss of contaminants to the environment, it is generally preferred that the polymer be in the form of a latex, i.e. as an aqueous colloidal dispersion. Representative organic polymers include natural rubber, synthetic rubbers such as styrene / butadiene rubbers, isoprene rubbers, butyl rubbers and nitrile rubbers, and other ethylenically unsaturated rubber or resin polymers that form a film, preferably at or below room temperature. although in special cases a polymer may be used which is film-forming at the temperature used to form the web. Non-film-forming polymers may be used in the blends, provided that the resulting blend is film-forming. Polymers made to form a film using plasticizers can also be used. Polymers that are already available in latex form are preferred - especially water-repellent polymers prepared by emulsion polymerization from one or more ethylenically unsaturated monomers. Representative such latices are described in U.S. Patent 3,640,922 (column 1, line 61-column 2, line 34). This section (especially column 2, lines 2-9) gives preference to latices of polymers and copolymers, <% 4,64675, which do not contain a substantial part of hydrophilic groups. For use in this invention, the latexes preferably have some ionic hydrophilic groups, but must be free of sufficient non-ionic colloidal stabilization to interfere with fiber agglomerate formation. Such nonionic, colloid stabilization could be achieved with nonionic emulsifiers or in the presence of copolymerized monomers having hydrophilic groups of the same nature as those in nonionic emulsifiers, for example hydroxyl and amide groups. Thus, if monomers containing such hydrophilic groups are present as polymerized ingredients in latex polymers, these monomers are present in small amounts, such as less than about 10%, usually less than about 5% by weight of the polymer, for best results. Although very small amounts of nonionic emulsifiers may be acceptable in some combinations, their use is generally not advantageous and should not be used in amounts sufficient to interfere with the destabilization step of the process.

The latex combinations used in this invention are selected from latexes in which a polymer as described above remains in the aqueous dispersion due to ion stabilization. Such ionic equilibration is achieved, for example, by using an ionic surfactant or small amounts of a monomer containing an ionic group during the emulsion polymerization associated with the preparation of the latex. The small number of ionic groups bound to the polymer generally gives a charge of about 0.7 milliequivalents per gram of polymer in the latex. It is generally preferred that the latex component used in this invention have a polymer-bound charge of about 0.03 to 0.4, preferably about 0.09 to 0.18 milliequivalents per gram of polymer in the latex, especially when the charge is provided. carboxylic salt groups. The term "polymer-bound" with respect to ionic groups or charges refers to ionic groups or charges that are not desorbable from the polymer. Such ionic groups or charged substances are obtained, as mentioned above, by copolymerizing the ionic group-containing monomer or by other means, such as inoculation, by attaching (with covalent bonds) catalyst moieties to the polymer, in particular sulphate groups from persulphate catalysts or other. 64675 non-ionic groups already attached to the polymer by covalent bonds into ionic groups.

The ionic groups are preferably carboxylic salt groups, especially alkali metal and arammonium carboxylate groups, or quaternary ammonium salt groups, but other anionic and cationic groups are also useful; e.g., sulfate, sulfonate, and amino groups. Carboxyl salt groups are quite preferred.

For latex combinations with little or no detectable amount of ionic groups bound to the polymer, ionic stabilization is achieved with adsorbed ionic surfactants. Small amounts of ionic surfactant can be used with latexes with bound ionic groups, but increasing amounts of surfactant in excess of those required for adequate stabilization tend to make the proper selection of other components of the system more critical and complicate formation.

Anionic and cationic surfactants are well known in the art and suitable agents can be selected, e.g., from those listed in the annual publication "McCutcheon's Detergents and Emulsifiers", e.g. in the 1973 edition (published by McCutcheon's Division, Allured Publishing Corporation, Ridgewood, NJ). Examples of nonionic surfactants are also given in the above-mentioned literature reference.

Particularly preferred latexes (i.e., latexes having a bound charge of from about 0.09 to about 0.18 milliequivalents / g of polymer) generally perform best in the process and provide the best mixed web as a whole. When these particularly preferred latices are used in the process, the method of the colloid destabilization step and the choice of the quantity and qualities of the other ingredients are of less importance within the limits described. Observing the behavior of such preferred latexes during the process provides clues as to the choice of various other components to be used when it is desired to use latexes that are inexpensive and functional, but are not particularly preferred. For example, when performing the colloid destabilization step by a method using a flocculant having the opposite charge as the latex, the appearance and nature of the flocculated material formed using particularly preferred latexes is controlled by one skilled in the art in the critical selection of other components when latex is not particularly preferred. , but which can be used - in particular a latex with a higher charge than the preferred latexes.

However, there are cases where, for practical reasons, it is advantageous to use latices with a bound charge greater than 0.8 and even greater than 0.4 milliequivalents per gram of polymer in the latex, e.g. when it is desired that the bonded ionic groups, in addition to their stabilizing function, interact to a greater extent with other beneficial components of the combination.

The charge / mass ratio, expressed herein in milliequivalents per gram of polymer in the latex, may not (and generally does) correspond to, for example, a milliequivalent portion of an ionic group-containing monomer polymerized with nonionic, water-repellent monomers by emulsion polymerization to form a latex. These differences arise (1) because some ionic monomer polymerizes within the latex particle and thus does not affect the stabilization of the dispersion of polymer particles and will not be measured, (2) the ionic monomer may homopolymerize or copolymerize to form varying amounts of water-soluble polymers, or (3) does not polymerize completely like other monomers. In general, as the proportion of ionic monomer relative to total monomer increases, the proportion of ionic groups of ionic monomers on the surface of the particle decreases and the number of ionic groups in the latex moieties or groups forming ionic water-soluble polymers increases, respectively. Since too much excess of water-soluble polymers, either anionic or nonionic, can cause problems in this process, it is generally desirable when using bound charges at higher concentrations, (a) use latices for which special precautions have been taken to reduce the formation of water-soluble polymer. , or (b) adding to the combination agents that render the water-soluble polymers insoluble, or (c) removing some or all of such water-soluble polymers.

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Latexes of any readily available size are useful in the practice of this invention, but average particle diameters between about 0.10 and n are preferred. 0.26 μm (about 1000 to about 2600 Angstroms) - especially between about 0.12 to about 0.18 μm (about 1200 to about 1800 Å). Because the latex is diluted during the process, the dry matter content of the latex upon delivery is not critical.

