DK153575B - PROCEDURE FOR THE WETMAKING OF A HIGH COAT FILM AND SELF-SUSTAINING FILM MADE BY THIS PROCEDURE - Google Patents

Description

in

DK 153575B

The present invention relates to a process for producing pigmented nonwoven films and films made by this method.

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Paper has been described as a foil material made from many small separated taverns (usually cellulose fibers) that are bonded together. Small amounts of latex have been used for papermaking. Fillers have also been used to improve certain properties of the paper, although the strength of the film 10 is thereby reduced. The amount of fillers heretofore used in papermaking on ordinary equipment such as the Fourdrinier machine has generally not exceeded 30 or 35% of the total dry weight of the film, although up to 40% has been described as possible .

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The retention of fillers in the film during formation has been recognized as a significant problem.

The use of asbestos in the manufacture of other types of tavern films has been practiced for many years. Such sheet films 20 have been advantageously used for the manufacture of products such as floor coverings and sound-absorbing paper. However, evidence has been found that asbestos fibers are harmful to human health. In some countries, the use of asbestos has been banned and serious restrictions on its use are being considered in the United States. New systems that do not use asbestos are therefore highly desirable. So = forming new asbestos-free systems can advance the technique, even if their overall properties are no better than the properties of the asbestos-containing materials. Where the properties or methods of manufacture are improved, then forming systems would be a great advantage.

It would be particularly advantageous if a new approach to the production of high-content paper, and especially asbestos-free products, could be carried out at existing plants, so that large new capital investments would not be required.

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DK 153575B

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The process and product of the invention include the combination of a water-dispersible fiber, a film-forming water-insoluble organic polymer, and an inorganic filler in the form of a wet-formed film.

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The invention relates to a process for preparing a high filler tavern film at the following steps: I Preparation of an aqueous dispersion of water dispersible tavern, 1 ° II Mixing this dispersion with: (A) a finely divided, essentially water-insoluble, non-fibrous inorganic filler; and 15 (B) a binder containing a film-forming, water-insoluble organic polymer in the form of an ionically stabilized latex; III. Colloidal destabilization of the resulting mixture to form a tavern agglomerate in aqueous suspension; dewatering the aqueous suspension on a porous support to form a moist web, and V Drying the web, and the process is characterized in that the mixture obtained after step II contains: 1-30% tavern 60 - 95% filler 25 - 30% latex .. .....

the percentages being based on the dry weight and the total dry weight, and that the ionically stabilized latex is without sufficient non-ionic stabilization to interfere with the formation of a tavern agglomerate.

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Essential features of the process and product are a low amount of fiber and a high amount of inorganic filler, and that the process is easily carried out on ordinary papermaking equipment and that the product has good properties. The preferred wet-made asbestos-free high-filler tavern films are suitable as full or partial substitutes for asbestos films for many of these applications, but are not limited to these applications. Representative applications of these foils are sound-absorbing paper, vinyl flooring backing, wrap sheet paper, roofing = lining paper, for insulating pipes, such as insulating paper, heat-deflating paper, cooling tower wrapping, electrically resistant paper and paper products.

The product and process of the invention requires a water-dispersible fiber, a film-forming water-insoluble organic polymer, and a finely divided water-insoluble non-fibrous inorganic filler. In the preferred method, a flocculant is also required.

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The fiber or tavern is any water-insoluble natural or synthetic water-dispersible fiber or mixture of such fibers.

As a rule, water dispersibility is provided by a small amount of ionic or hydrophilic groups or charges of sufficient size to provide a stable aqueous dispersion. Either long or short fibers or mixtures thereof are useful, but short fibers are preferred. Many of the fibers from natural materials are anionic, e.g. wood pulp. Some of the synthetic fibers are processed to make them slightly ionic, ie. anionic or cationic. Glass fibers, chopped glass, blown glass, recycled waste paper, cellulose from cotton = woolen and linen cloths, mineral wool, synthetic wood pulp such as those made of polyethylene, straw, straw, ceramic fiber, nylon fiber, polyester fiber and similar material = 35 kinds are useful. Particularly useful fibers are the cellulosic fibers and lignocellulosic fibers, commonly called wood pulp, of the various kinds from hardwood and softwood such as rock-milled wood, steam-heated mechanical pulp, chemical mechanical pulp, semi-chemical pulp and chemical pulp. Special examples are unbleached sulfite pulp, bleached sulfite pulp, unbleached 40 4