In preparing several of these latexes of different compositions useful in the invention, it is preferable to use a known chain transfer agent, such as various long chain mercaptans, bromoform, and carbon tetrachloride, although other agents may be used.

The excipients used in the practice of this invention are finely divided, substantially water-insoluble, inorganic substances. Such substances include, for example, titanium dioxide, amorphous silica, zinc oxide, barium sulfate, calcium carbonate, calcium sulfate, aluminum silicate, clay, magnesium silicate, diatomaceous earth, aluminum trihydrate, magnesium oxide of two or more, Magnesium hydroxide is particularly well suited for use in the manufacture of a product having good properties with conventional papermaking equipment available, in addition to contributing to the good refractory and microbiological resistance of the product and is advantageous. However, calcium carbonate is sometimes preferred, especially for applications where economic factors are particularly important because it is readily available, gives good structure, works well in the process, and can use impure grades such as ground limestone. The particle size of the fillers is such that the diameter of the main part is less than 50 Atm. The average diameter is generally greater than about 0.1 microns, and preferably is about 0.1 to about 20 microns. For preferred embodiments, the fillers should be asbestos-free.

In many embodiments of the process of this invention, a flocculant (sometimes also referred to as a precipitation aid) is highly preferred. Such flocculants are water-dispersible, preferably water-soluble, ionic compounds or polymers, i.e. compounds or polymers having a positive or negative charge. For the method, a flocculant having the opposite charge to the latex ionic stabilizer is usually selected. If the latex has a negative charge, the flocculant has a cationic charge and vice versa. However, when combinations of two or more flocculants are used, the charge of all of them need not be the opposite of the initial charge of the latex.

Representative flocculants are cationic starch? water-soluble inorganic salts such as alum, aluminum urea sulfate, calcium chloride and magnesium chloride; an ionic latex having the opposite charge (+ or -) to the binder latex, e.g. cationic latex or anionic latex? water-soluble, ionic, synthetic organic polymers such as polyethyleneimine and various ionic polyacrylamides such as carboxyl-containing polyacrylamides; copolymers of acrylamide with dimethylaminoethyl methacrylate or diallyldimethylammonium chloride? polyacrylamides modified other than by copolymerization to obtain ionic groups? and combinations of two or more of the foregoing added are particularly preferred when the latex used is anionic. Polymer flocculants are preferred because they are more effective, tend to produce less water sensitive products, and provide better shear strength with the paper stock.

The preferred method of making the products of this invention is particularly well suited for use in a test sheet forming apparatus or conventional, continuous papermaking equipment such as a flat wire machine, a cylinder machine, a suction machine such as a Rotaformer machine or a handboard machine. Other well-known variants of such devices are also suitable for use in the practice of this invention, for example a planar wire machine with successive headboxes or multi-cylinder machines in which, if desired, different pulps can be used with different cylinders in one or more layers to form a finished board. , to vary the composition and properties.

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For further details, reference is made to the general summary of paper and papermaking found in Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Publishers, Inc., NY 14 (1967), pages 494-510, where sheet formation and suitable equipment are described on pages 505- 508.

The invention also relates to a process for preparing a fibrous web rich in fillers, wherein (I) an aqueous dispersion is prepared from water-dispersible fibers; (II) the resulting dispersion is mixed with: (A) a finely divided, substantially water-insoluble, non-fibrous, inorganic filler, and (B) a binder containing a film-forming, water-insoluble organic polymer in the form of an ionically stabilized latex; (III) the resulting mixture is colloidally destabilized to form a fiber agglomerate in an aqueous slurry; (IV) on a porous substrate, the aqueous slurry is divided and drained from it to form a wet web; and (V) drying the web; characterized in that the mixture obtained in step (II) contains, on a dry weight basis, of the total dry matter content: 1 to 30%, preferably 5 to 15%, fibers, 60 to 95%, preferably 75 to 90%, filler, 2 to 30% , preferably 5 to 15%, latex, and that the ionically stabilized latex does not have sufficient non-ionic stabilization to interfere with the formation of the fiber agglomerate, the percentages being by weight and calculated on the total dry matter.

In the process according to the invention, the fibrous material is subjected to mechanical treatment in the presence of water in a manner richly described in the field of papermaking as pulping and grinding.

The cellulosic fibers are usually ground to a Canadian Standard Freeness (CSF) of about 350 ml to about 700 ml, preferably about 400 ml. 600 ml, 0.3% precipitate. Synthetic fibers are mechanically treated in the same way, but unless they have been specially treated they do not fibrillate to give the same degree of dispersion obtained with cellulosic pulps, so the Canadian Standard test is not suitable for such materials. The fiber content of the man-made fibers is generally either about 1 cm, preferably about 0.3 to about 0.6 cm.

The consistency of the pulp thus obtained (% by weight of dry fiber) is usually about 0.1 to about 6%, preferably about 0.5% to about 3%.

When mixing the fibers and other components of the web, water is added at the same time to reduce the consistency of the resulting stock to a value usually between about 0.1 and about 6%, preferably about 1 to about 5%. Part of the dilution water is preferably zero water or process water, which is returned from the later stages of the web-making process. Alternatively or in addition, some process water may be used in the fiber milling step. Usually, the filler, diluent water, and latex, which are generally pre-diluted to a lower dry matter content than it was at the time of manufacture, are added (usually, but not necessarily, respectively) to the fiber dispersion with stirring. At least a portion of the required colloidal de-stabilization may occur simultaneously with the mixing of the fibers, filler, and latex, either by the interaction of the required components or by the simultaneous addition of other optional wet-end additives such as those mentioned below. Mechanical shearing due to mixing and transfer of substances through the used equipment can cause or help destabilization. However, the combination of mixing and destabilization steps results in a fibrous agglomerate in an aqueous slurry having a concentration of 100 g of dry matter in 13,500 ml of aqueous slurry, which should drain in about 4 to about 120 seconds, especially about 15 to about 60 seconds. and preferably about 30 -n. 45 seconds in a 25.4-30.5 cm (10-12 ") Williams Standard Sheet Mold with a 5 cm outlet and 76.2 cm water column fitted with a standard 100- "mesh", a stainless steel screen (wire size 0.1143 mm) to provide at least 85% dry matter retention in a single pass, which dry matter contains at least 60% by weight filler.In addition, in preferred embodiments, the drained water is substantially clear. a preferred method of performing (or supplementing) destabilization is to mix with other components a flocculant, i.e., a water-dispersible or water-soluble ionic compound having a charge opposite to (+ or -) ionic stabilization, sufficiently, generally less than n 1%, calculated on the total dry weight of the components When the flocculant is used, it is added in such a way that destabilization can take place before the partitioning and draining step. the flocculant is added in the pulp box or at such a point in the mass transfer compartment of the device that there is sufficient time to achieve the desired effect, but not so much that the resulting flocculated mass is subjected to excessive shearing. After partitioning and draining the resulting aqueous dispersion, the web thus obtained is optionally wet-pressed and dried with equipment commonly used in papermaking.