DK 153575B

The film-forming water-insoluble organic polymer which is usable in its design. The invention is natural or synthetic and may be a homopolymer, a copolymer of two or more ethylenically unsaturated monomers or a mixture of these polymers. In order to facilitate the manufacture of the product 5 and to limit the loss of pollutants to the environment, it is generally advantageous for the polymer to be in the form of a latex, ie. an aqueous colloid dis = persion. Representative organic polymers are natural rubber, synthetic rubber sugars such as styrene / butadiene rubber = isoprene rubber, butyl rubber and nitrile rubber, and other rubbery or resinous polymers of ethylenically unsaturated monomers which are film-forming, preferably at in particular case, a polymer which is film-forming at the temperature used to make the film may be used. Non-film-forming polymers can be used in mixtures, provided that the resulting mixture is film-forming. Polymers made film-forming using plasticizers can also be used. Polymers readily available in latex form are preferred, especially hydrophobic polymers prepared by emulsion polymerization of one or more ethylenically unsaturated monomers. Representative of these latexes are those described in U.S. Patent No. 3,640,922, from column 1, line 61 to column 2, line 34. This of = 25 sections (especially column 2, lines 2-9) suggests a preference for latexes of polymers and copolymers which do not have a significant amount of hydrophilic groups. For use in the present invention, the latexes preferably have some ionic hydrophilic groups, but may not have sufficient non-ionic colloidal stabilization that could interfere with the formation of the fibrous agglomerate. This nonionic colloidal stabilization could be provided by nonionic emulsifiers or by the presence of copolymerized monomers having the kind of hydrophilic groups found in nonionic emulsifiers, e.g. hydroxyl and amide = groups. Therefore, if monomers with such hydrophilic groups are polymerized constituents of the latex polymers, ml

DK 153575B

These monomers may be present in small amounts such as less than ca. 10%, usually less than approx. 5% of the weight of the polymer to give the best results. Although very small amounts of nonionic emulsifiers can be tolerated in some materials, their use is usually not advantageous and should not be used in amounts sufficient to generate the destabilization of the process.

Latex materials for use according to the invention are selected from latexes in which a polymer as described above is kept in aqueous dispersion by ionic stabilization. This ionic stabilization is achieved e.g. using an ionic surfactant or small amounts of a moiety containing an ionic group during the emulsion polymerization to prepare the latex. The small amount of 15 ionic groups attached to the polymer will generally give less than about 10 0.7 milli equivalent charge per grams of polymer in the latex. It is usually preferred that the latex component of the present invention has a charge bonded to the polymer of from about 0.03 to 20 approx. 0.4, especially from about 0.09 to about 0.18 milli equivalent per grams of polymer in the latex, especially when the charge is due to carboxylic acid salt groups. The term "bound to the polymer" with respect to ionic groups or charges refers to ionic groups or charges which cannot be desorbed from the polymer. Material containing ionic groups or charges can be obtained as mentioned above by copolymerization of a monomer containing ionic groups or by other means, such as grafting, by bonding (through covalent bonds) of catalyst fragments = 30 ments to the polymer, especially sulfate groups from persulfate. = catalysts, or by conversion to ionic groups of nonionic groups already bound to the covalent bond polymer.

The ionic groups are advantageously carboxylic acid salt groups, especially alkali metal and ammonium carboxylate groups, or

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6 'ternary ammonium salt groups, but other anionic and cationic groups are useful, e.g. sulfate, sulfonate and amino groups. Carboxylic acid salt groups are particularly advantageous.

For latex materials which have no or little detectable amount of ionic groups attached to the polymer, the ionic stabilization of adsorbed ionic surfactants is provided. Small amounts of ionic surfactants can be used for latexes having bonded ionic groups, but increasing amounts of surfactants above the amounts required for adequate stabilization tend to make proper selection of the other components of the system more critical and complicate formation.

Anionic and cationic surfactants are well known, and suitable materials of these classes may be selected e.g. Among those listed in the annual releases of "Mc Cutcheon's Detergents and Emulsifiers" such as the 1973 issue published by McCutcheon's Division Allured Publishing Corpo = ration, Ridgewood, New Jersey. Examples of nonionic surfactants are also found in the above reference.

The particularly preferred latexes (i.e., latexes having from ca.

0.09 to approx. 0.18 milli equivalent bonded charge per gram polymer) generally performs best in the process and, overall, provides the best composite film. When these 25 particularly preferred latexes are used for the process, the method of colloidal destabilization as well as the selection of the amount and nature of the other constituents within the limits described above are less demanding. With these latexes, observing the behavior during the process gives path = 30 conduit for selecting the various other components to be used when one wishes to use latexes within the preferred and usable limits but outside the particularly preferred limits. By way of illustration it can be mentioned that by performing the colloidal destabilization of the process

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7 using a flocculant having a charge opposite to the latex, the appearance and nature of the flocculated material, when using the particularly preferred latexes, will assist the person skilled in the difficult choice 5 of the other components when using a latex. outside the particularly preferred but within the usable limits, especially with higher bonded latex.

However, there are cases in which it is preferable to use latexes with a bound charge above 0.18 and even above 0.4 milli equivalent charge per special purpose. grams of polymer in the latex, e.g. where the bound charge is cationic, where recycling of the material is desirable or where, in addition to their stabilizing role, the bound ionic groups are desired in greater amounts to perform other advantageous reactions with other components of the material.