The process temperature used in the wet web formation step is typically in the range of about 4.4 ° C (40 ° F) to about 54 ° C (130 ° F), although temperatures outside these limits may be used provided that they are at the freezing point of the aqueous dispersion. above and below the temperature at which the latex polymer used would soften excessively. Sometimes temperatures higher than ambient conditions promote faster runoff.

Also useful in the practice of this invention are small amounts of various other wet end additives of the type commonly used in papermaking. Such substances include antioxidants, various hydrocarbon and natural waxes, especially in the form of anionic or cationic emulsions; cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose; water-soluble organic dyes, water-insoluble but water-dispersible, color pigments such as kimro, vat dyes and sulfur dye; starch, natural gums such as guar gum and John's bread gum, in particular their anionic and cationic derivatives; nonionic acrylamide polymers; strength-improving resins such as melamine-formaldehyde-di-resins, urea-formaldehyde resins, and various types of hardeners such as sulfur-containing vulcanizing agents and additives. Additional amounts and / or species of anionic or cationic surfactants may also be added in small amounts at various points in the process, if desired. Nonionic surfactants should be used 12,64675 sparingly, if at all.

In general, either pulp or surface sizing can be used in conjunction with the features of this invention.

The densities of the products obtained by the method described above vary widely, such as between about 480-2400 kg / m3. Due to the high proportion of filler in the weight of the products, the filler selected for a particular product has a significant effect on the density and other properties of the product.

The thickness of the formed web can vary between about 0.076 and 3.175 mm, the preferred value depending somewhat on the intended use. In general, however, the thickness is between 0.381 and 1.651 mm.

The method according to the invention gives water-felted, self-supporting webs with a high filler content, whereby a large part of the added filler is retained in the webs. The term "water-felted web" commonly used in the art refers to a web deposited from a dilute aqueous slurry having a dry matter content of usually 4% or less. While the filler forms the major part of the web, latex and fibers are also retained in the web in large proportions. The retention of all dry matter used in the process on the web is generally greater than 85% by weight and in preferred embodiments is greater than 95%.

The method and product of this invention have many advantages. Compared to prior art paper webs, the web has less moisture when it leaves the wet end of the machine. Thus, at the same basis weight of the web, less energy is required to dry the web and the machine can be run faster or a thicker web can be dried. The new method can be implemented using newly designed and available equipment that is commonly owned by paper manufacturers. Easily available raw materials are used. Much of the raw material is a cheap filler and the overall cost is low. The density can be changed simply by selecting the filler. Preferred embodiments are also an asbestos shirt.

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The following examples illustrate ways in which this invention may be practiced.

All parts and percentages are by weight unless otherwise indicated. Components marked with a letter symbol, e.g. latex A, are explained in Tables A, B, C and D.

Table A Fillers

Symbol Description A Magnesium hydroxide; particle size 5-10 μm, as an aqueous slurry 58% dry matter content.

B Calcium carbonate; ground chalk No. 9} average particle size 15 μm.

C Zinc oxide; particle size less than that 1% retained on the Tyler 325 mesh screen.

D Titanium dioxide; particle size less than that 0.2% is retained on the Tyler 325 mesh screen.

E A mixture of 50% filler A and 50% filler N.

F A mixture of 80% filler A and 20% filler B.

G A mixture of 60% filler A and 40% filler B.

H Barium sulphate; average particle size 2.5 Aim.

J Talc, average particle size 2.7 μm.

K H.T. clay, average particle size 0.8 μm.

L Alumina trihydrate; 75% mesh passes through a 325 mesh Tyler screen.

M Magnesium carbonate; particle size, 90% passes through a 200-mesh Tyler sieve.

N Expanded perlite; particle size, 1-16% retained on a 325-mesh Tyler sieve.

O Magnesium hydroxide; particle size 5-10 μm, as a powder.

_ “I.

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Table A (continued)

Symbol Description P Water-washed, paper filler grade clay, average particle diameter 3 yum.

Q Talc, average particle size 9 yum.

Table B Latexes

Symbol Description A Mixture of 65 parts (on a solid basis) of a latex of a copolymer of 56% styrene and 44% butadiene, prepared with 1% bromoform form transfer agent and containing 0.5 % disodium salt of dodecyldiphenyl ether disulfonic acid and 4% modified resin soap, the percentages based on the weight of the copolymer, and 35 parts of latex C and a further 0.2%, based on the total weight of the polymer in the mixture, of tridecyl sodium sulfate with 0.02 bound charge .06 milliequivalents / granule of polymer.

B. A mixture of 75 parts (on a solid basis) of a copolymer of 50% styrene and 50% butadiene, a latex prepared with 1% bromoform chain transfer agent and containing 0.5% dodecyldiphenyl ether disulfonyl the disodium salt of the acid and 4% modified resin soap, the percentages being based on the weight of the copolymer, and 35 parts (on a solid basis) of latex G, the bound charge of the mixture being between 0.02 and 0.06 milliequivalents / gram of copolymer.

C. Latex of a copolymer containing 41% styrene, 55% butadiene, 3% itaconic acid and 1% acrylic acid, prepared with 1,75% bromoform-ket Juns displacer and containing 0,5% disodium salt of dodecyldiphenyl ether disulphonic acid, wherein the percentages are calculated on the weight of the polymer in the latex. The bound charge is 0.144 rr.il-equivalent of weak acid (carboxyl) and 0.058 milliequivalents of strong acid (sulfate) / gram of copolymer.

D A mixture of 80 parts of latex C with 20 parts of latex G and having a bound charge of between 0.15 and 0.2 milliequivalents / gram of polymer.

E A mixture of 80 parts of latex C and 20 parts of a latex of a copolymer of 80% styrene and 20% butadiene containing 0.1% of the disodium salt of dodecyldiphenyl ether disulphonic acid, the bound charge of the mixture being between 0, 15 -0.2 milliequivalents / gram of copolymer.

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F Latex-like mixture, except that latex G

the amount is 30% instead of 35%, the bound charge of the mixture being between 0.02 and 0.06 milliequivalents / gram of polymer.

G Latex of a copolymer of 81% styrene, 17% butadiene and 2% acrylic acid, prepared with 2% carbon tetrachloride chain transfer agent and containing 0,2% tridecyl sodium sulphate, calculated on the weight of the copolymer latex. The bound charge of the latex is 0.065 milliequivalents / gram of copolymer.

H A mixture of 70 parts (on a solid basis) of a latex of a copolymer of 50% styrene and 50% butadiene, prepared with 1% of a bromoform chain transfer agent and containing 0,5% of the disodium salt of dodecyldiphenyl ether disulphonic acid and 4% modified resin soap, calculated as a percentage by weight of the copolymer, and 30 parts (on a solid basis) of latex C, the bound charge of the mixture being between 0.07 and 0.1 milliequivalents / gram of copolymer.

J Polychloroprene latex stabilized with rosin soap and having essentially no measurable bound charge at all.

K Latex of a copolymer containing 95.5% ethyl acrylate, 2% acrylamide and 2.5% N-methylolacrylamide, containing 0.5% sodium lauryl sulphate and having an average particle diameter of 0.09 μm , wherein all percentages are based on the weight of the copolymer and the bound charge is less than 0.03 mil equivalent / g of copolymer.

L Latex of a copolymer containing 65% styrene and 35% butadiene prepared with 0.2% dodecanethiol chain transfer agent, stabilized with 4% dodecylbenzyltrimethylammonium chloride surfactant and having an average particle diameter of 0.075 μm , all percentages being based on the weight of the copolymer, the bound charge being less than 0.02 milliequivalents / g of copolymer.

M Latex of a copolymer containing 90% vinylidene chloride, 5% butyl acrylate and 5% acrylonitrile, obtained by co-polymerisation of the monomer with 1,4% of sulphoethyl methacrylate, with an average particle diameter of 0,12 μm, all percentages being calculated by weight of the copolymer the bound charge is between 0.03 and 0.04 milliequivalents / g of copolymer.

16 64675 N A mixture of 70 parts (on a solid basis) of a copolymer of 49% styrene, 50% butadiene and 1% itaconic acid, a latex prepared in the presence of 6% carbon tetrachloride and containing 0.75% sodium salt of dodecyldiphenyl ether-disulfonic acid, and 30 parts (on a solid basis) of latex G. The bound charge of the mixture is 0.116 milliequivalents of weak acid (carboxyl-1i) and 0.031 milliequivalents of strong acid (sulfate) / g of polymer in the mixture, all percentages being calculated by weight.

0 Latex of a copolymer containing 48% styrene, 50% butyl acrylate and 2% acrylic acid, containing 0.5% disodium salt of dodecyldiphenyl ether-disulfonic acid, calculated as a percentage by weight of the copolymer. The bound charge of the latex is 0.071 milliequivalents of acid (carboxyl) / g of copolymer.

P "0" -like latex, except that the copolymer consists of 46% styrene, 50% butyl acrylate and 4% acrylic acid, and the bound charge of the latex is 0.092 milliequivalents (carboxyl) / g copolymer.

Q Latex of a copolymer containing 69% vinylidene chloride, 4.9% butyl acrylate, 24.7% acrylonitrile and 1.4% 2-sulfoethyl methacrylate. The bound charge is 0.039 milliequivalents / g of copolymer.

R Latex prepared by emulsion copolymerization of 35% styrene, 55% butadiene and 10% acrylic acid with 8% carbon tetrachloride chain transfer agent in the presence of 0.75% ammonium persulphate catalyst and 0.5 parts of dodecyldiphenyl ether disatrazine acid, all percentages are calculated on the total monomer weight. The bound charge is 0.268 milliequivalents of weak acid (carboxyl) and 0.091 milliequivalents of strong acid (sulfate) / g of copolymer. The pH of the latex is 3.4.

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Table C Fibers

Symbol Description fr Bleached coniferous coniferous land.

3 Bleached hardwood graft pulp.

C. A mixture of 50% fiber A and 50% fiber B.

3 Unbleached "southern pine".

3 Unbleached "northern Softwood".

P Unbleached sulphite softwood pulp.

G SWP-fibrillated polyethylene; E-400, fiber length 0.9 mm.

H SWP-fibrillated polyethylene; R-830, fiber length 2.0 mm.

I SWP-fibrillated polyethylene; R-990, fiber length 2.5 mm.

J A mixture of 50% fiber I and 50% fiber D.

K A mixture of 25% fiber I and 75% fiber D.

L A mixture of 50% fiber G and 50% fiber D.

M Polyester (polyethylene terephthalate); denier per thread 6.0; fiber length 0.135 mm.

N Nylon 66; denier per strand 3.0; fiber length 0.25 mm.

0 Säteri; denier per strand 5.5; fiber length 0.135 mm.

P Stone wool.

Q A mixture of 50% fiber D and 50% fiber?

R A mixture of 75% fiber E, 12.5% polyethylene terephthalate fiber, 3 denier per fiber; 0.635 cm in length, plus 12.5% starch-bonded and glass fibers, 0.635 cm in length and 6 / am in diameter.

Table D Flocculants

Symbol Description A Copolymer of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulphate (Eetz 1260) and having an Ostwald viscosity of 17 centipoises in a 0,5% aqueous solution containing 3% sodium chloride at 25uC.

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Symbol Description B The Mannich reaction product of polyacrylamide, formaldehyde, and dimethylamine quaternized with methyl chloride to give the resulting quaternized product of the grade described in U.S. Patent 4,010,131 and having a Ostwald viscosity of 30 centipoise of 0.5%. as an aqueous solution containing 3% sodium chloride at 25 ° C.