The ratio of charge to mass expressed in the present = the description as milliequivalents of charge per grams of polymer in the latex do not necessarily respond (and generally do not) e.g. to the amount of milliequivalents of monomer in = 20 containing an ionic group copolymerized with the nonionic hydrophobic monomers by emulsion polymerization to form the latex. These differences occur (1) because some of the ionic monomer is polymerized within a latex particle and thus is not effective in stabilizing the dispersion of polymeric particles and is not measured, (2) the ionic monomer can homopolymerize or copolymerize to form varying amounts of water-soluble polymers, or (3) in some cases, the ionic monomer does not polymerize as completely as the other 30 monomers. As the amount of the ionic monomer relative to the total monomer increases, in general, the amount of the ionic groups in the ionic monomers that are on the surface of the particle and the amount buried inside the latex particles decrease, or which form ionic 35 water soluble polymers grow. Then an excessive profit

DK 153575B

8 of water-soluble polymers, either anionic or nonionic, can cause problems in the present process, it is generally desirable where larger amounts of bound charges are used (a) to use latexes 5 for the preparation of which are made special measures to reduce the formation of water-soluble polymer, or (b) to add materials to the mixture which will insoluble the water-soluble polymers or (c) to remove some or all of these water-soluble polymers.

Latexes of any usually obtainable particle size are useful for carrying out the invention, but average pairs diameter of approx. 1,000 to approx. 2,600 angstroms are preferred, especially from approx. 1,200 to approx. 1,800 angstroms. As the latex is diluted during the process, its solids content, as it is added, is not essential.

For the preparation of many of the latexes of various compositions useful in the invention, it is advantageous to use a chain transfer agent of known nature, such as, but not limited to, the various long chain mercaptans, bromoform and tetrachloro carbon.

The fillers used to carry out the invention are 25 finely divided, essentially water-insoluble, inorganic materials. These materials include e.g. titanium dioxide, amorphous silica, zinc oxide, barium sulfate, calcium carbonate, calcium sulfate, aluminum silicate, clay, magnesium silicate, diatomaceous earth, aluminum trihydrate, magnesium carbonate, partially calcined dolomitic limestone, magnesium hydroxide and mixtures of two or more. Magnesium hydroxide works particularly well on commonly available papermaking equipment to form a product with good properties, contributes to flame resistance and resistance to biological attack, and is preferred. However, sometimes calcium carbonate is preferred, especially for applications where the economic factors are particularly important because it is readily available, provides a good structure, works well in the process, and the impure qualities such as formulation

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light limestone, can be used. Part of the bulk of the fillers is such that the predominant amount is less than 50 microns in diameter. The average diameter is generally above approx. 0.1 microns, and is preferably from ca. 0.1 to approx.

20 micrometers. For preferred embodiments, the filler must be free of asbestos contamination.

In many embodiments of the method of the invention, a flocculant or destabilizer (sometimes called a deposition aid) is very advantageous. These flocculants are water dispersible, preferably water-soluble ionic compounds or polymers, i.e. compounds or polymers having a positive or negative charge. For the process, a flocculant having a charge opposite to the ionic stabilization of the latex is usually selected. If the latex has a negative charge, the flocculant will have a cationic charge and vice versa. When combinations of two or more flocculants = 20 agents are used, they are not necessarily of opposite charge than the initial charge of the latex.

Representative flocculants are cationic starch, water-soluble inorganic salts such as alum, aluminum sulphate = 25 barrels, calcium chloride and magnesium chloride, an ionic latex having a charge opposite to the (+ or -) charge of the binder = the latex, e.g. a 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 diallyldime dimethyl ammonium chloride, modified by polyacrylamide, polyacrylamide, have ionic groups, and combinations of two or more of the above added 35 simultaneously or sequentially. Quaternized polyacrylamide = 10

DK 153575B

derivatives are particularly advantageous when the latex used is anionic. Polymeric flocculants are preferred because they are more efficient, usually giving less water sensitive. with products and gives the material for the paper making 5 better shear stability.

The preferred method of making the products of the invention is particularly suitable for being performed on apparatus for forming foil with or without conventional continuous papermaking equipment such as a Fourdrinier machine, a cylinder machine, suction machines such as a rotor mold or a cardboard plant. Also suitable for use in the practice of the invention are other well-known modifications of such equipment, e.g. a Fourdrinier machine with secondary head boxes or multi-cylinder machines in which different materials, if desired, can be used in different cylinders to vary the composition and properties of one or more layers that can be found in a finished cardboard. For details, refer to the general paper and cardboard inventory found in Kirk-Other, 20 Encyclopedia of Chemical Technology, Interscience Publishers, Inc., New York 14 (1967), pages 494-510, where the foil formation and its associated equipment is described on pages 505-508.

The preferred process requires the following steps: I. Providing an aqueous dispersion of from about

25% to approx. 15%, of a "water dispersible but water insoluble fiber".