C Aluna.

D High molecular weight polyacrylamide which is about 5% hydrolysed and has a viscosity of 23 centipoise measured at 25 ° C as a 0.5% aqueous solution.

E Terpolymer of acrylamide, dimethyldiallylammonium chloride and diethyldiallylammonium chloride with an Ostwald viscosity of 3.7 centipoises as a 0.5% aqueous solution containing 3% sodium chloride at 25 ° C.

In the examples, test sheets were prepared using a specially developed standard method, with the modifications shown in the specific examples. The fiber shown in the standard method (if cellulose fiber) is defibered to a Canadian Standard Freeness (CSF) of 500 ml and a consistency of about 1.2% by weight. The man-made fibers are dispersed in water with a TAPPI disintegrator (600 rpm), but no Canadian Standard Freeness measurement is performed. To the resulting aqueous dispersion (5 g of fibers) (weight) is further mixed with a predetermined amount of water to give a final volume of 2000 ml. Stirring is continued while adding 80 g of the indicated filler as a powder, except, when mentioned, as an aqueous slurry, followed by 15 g of the latex, calculated on the dry matter. The resulting mixture is mechanically cut in a Jabsco centrifugal pump for 15 seconds, followed by mixing with a laboratory stirrer with a three-bladed propeller on one arm rotating at 900 rpm, while slowly adding a 0.1% aqueous solution of the flocculant shown until the main aqueous solution is present. Sufficient (n-62 ml) of the resulting stock to give 3 g of dry matter, dilute to L000 ml with Five and measure the Canadian Standard Freeness TAPPI according to T 227 M-58. The Freeness sample is returned to the stock, which is then diluted to 13,500 ml and the sheet is formed on a (25.4 x 30.5 cm) Williams Standard Sheet Mold and the draining time is recorded on an 10O mesh screen. The resulting wet sheet is transferred from the wire cloth to the press, pressing approx. 7x10 kg / m using two suction cartons to draw water from the sheet. The sheets are stacked alternately with the suction cartons 3a are wet pressed at a pressure of 352x10 kg / m. The partially dried sheets are weighed and dried in a sheet dryer at a plate temperature of 116-121 ° C (240-250 ° F), alternating sheets of sheet against the plate at 0.5-1 minute intervals. The resulting dried sheets are weighed to determine the total amount of solids retained on the sheet. Since enough ingredients have been used to make 100 g sheets with complete retention, the dry weight also represents the retention process.

Examples 1-14

Test sheets are prepared from the latex shown, the unbleached southern pine graft pulp, and the fillers shown using flocculant A by the standard method described above, using the latices and fillers shown in Table I.

The values associated with sheet fabrication are shown in Table I. The properties of the sheets are shown in Table II.

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The test sheets are made of the latex shown, the type of fiber shown, which has been defibered as shown. Canadian Standard Freeness (CFS), for the filler shown and the flocculant shown, using the standard method described above (see Table III). The manufacturing values of the sheet are shown in Table III and the properties of the sheet in Table IV.

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Examples 43-46

Test sheets are prepared by the standard method described above, wherein the fiber is fiber D, and the types of filler, latex, and flocculant are shown in Table V. The properties of the sheets are shown in Table VI.

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Examples 47-49

The test sheets are prepared by the standard method described above, wherein the fiber is unbleached softwood pulp, the latex is latex B, the filler is filler A and the flocculant is A, B or C. In addition to the flocculant, to complement the flocculation. The values for the preparation of test sheets are shown in Table VII. The properties of the sheets are shown in Table VIII.

Table VII Manufacture of sheets

Example Flocculant Pulp Drain time

n: o_ C (a) A (b) B (b) CSB

ml_ml_ml_ml_s_ 47 12 0 0 600 50 48 6 54 0 700 29 49 6 0 80 650 24 (a) 5% aqueous solution (b) 0,1% aqueous solution 3i 64 67 5 Λ m o m

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Examples.it 50-53

The test sheets are prepared by the standard method described above, with the fiber, latex and flocculant appearing in Table IX and the filler being filler A. The values for sheet preparation are also shown in Table IX. Samples of the sheets are placed in a tropical chamber maintained at 100% relative humidity and 32.2 ° C (90 ° F) and previously inoculated with Aspergillus Niger, Trichoderma viridie, Aureobasidium pullulans, Chaetomium globosum and unidentified Penicillium. species. After 21 days and 49 days, the samples were checked for visible evidence of microbiological activity and the loss values of tensile strength at room temperature are measured with 7.6 cm long strips with a tension of 2.5 cm. For comparison, test sheets are prepared from 85 parts of asbestos (Johns Manville, Paperbestos No. 5) and 15 parts of latex C (Comparative Example A-1) and 85 parts of asbestos and 15 parts of latex N (Comparative Example A-2). The test values are shown in Table X.

Visual evaluation is based on a free-to-determine scale for visible evidence of microbiological effect as follows: 0 = no effect 1 = very mild effect 2 = mild effect 3 = moderate effect 4 = severe effect 5 = very strong effect

Tensile strength tests, except for the length of the test strip, are performed as described after all examples. Table where the tensile strength value shown in X is the percentage change in tensile strength between test strips and reference strips, which are similar to and made simultaneously and are kept outside the tropical chamber for the same length of time.

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Test sheets are prepared by the standard method described above, except that different ratios of fibers, latex and filler are used. The fiber is unbleached softwood graft pulp, the latex is latex B, the filler is filler B and the flocculant is flocculant A. The values are given in Table XI.

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Examples 61-62

The test sheet (Example 61) is prepared from unbleached softwood graft pulp, latex F, filler 0 and flocculant A by the standard method described above. A second test sheet (Example 62) is prepared in the same manner except that 0.25 parts of cationic polyamide-epichlorohydrin resin (Kymen e 557) is added as a 0.132% aqueous solution to the aqueous fiber dispersion before mixing the filler and latex. The values are shown in Table XII.