II. Thus, mixing of (A) from ca. 70% to approx. 90% of a finely divided, generally water-insoluble, non-fibrous inorganic filler; and (B), from about 5% to approx. 15% of a binder = 30 agent containing a film-forming water-insoluble organic polymer in the form of an ionically stabilized latex.

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11 III. Colloid destabilization of the resulting mixture to form a fibrous agglomerate in aqueous suspension.

IV. Distribution and dewatering of the aqueous suspension on a porous support such as a wet web forming wire and V. drying the web.

The previous percentages are by weight based on the total dry weight.

In carrying out the invention, the fibrous material is subjected to mechanical action in the presence of water in a manner that is variously described in the papermaking as pulping, milling or refining. Cellulosic fibers for the present invention are usually refined to a Canadian Standard Freedom (CSF) at a 0.3% consistency of from approx. 300 milliliters to approx. 700 milliliters, preferably from approx. 400 milliliters to approx. 600 milliliters. Synthetic fibers are similarly processed mechanically, but unless specially treated, they do not fibrillate, which is why they do not have the same dispersion range as that obtained with cellulose pulp, so that the Canadian standard freedom test is not particularly suitable for such materials. The synthetic fibers generally have a fiber length up to approx. 9.5 mm, preferably from ca. 3.17 mm to approx. 6.35 mm.

The consistency (percent by weight of dry fibrous material) in the material thus obtained is generally from 0.1% to ca. 6%, preferably from ca. 0.5% to approx. 3%.

In the blending of the fiber with other components to the foil, additional water is added to reduce the consistency 30 of the resulting material to a value which is generally 12

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is in the range of approx. 0.1% to approx. 6%, preferably from ca. 1% to approx. 5%. Part of the dilution water is preferably white water or process water, recycled from later stages in the film production. Alternatively or additionally, no = 5 of the process water can be used in the step of refining the fiber. Usually, the filler, dilution water and latex, which are generally pre-diluted to a lower solids content than that with which it is prepared, are added to the fiber dispersion with stirring (usually = 10, but not necessarily in the order mentioned). ). At least some of the necessary colloidal destabilization may occur simultaneously with the mixing of the fiber, filler and latex, either through mutual action between the necessary components or through the simultaneous addition of other optional wet additives such as those listed below. The mechanical displacement caused by mixing and transferring the materials through the plant used may cause or contribute to destabilization. However, the combination of the mixture and the destabilization produces a fibrous agglomerate in aqueous suspension which, with a concentration of 100 g of solid in 13,500 milliliters of the aqueous suspension, should drain within a time of approx. 4 seconds to approx. 120 se = customers, especially from approx. 15 seconds to approx. 60 seconds, and 25 preferably from ca. 30 seconds to approx. 45 seconds in a 25.4 x 30.5 cm Williams standard foil mold having a 5.08 cm exit = increase 76f2 cm water reservoir and equipped with a standard 100 mesh stainless steel screen (wire size 0.114 mm) so that at a single passage is obtained at least 85% back = 30 solids containing at least 60% by weight of filler. Furthermore, in the preferred embodiments, the drainage water is essentially clear. An effective and preferred method for carrying out (or completing the execution) of the destabilization is the mixing with the other components of a flocculant, ie. a water dispersible or water-soluble ionic compound having a charge with opposite sign of the charge of the ionic state =

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13 bilization in sufficient quantity, this amount being in general less than about. 1% based on the total dry weight of the components. When a flocculant is used, it is added so that the destabilization can take place before distribution and dewatering. With continuous foil forming apparatus such as the Fourdrinier machine, the flocculant is added at the material box or at such a point in the material transfer part of the apparatus that there is sufficient time for the desired effect to take place, but not so much that the resulting flocculated material is subjected to unnecessary shear forces. After partitioning the dewatering of the resulting aqueous dispersion, the resulting wet web is optionally wet-pressed and then dried with equipment usually used in papermaking.

The temperature of the process through the step of forming the wet web is generally in the range of about 4.4 ° C to approx. 54 ° C, but temperatures outside this range may be used provided they are above the freezing point of the aqueous dispersion and below the temperature at which the la = tex polymer would become too soft. Sometimes, temperature under ambient conditions promotes faster drainage.

Also useful for carrying out the invention are small amounts of various other wet added additives of the types commonly used in papermaking. These materials include antioxidants, various hydrocarbons and natural waxes, particularly in the form of anionic or cationic emulsions, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, water-soluble organic dyes, water-insoluble but water-dispersible dye pigments, and dye dyes such as carbon black , starch, natural gums such as guar gum and johannesburg gum, especially their anionic and cationic derivatives, non-ionic acrylamide polymers, strength enhancing resins such as melamine-formaldehyde resins, urea-formaldehyde = 14

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resins and curing agents of various types such as the sulfur-containing vulcanizing agents and auxiliary compounds, 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. Non-ionic surfactants should be used sparingly, if at all.

Optionally, either internal or external bonding can be used in accordance with the method of the invention.