Table XII

Example Example 61 62 Flocculant A, ml 150 150 stock CSF, ml 755 600 draining time, s 50 110 sheet thickness, mm 1,270 1,143 sheet weight, g (% retention) 94.9 87.0 density, kg / m3 1094.1 1094.1 tensile strength, kN / m2 5516 6481 tensile strength, kN / m2 177 ° C (350 ° ^) 2069 2206

Examples 63-6U

Test sheets are prepared from latex N, fiber R and the amount of filler shown using flocculant E according to the standard method, except that the wet strength additive cationic polyamide-epichlorohydrin resin with 12.8% nitrogen is added after the filler in the amount shown in Table XIII and 1% dry. based on the total amount of the substance, the anionic emulsified hydrocarbon wax is added after the latex. The values are summarized in Table XIII.

m.% 38,64675

Table XIII

Example Example 63_ 6U

filler P,% (solids) 77 filler Q,% (solids) - 77 latex N,% (solids) 15 15 fiber R,% (solids) 8 3 flocculant E, kg / tonne dry matter 1,118 0 , 54 wet strength additive, kg / ton dry matter 3.63 5.18 draining time, s 50 54 sheet density, kg / m ^ 1209.4 1185.4 2 tensile strength, room temperature, kN / m 14314 1198 tensile strength, hot , kN / m 5261 3461 tensile strength, DOP, kN / m2 6516 4654 tensile strength, water, kN / m2 7847 3012 elongation, room temperature,% 3.5 2.7 elongation, 177 ° C (350 ° F) 2.3 2 .0 elongation, DOP,% 3.3 2.3 elongation, water,% 6.3 5.0 * Water uptake,% 3.9 5.5 water swelling,% (length) 0.38 0.22 Samples were 15 cm in length, not less than 10 cm in length.

The products of these examples were particularly suitable for use in floor covering combinations due to their properties, especially in the presence of dimensional stability.

Examples 65-70 Using the standard method, except that the mechanical shearing step with a Jabsco centrifugal pump was omitted, test sheets are prepared from the latex, fiber E and filler Q shown using flocculant E in the ratios of latex, fiber and flocculant to and the total amount of fiber, all calculated on the dry matter. The amounts are also chosen so as to obtain test sheets which theoretically weigh 75 g instead of 100 g and reduce the dilution water of the stock accordingly. The values are shown in Table XIV.

39 64675

Table XIV

. χ

Example no.

65__66_ 67X 68 69 70

Latex, species O O P P Q A

amount,% (a)

Fiber E, amount,% (a) 6 10 6 10 6 10 Flocculant E, amount, kg / tonne (a) 3.00 1.82 3.63 2.13 3.63 2.13

Drainage time, p 97 59 64 41 122 61

Tensile strength, room temperature, kN / irT 13431 10777 12887 13318 11811 10811 (a) = calculated on dry matter * = retention percentage is greater than 92 in all these examples.

Example 71 and Comparative Example 71-C A portion of latex R is mixed with 8% (based on the dry matter of the latex) of carbon tetrachloride. The resulting product is centrifuged. The aqueous whey is removed and the remaining solid is washed with water. The resulting moist solid is redispersed in water by vigorously stirring the solid and water for 30 minutes to 1 hour. The resulting dispersion is latex R-1 and has a pH of 3.8.

Except that theoretically sufficient amounts are made to make a 30 g sheet instead of a 100 g sheet and the stock dilution water is reduced accordingly, a standard method is used to make target sheets for each of the latices R and R1 in 15% corresponding latex, 15% fiber E and 75% filler K (on a dry matter basis, calculated on the weight of latex, fiber and filler) using 127 ml of a 0,1% aqueous solution of flocculant E. Wet test sheets are formed with each latex R-1 (Example 71) and latex R (Comparative Example 71-C) with flow times of 20 and 29 seconds, respectively. In Example 71, there is only a barely detectable amount of foam in the manufacture of the stock only on the sheet when the wet test sheet is dried. Höyle-löLrni.sa iai'MMi flakes during the addition to the air (Yin big progress easily. However, in Comparative Example 71-C, a large amount of • ♦ «40 6 4 6 7 5 foam and foam is produced during the preparation of the stock. So strong adhesion of the dried test sheet to the wire and suction board so that the sheet cannot be removed from the wire.

The bound charge of latex R and latex R-1 is the same because the method for preparing latex R-1 from latex R does not change the existing bound charge (from carboxyl groups). A significant difference is that water-soluble components are removed from latex R, e.g. surfactants and acrylic acid polymers or copolymers having a sufficiently low molecular weight and a sufficiently high carboxyl content to be water-soluble. These results are consistent with the view that excessive amounts of water-soluble polymers, such as surfactants and ionic polymers, are detrimental to the practice of this method.

Examples 72 and 73

The aqueous fiber dispersion is prepared from bleached southern pine branch pulp and water to a consistency of about 4% in a Black Clawson Hydrapulper. The crude dispersion is pumped into a refining chamber and ground to a Canadian Standard Freeness value of 500 ml by circulating through a Sprout-Waldron Twin-Flow Refiner. Filler-rich sheets for Examples 72 and 73 are made from fiber dispersion, latex and filler in the proportions shown in Table XV on a 78.7 cm flat wire machine with phosphor bronze, longitudinally selected wire, 4 flat boxes between chest roll and suction roll, first wet press, first wet press a dryer between the surface gluing press compartments and a 7-roller calendar. The fiber dispersion, filler, water and latex diluted to a dry matter content of 25% are added to the machine type, respectively, whereby the amount of water added is calculated to give a consistency of 4%. The resulting mass is transferred by means of a pulp pump through the pulp valve and then through the vane pump to the headbox. The flocculant shown in Table XV is added between the pulp pump and the pulp valve and some process water from later stages of the process is returned to the system between the pulp valve and the vane pump so that the stock consistency in the headbox is as shown in Table XV. From the headbox, the stock is fed to a wire running at 6.1 meters per minute, where the process water drains to form a wet web, from which excess water is removed by means of four suction boxes before the wire is sucked on the shoulder from the wire. After the two 64675 41 compression steps have further reduced the water content, the web is fed through a dryer and a calender. The process and property values for the filler-rich sheets thus formed are shown in Table XV.

Table XV

Example 72 Example 73

Filler A,% (based on dry matter) 75 8C

Latex C,% (calculated on the dry matter) 15

Latex F,% (calculated on the dry matter) - 15

Bleached softwood graft pulp,% (calculated on dry matter) 10 5 Gelling agent A, kg / tonne of dry matter - o, 64 Gelling agent B, kg / tonne of dry matter 5.45

Consistency in the vat,% 4.0 4.0

Consistency in the headbox,% 3.31 1.22

Canadian Standard Freeness number in the headbox, incl. 603 668

Machine speed, m / min. 6.1 6.1 Wet pressing, 1 press, line pressure, kg / cm 3.58 3.58 2 press, line pressure, kg / cm 12.53 12.53

Arrest,% 09 102

Thickness, mm 0.721 0.704

Density, kg / m3 937.1 905.0

Tensile strength, machine direction, kN / m ^ 5061 3172 transverse direction, kN / in 3572 2820

Hot tensile strength, machine direction, kN / m ^ 2951 1310 transverse direction, kN / m ^ 2275 607 DOP tensile strength, machine direction, kN / m ^ 3737 931

Elongation, room temperature,% machine direction 3.1 2.0 transverse direction 2 * 3 3.8

Elongation, hot,% machine direction 2.0 1.7 cross direction ^ Ό 2.8

Elongation, DOP, machine direction,% 2.3 1.7 Steepness, machine directionI a

TuLor · 119 119 POP 81 29 water 20 29 42 64675

Table XV (cont.)

Example Example __—-- 73

Stiffness, CD

Taber 81 72 DOP 96 12 water 14 19

Elmendorf tear strength, g-cm machine direction 24.8 16.7 cross direction 24.7 11.7

Mullen puncture barrier cheese, fcN / m 168.2 105.5 water uptake,% 14.1 10.3 toluene uptake,% 49.9 59.2 limiting oxygen index (L.P.I.) 47 53

Example 79

The aqueous fiber dispersion is prepared to a consistency of about 9% from unbleached northern softwood branch pulp and water in a Black Clawson Hydrapulper. The crude dispersion is pumped into a refining chamber and ground to a Canadian Standard Freeness value of 500 ml by circulating through a Sprout-Waldron Twin-Flow Refiner. Filler-rich sheets for Example 79 are prepared from a fiber dispersion, the latex shown, the filler shown, and a wet strength additive which is a cationic polyamide-epichlorohydrin resin having 12.8% nitrogen and a viscosity at 25 ° C of 90-65%. , all in the proportions shown in Table XVI, using a flat wire machine with (a) a 91.4 cm wide plastic wire (b) a headbox equipped with a split-type inlet, a homogenizer roller and a Neilson lip opening, (c) a suction roller, ( (d) a through-iron press, (e) an iron counter-press, (f) a drying section comprising 7 and 5 dryers / with fixed casting shafts and 2 felt dryers at the bottom and the blankets of the first section at the top, and (g) a calender with 8 rolls with fiber rolls. Fiber dispersion, filler »wet strength additive, water and latex diluted to 25% dry matter content are added to the machine type, here In order, add an amount of water that is calculated to give 9%. The Cautu pulp is transferred by means of a pulp pump through a pulp valve and then through a vane pump to the headbox. The flocculant shown in Table XVI is added between the pulp pump and the pulp valve and some process water from later stages of the process is returned to the system between the pulp valve and the vane pump so that the stock consistency in the headbox is as shown in Table XVI. From the headbox, the stock is transferred to a wire with a speed of 12.2 m / min and from or to which the process water flows, forming a wet web, from which excess water is removed by means of ira-boxes before or after removing the web from the wire at the suction roll. After the two compression steps have further reduced the water content, the web is fed through a dryer and a calender. The process and property values for the filler-rich web thus formed are shown in Table XVI.

Table XVI

Example 74 Filler B,% (calculated on dry matter) 72.5 latex N,% (calculated on dry matter) 7.5 fiber E,% (calculated on dry matter) 10.0 flocculant E, kg / ton dry matter 0.41 consistency in vine,% 4.0 consistency in headbox,% 1.7

Canadian Standard Freeness number in headbox, ml 568 machine speed, m / min. 12.2 wet compression, 1st press, line pressure, kg / cm 17.9 2nd press, line pressure, kg / cm retention,% 90 thickness, mm 0.584 3 density, kg / m 802.5 tensile strength, machine direction, kN / m ^ 11032 transverse direction, kN / m 4482 stiffness, transverse direction

Table 48

Elmendorf tear strength, g-cm machine direction 136 transverse direction 160 2

Mu 11en puncture strength, kN / m 225.1 fuel oil uptake,% 64.4

The various tests are performed as described below with the additional modifications shown in the specific examples.

44 6 4 6 7 5

Canadian Standard Freeness Number (CSF)

The number, in milliliters, is determined according to TAPPI standard T227-M-58 with a sample containing 3 g of dry matter diluted to 1000 ml with water.

Elmendorf tear-resistant new

The test is performed according to TAPPI method T414-ts-65. Results are presented as the average of at least 3 samples.

Elongation,%

Elongation at room temperature, elongation at 177 ° C (350 ° F) (hot), elongation, OOP, and elongation, water, are determined at 15.2 cm (6 in.) At the same time as the corresponding tensile tests - see . described below.

Restrictive Oxygen Index (L.Q.I.) L.O.I. determined according to test method ASTM D 2863-74.

Mullen burst strength

The TAPPI test method D 403-os-76 is followed, except ·; that the test is performed on thicker sheets. The results shown are the average of four or five samples, ί Retention,% \ The substances for the test sheets are added in amounts sufficient to give sheets weighing 100 g. Thus, the dry weight of product l also represents the percentage of solids retention; the ark.

K

\ For Tasain made with a TasQ wire machine, the retention percentage is proportional to the proportion of filler left in the web. Test samples; the incineration is carried out under conditions such that the filler residue is retained (calculated as a percentage by weight) but the other components are removed. The percentage of ash is multiplied by an appropriate coefficient for the changes caused by combustion in the filler (e.g. Mg (OH) 2 ~> MgO) to determine the percentage of filler in the sheet. From the content of filler found on the sheet (%) and the content of added filler (%) (calculated on the dry matter), calculate the concentration remaining on the web as a percentage of the average of the three samples.