The bulk weight of the products prepared by the method described above covers a wide range such as from about 3 to about 3 times. 480 kg per m to approx. 2,400 kg per m. Since the filler constitutes such a large amount of weight of the product, the identity of the filler selected for a given product has a significant effect on the body weight and the other properties of the product.

The thickness of the foil produced can vary from approx.

0.076 mm to approx. 3.17 mm, the preferred value being dependent on some of the intended use. However, the thickness is 20 in general from approx. 0.38 mm to approx. 1.65. ram.

The process according to the invention results in the preparation of wet-made self-supporting films with a high content of filler, where a large part of the added filler is retained in the films. As is common in this art, the term "wet-made foil" refers to a foil deposited from a dilute aqueous suspension which generally has a solids content of 4% or less. Filler = fat makes up most of the foil, but the latex and fiber are also retained in the foil in large quantities. Retention 30 in the foil of all the solids used in the process is generally greater than 85% by weight and in the preferred embodiments greater than 95% by weight.

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The method and product of the invention have many advantages. Compared to previously known paper foils, there is less moisture in the foil as it exits the wet end of the machine. Therefore, with the same weight basis for the foil = 5, less energy is needed to dry it, and the machine can be operated faster or a thicker foil can be dried. The new method can be carried out using the known and available plants of the kind commonly used in paper mills. Easily accessible raw = 10 materials used. A large part of the raw materials are car = equal fillers and the total cost is low. Space = weight can be changed simply through the choice of filler. The preferred embodiments are also asbestos-free.

The following examples illustrate ways in which the present invention can be carried out, but are not to be construed as limiting the invention. All parts and percentages are by weight unless otherwise expressly stated. Components identified by letter, e.g. latex A, be be = 20 written in Tables A, B, C and D.

Table A

Fillers 25

Ident i f i cat i on Describe A Magnesium hydroxide, particle size 5-10 3q microns, which is in aqueous slurry with 58% solids.

B Calcium carbonate, No. 9 whitewash, portion size 15 microns.

35 C Zinc oxide, part in boiler larger, see less than 1% retained on Tyler 325 mesh screen.

D Titanium dioxide, particle 1 larger, less than

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Identification Description 16 g E Mixture of 50¾ of filler A and 50¾ of filler N.

F Mixture of 80¾ of filler A and 20¾ of filler B.

10 G Mixture of 60¾ of filler A and 40¾ of filler B.

H Barium sulfate, average particle size 2.5 2.5 microns.

j Talk, average particle size 2.7 mi.

-, q K H.T. clay, average in t spare t in ke 1 s dry re 1 see 0.8 microns.

L Alum ini umoxy dtr in hydrate, particle size 75¾ through 325-mesh Tiller screen.

25 M Magnesium carbonate, particle size 90% through 200 mesh screen screen.

N Expanded perlite * particle size.se 1-16% retained on 325-mesh Tyler screen.

30 0 Magn in umhydroy.i d, par t in ke 1 larger 1 see 5-10 mi chromium as a powder.

P Quality washable clay for paper filler, average particle diameter 3 microns, Q Talk, average particle size 9 micro meters.

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TABLE B

latexes

Identification Description A A mixture of 65 parts (based on solid 5) of a latex of a copolymer of 56% styrene and 44% butadiene prepared with 1% bromoform chain transfer agent and containing 0.5% of the disodium salt of dead = cyldiphenyl ether disulfonic acid and 4% of a modified rosin soap, the percentages being based on the weight of the copolymer, with 35 parts of latex G and an additional 0.2% calculated on the total polymer weight in the mixture of tridecyl sodium sulfate, which mixture has a bound charge between 0.02 and 0.06 milli equivalent per grams of polymer.

B A mixture of 75 parts (on a solid basis) of a latex of a copolymer of 50% styrene and 50% butadiene prepared with 1% bromoform chain transfer agent and containing 0.5% of the disodium salt of dead = cyldiphenyl ether disulfonic acid and 4 % of a modified rosin soap, which percentages are based on the copolymer weight, 25 by 25 parts (on a solid basis) of la = tex G, which mixture has a bound charge between 0.02 and 0.06 mill equivalent grams of copolymer.

C A latex of a copolymer of 41% styrene, 55% butadiene, 3% itaconic acid and 1% acrylic acid prepared with 1.75% bromoform chain transfer agent and containing 0.5% of the disodium salt of the dodecyl diphenyl = herdisulfonic acid, which percentages is calculated on the weight of polymer in the latex.

The bound charge is 0.144 milliequivalents = slightly weak acid (carboxyl) and 0.058 milli = equivalent strong acid (sulphate) per liter. grams of copolymer.

40 D A mixture of 80 parts of latex C with 20 parts of latex G with a bound charge between 0.15 and 0.2 milliequivalents per minute. grams of polymer.

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Identification Description E A mixture of 80 parts of latex C and 20 parts of latex of a copolymer of an 80% styrene and 20% butadiene containing 0.1% 5 of the disodium salt of the dodecyl diphenyl = herdisulfonic acid, which mixture has a bound charge between 0, 15 and 0.2 milli = equivalent per grams of copolymer.

F A mixture such as latex A except that the amount of latex G in the mixture is 30% instead of 35%, which has a bound charge between 0.02 and 0.06 milli = equivalent per liter. grams of polymer.

G A latex of a copolymer of 81% styrene / 17% butadiene and 2% acrylic acid made with 2% tetrachlorocarbon chain transfer agent and containing 0.2% tridecylna = triumphate, which percentages are based on the weight of copolymer in the latex. The 20 bound charge of the latex is 0.065 milli = equivalent per grams of copolymers.

H A mixture of 70 parts (based on solids) of a latex of a copolymer of 50% styrene and 50% butadiene prepared with 1% bromoform chain transfer agent and containing 0.5% of the disodium salt of dodecyldiphenyl ether disulfonic acid and 4% of a modified rosin soap, which percentages are based on the copolymer weight, 30 by 30 parts (based on solids) of latex C, which mixture has a bound charge between 0.07 and 0.1 milliequivalents per minute. grams of copolymer.

J A polychloroprene latex stabilized with a rosin acid soap with substantially no measurable bound charge.

K A latex of a copolymer of 95.5% ethyl = acrylate, 2% acrylamide and 2.5% N-methylol = acrylamide containing 0.5% sodium luu = 40 rylsulfate with an average particle diameter of 900 Angstroms, all percentages being calculated on the weight of copolymer and having a bound charge less than 0.03

Identification Description 19

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L A latex of a copolymer of 65% styrene and 35% butadiene prepared with 0.2% dodecane = ethiol chain transfer agent stabilized 5 with 4% dodecylbenzyltrimethylammonium chloride as surfactant and with an average particle diameter of 750 Angstroms, all percentages being by weight based on the copolymer weight, and 10 having a bound charge less than 0.02 milliequivalents per liter. grams of copolymer.

M 'A latex of a copolymer of 90% vinylidene = chloride, 5% butyl acrylate and 5% acrylonitrile, obtained by simultaneous polymerization of 15 monomers with 1.4% sulfoethylmethacrylate and having an average pair = 1200 Angstrom, with all percentages being based on the copolymer weight and having a bound charge between 20 0.03 and 0.04 milliequivalents per liter. grams of co = polymer.

N A mixture of 70 parts (based on solids) of a latex of a copolymer of 49% styrene, 50% butadiene and 1% itaconic acid 25 prepared in the presence of 6% tetrachloro = carbon and containing 0.75% of disodium = unsalted of Latex G. of 30 parts (solid solids = ferric acid) of the mixture has a bound 30 charge of 0.116 milliequivalents of weak acid (carboxyl) and 0.031 milliequivalents of strong acid (sulphate) per liter. grams of polymer in the mixture and all percentages are based on the weight of the respective copolymer.

A latex of a copolymer of 48% styrene, 50% butyl acrylate and 2% acrylic acid indenol = 0.5% of the disodium salt of dodecyl = diphenyl ether sulfonic acid, the percentages being based on the copolymer weight. The La = 40 tex has a bound charge of 0.071 mil = equivalent acid (carboxyl) per liter. grams of copolymer.

P A latex such as "0" except that the copolymer composition is 46% sty = 45 pure, 50% butyl acrylate and 4% acrylic acid, and

Identification Description 20

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the bound charge is 0.092 milliequivalents (carboxyl) per liter. grams of copolymer.

Q A latex of a copolymer of 69% vinylidene = 5 chloride, 4.9% butyl acrylate, 24.7% acrylo = nitrile and 1.4% 2-sulfoethyl methacrylate.

The bound charge is 0.03 milliequivalents per liter. grams of polymer.

R A latex prepared by emulsion copolymer = 10 merization of 35% styrene, 55% butadiene and 10% acrylic acid in the presence of 8% tetra-chloro carbon chain transfer agent, 0.75% ammonium persulfate catalyst and 0.5 part of the disodium salt of dodecyldiphenyl acid = 15 etherdisulfonic acid , where all percentages are based on the total monomer weight. The bound charge is 0.268 milliequivalents of weak acid (carboxyl) and 0.091 milliequivalents = lent strong acid (sulphate) per liter. grams of copoly = 20 mer. The pH of the latex is 3.4.

TABLE C

fibers

Identification Description A Bleached conifer 25 B Bleached hardwood C Blend of 50% of fiber A and 50% of fiber

B

D Unbleached pine (pinus palustris) E Unbleached northern state pine.

30 F Unbleached sulphite pine wood G SWP fibrillated polyethylene, E-400 fiber = length 0.9 mm.

Identification Description 21

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H SWP fibrillated polyethylene R-830, fi = ber length 2.0 mm, In SWP fibrillated polyethylene R-990, fi = 5 berl length 2.5 mm.