; Stiffness, Taber

Taber stiffness (g-em) is determined according to TAPPI Standard Method T 489-03-76, except that the results of the three samples are averaged unless otherwise indicated. The value obtained is corrected to the thickness of 0,076 cm (30 mil) by multiplying by the factor:

II

45 64675 _ (30) 3 ________ (0,00254) 3 x [thickness of test sample in sows]

For separation from modified Taber stiffness tests (DOP and water - as explained below), the TAPPI method referred to herein is sometimes referred to as Taber Stiffness, Reg. ".

Stiffness, DOP

DOP stiffness (g-cm) is determined in the same way as Taber stiffness, except that the samples are soaked in dioctyl phthalate 18-24 hours before assembly and the value shown is the average of the two samples.

Stiffness, water

Water stiffness is determined in the same manner as Taber stiffness, except that the samples are soaked in water for 18-24 hours before testing and the value shown is the average of the two samples.

Tensile strength, room temperature (R.T)

The sheets are cut into 2.5 cm x 20.3 cm strips and the minimum thickness in the test area is determined. The test strip is placed on an Instron testing machine with a tension interval of 15.2 em. While the Inst-ron is operated at a drawhead speed of 2.5 cm / min, the elongation and the number of kilograms when the strip breaks are recorded.

2 The stress (kN / m) at break is calculated by dividing the force at break by the thickness of the sample. The results are presented as the average of three samples.

Tensile strength, hot

The hot tensile strength is tested in the same way as at room temperature, except that just before the test, the test specimen is incubated at 177 ° C (350 ° P) for 1 minute with the jaws attached to the test machine.

Tensile strength, POP

The DOP tensile strength is tested in the same way as the tensile strength at room temperature, except that the test sample is soaked in dioctyl phthalate 24 hours before testing.

Tensile strength, water

The water tensile strength is determined in the same way as the DOP tensile cheese, except that the soaking takes place in water.

46 64675

Toluene pickup

A suitable sample (5.1 cm x 10.2 cm) is dissolved in toluene for 15 seconds, the amount of weight absorbed is recorded and the absorption is calculated as a percentage by weight.

Absorption of fuel oil

The absorption of the fuel oil is measured in the same way as the absorption of toluene, except that the soaking takes place in the fuel oil.

Water pickup

Water absorption is determined in the same way as toluene absorption, except that soaking takes place in water for 24 hours.

Swelling in water

Swelling in water is determined from a sample similar to that used for water absorption and is calculated from the increase in sample length as a result of soaking in water over 24 hours.

Charge / mass ratio

The bound charge per gram of polymer in the latex is measured by conductometric titration after removal of water-soluble ionic substances. If a sufficient bound charge is present, the latex can often be centrifuged after the addition of, for example, 3% (based on the dry matter of the latex) carbon tetrachloride, the whey phase is separated, the remaining solids are washed and then redispersed with vigorous stirring in water. Conductometric titrations are performed with redispersed solids. Ion exchange methods can also be used to remove ionic water-soluble substances from latexes with a sufficiently bound charge to be stable until the conductometric titration is completed. For latexes with insufficiently bound charge, small amounts of nonionic surfactants are added prior to the ion exchange process to be stable.

Claims (10)

47 64675 A water-felted, self-supporting web consisting essentially of a combination of (A) water-dispersible fibers, (B) a film-forming, water-insoluble organic polymer, and (C) a water-insoluble, non-fibrous, inorganic filler, characterized in that it contains 1-30% fibers, 2-30% organic polymer and 60-95% filler. Web according to Claim 1, characterized in that the organic polymer is obtained from ethylenically unsaturated monomers by emulsion polymerization and, in latex form, has a bound charge of 0.03 to 0.4 milliequivalents / g of polymer. A method of making a filler-rich fibrous web, comprising (I) preparing an aqueous dispersion of water-dispersible fibers; (II) the resulting dispersion is mixed with: (A) a finely divided, substantially water-insoluble, non-fibrous, inorganic filler, and (B) a binder containing a film-forming, water-insoluble organic polymer in the form of an ionically stabilized latex; (III) the resulting mixture is colloidally destabilized to form a fiber agglomerate in an aqueous slurry; (IV) on a porous substrate, the aqueous slurry is divided and drained from it to form a wet web; and (V) drying the web; characterized in that the mixture obtained in step (II) contains, based on the dry weight, the total amount of dry matter: 1 to 30%, preferably 5 to 15%, fibers, 60 to 95%, preferably 75 to 90%, filler, 2 to 30% , preferably 5 to 15%, latex, and that the ionically stabilized latex does not have sufficient nonionic stabilization to interfere with the formation of the fiber agglomerate. Process according to Claim 3, characterized in that in the colloidal destabilization step (III) a fibrous agglomerate in an aqueous slurry is obtained, characterized in that at a dry matter content of 1.8 64675 per 100 g in 13,500 ml the slurry has a draining time onn. 4 to 120 s in a 25.4 cm x 30.5 cm (10 "x 12") Williams Standard Sheet Mold with 5.1 cm (2 ") outlet and 76.2 cm: n (30 ") water column fitted with a 100-mesh stainless steel sieve with a wire diameter of 0.0114 cm (0.0045") and that at least 85% of the total dry matter of the fiber agglomerate remains in the wet web during step (IV) run-off an amount of filler containing at least 60% by weight of filler. Process according to Claim 3, characterized in that the bound charge of the organic polymer in the latex is less than 0.7 milliequivalents / g of polymer. Process according to Claim 5, characterized in that the bound charge of the organic polymer in the latex is 0.03 to 0.4 milliequivalents / g of polymer. Process according to Claim 4, characterized in that the content of the aqueous fiber dispersion is 0.1% to 6%, the fibers are cellulose fibers and the flow time of the fibrous agglomerate is 15 to 60 s. Process according to Claim 3, characterized in that the amount of fiber is 5 to 15%, and the latex contains copolymerized styrene and butadiene. Process according to Claim 3, characterized in that the latex is a mixture of at least two different latex compositions and in that at least one of the latexes contains a copolymer of an ethylenically unsaturated carboxylic acid. Process according to Claim 3, characterized in that the destabilization step is carried out by mixing in the product of steps (I) and (II) a sufficient amount of a water-soluble or water-dispersible ionic compound or polymer having a charge opposite to the ionic stabilization of the latex. 64675 49