J Mixture of 50% of fiber I and 50% of fi = ber D, K Mixture of 25% of fiber I and 75% of fiber D.

10 L Mixture of 50% of fiber G and 50% of fiber D.

M Polyester (polyethylene terephthalate) denier per. filament 6.0, fiber length 0.135 mm.

N Nylon 66, denier pr. filament 3.0, fiber = 15 length 0.25 mm.

0 Rayon, denier pr. filament 5.5, fiber length = the 0.135 mm.

P Mineral wool Q Mixture of 50% of fiber D and 50% of fiber 20 P.

R Blend of 75% of fiber E, 12.5% of polyethylene = lenterephthalate fiber with 3 deniers per fila = ment and 6 mm length and 12.5% starch ape = pretreated glass fibers with a length of 6 mm 25 and a diameter of 6 microns.

TABLE D

flocculants

Identification Description

DK 153575B

22 A A copolymer of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulphate (Betz 1260) with a Ostwald vis = 5 quality of 17 centipoises as a 0.5% aqueous solution containing 3% sodium chloride at 25 ° C.

B A Mannich reaction product of polyacrylic 2 3 amide, formaldehyde and dimethylamine which is quaternized with methyl chloride and the resulting quaternized product is of the kind described in U.S. Patent No. 4,010,131, which reaction product has a Ostwald viscosity of 30 cents = 15 tipoise as a 0.5% aqueous solution containing 3% sodium chloride at 25 ° C.

C Alum.

D A high molecular weight polyacrylamide approx. 5% hy = drolyzed and with oak viscosity of 23 cen = 20 tipoise measured at 25 C as a 0.5% aqueous solution.

E A terpolymer of acrylamide, dimethyldial = lylammonium chloride and diethyldiallylammonium chloride with a Ostwald viscosity of 3.7 centipoise as a 0.5% aqueous solution containing 3% sodium chloride at 25 ° C.

in the examples where handmade films are made, use = 2 tes a specially developed standard method with the modifications = 3 30s shown in the individual examples. By standard method = the fiber shown (if it is a cellulose fiber) is turned into pulp for a Canadian Standard Freedom (CSF) of 500 ml and a consistency of approx. 1.2% by weight. The synthetic fibers are dispersed in water with a TAPPI disintegrator (600 35 strokes), but no measurement of Canadian standard3 freedom is made. With a sufficient amount of the resulting aqueous dispersion to give 5 g of the fiber on a dry basis, an additional predetermined amount of water is mixed to give

DK 153575B

23 a final volume of 2000 ml. Stirring is continued, with its 80 grams of the filler shown being added as a powder except where shown as an aqueous slurry, followed by 15 grams based on the solid of the indicated 5 latex. The resulting mixture is subjected to mechanical shear forces for 15 seconds in a Jabsco centrifugal pump followed by stirring with a laboratory stirrer with two 3-bladed propellers on a shaft operated at 900 rpm. per minute, while slowly adding a 0.1% solution = 10 of the flocculant indicated until the aqueous phase is substantially clear. A sufficient amount (about 62 ml) of the resulting material to give 3 g of solid is diluted to 1000 ml with water and the Canadian standard = freedom is measured according to TAPPI standard T 227-M-58. Freedom Sample = 15 friend is sent back to the material which is then diluted to 13,500 ml, forming a foil in a standard 25.4 x 30.5 cm Williams standard foil form and recording the drainage time on a 100 mesh screen. The resulting wet foil is chewed from the wire in a press 2 at approx. 0.7 kg per cm using 2 suction papers 20 to absorb water from the foil. The sheets are alternately stacked with suction paper and pressed wet at 35.2 kgpr. cm. The partially dried foils are then weighed and dried on a foil dryer at a plate temperature of 116-121 ° C, with the sides of the foil alternately facing the plate at intervals of 0.5 to 1 minute. The 25 dried films obtained were weighed to determine the total amount of solids retained in the film. Since sufficient material is used to make a 100 gram film at complete retention, the dry weight also represents the percent retention.

Examples 1-14

Handmade films are made of the indicated latex, unbleached pine and the indicated fillers using flocculant A by the standard method described above, except where indicated. The data for the preparation of the 35 sheets are shown in Table I. The properties of the sheets are shown in Table II.

24

DK 153575B

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Examples 15-42 26

DK 153575B

Handmade films of the aforementioned latex, said kind of fiber are converted into pulp with the stated Canadian Standard Freedom (CSF), the filler listed and the flocculant listed by the standard method described above. Data on the film production are shown in Table III and the properties of the film in Table IV.

DK 153575B

27

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Examples 43-46 31

DK 153575B

Handmade foils are prepared by the standard method described above, in which the fiber is fiber D and the filler, latex and flocculant are the species listed in Table V. The foil properties are shown in Table VI.

DK 153575B

32

Ten

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4-> tn tn • h '' S d) in m in id §ω h ^>

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Examples 47-49 33

DK 153575B

Handmade foils are made at the above described ...........

standard method, in which the fiber is unbleached conifer, the latex is latex B, the filler is filler A, and flock = the coolant is as indicated. In addition to the flocculant, the indicated amount of alum was added first and stirred for 1 minute and then a sufficient amount of the second flocculant to complete the flocculation. The data for the preparation of the hand films is shown in Table VII. The self = 10 makers of the foils are shown in Table VIII.

DK 153575B

34 τι _

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Η ν_, w W

Examples 50-53 35

DK 153575B

Handmade films are prepared by the standard method described above, in which the fiber, latex and flocculant are as shown and the filler is filler A in the amount shown. The data for the foil manufacture are shown in Table IX. Samples of the foils are placed in a tropical chamber maintained at 100% relative humidity and 32.2 ° C and previously seeded with organisms including Aspergillus niger, Trichoderma viridie, Aurebasidium pullulans, Chae = 10 tomium globosum and unidentified species of penicillium.

After 21 days and 49 days, samples are examined for visible evidence of microbiological attack and values for tensile strength = loss at room temperature are measured on three strips that are 7.5 cm long and over a span of 2.5 cm. For comparison 15, handmade films are made from 85 parts of asbestos (Johns

Manville, Paperbestos # 5) and 15 parts of latex C (together = Equation Example A1) and 85 parts of asbestos and 15 parts of latex B (Comparative Example A2). Experimental data are shown in Table X.

20 The visual rating is based on an arbitrary scale of visible evidence of microbiological attack as follows: 0 = no attack 1 = very weak attack 25 2 = weak attack 3 = moderate attack 4 = strong attack 5 = very strong attack.

The tensile strength tests are performed except for the length of the test strip in the manner described after all the examples. The tensile strength data shown in Table X is the percent change in tensile strength between the test strips and the control strips of the same kind, which are produced simultaneously and kept for the same period outside the tropical

DK 153575B

36

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DK 153575B

37 m h o ό ro (1) σι | - - - * · -

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Examples 54-60

38 DK 153575B

Handmade foils are produced by the standard method described above, except that different proportions of fiber, latex and filler are used. The fiber is 5 unbleached conifers, the latex is latex B, the filler is filler = substance B, and the flocculant is flocculant A. The data is shown in Table XI.

DK 153575B

39

(DCM

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DK 153575B

Examples 61-62

A handmade foil (Example 61) of unbleached coniferous wood, latex F, filler 0 and flocculant A is prepared in the standard manner described above. Another handmade film 5 (Example 62) is prepared in the same way except that 0.25 parts of a cationic polyamide - epi = chlorohydrin resin (chymene 557) is added as a 0.132% aqueous solution to the aqueous fiber dispersion before mixing with the filler and latex. The data is shown in Table XII.

TABLE XII

Example Example 61 62

Flocculant A, ml 150 150

Paper making material = 15 ling CSF, ml 755 600

Drainage time, sec. 50 110

Foil thickness, mm 1.25 1.13

Foil weight (% retention) 94.9 87.0

Room weight, kg / m2 1093 1093 2 20 Tensile strength, kg / cm 56.2 66.1

Tensile strength, warm (177 ° C), kg / cm2 21.1 22.5

Examples 63-64

Handmade films of latex N, fiber R and 25 are made using the specified filler using flocculant E in the amount shown by the standard method except that a wet strength additive which is a cationic polyamide epichlorohydrin resin of 12, is added. 8% nitrogen, 1% total solids-based solids of an anionic emulsified hydrocarbon wax after the latex. The data are shown in Table XIII.

TABLE XXII

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Example Example 63__64

Filler P,% (on dry basis) 77 - 5 Filler Q,% (on dry basis) - 77

Latex N,% (on a solids basis) 15

Fiber R,% (on a solids basis) 8 8

Flocculant E, kg / ton dry matter 1.17 0.54 Wet strength additive, kg / ton dry matter 3.6 5.1 10 Drainage time, sec. 50 54

Sheet weight of foil, kg / jti ^ 1208 1154

Tensile Strength, R.T., kg / cm2 146 122 2

Tensile strength, warm, kg / cm 53.6 35.3 2

Tensile strength, DOP, kg / cm 66.4 47.5 2 15 Tensile strength, water, kg / cm 80.0 81.7

Extension, RT,% 3.5 2.7

Elongation, 177 ° C,% 2.3 2.0

Extension, DOP,% 3.3 2.3

Extension, water, S 6.3 5.0 20 ^ Water uptake,% 8.9 5.5 ^ Water swelling,% (length) 0.38 0.22 x The samples were 15 cm long instead of 10 cm.

The products of these examples are, by virtue of their properties, especially dimensional stability in the presence of water, particularly suitable for use in flooring materials.

Examples 65-70

Using the standard method, with the exception of the omission of mechanical shear forces in a Jabsco centrifugal pump, hand = 30 made foils of said latex, fiber E and filler Q un =

DK 153575B

42 using flocculant E in the amounts of latex fiber and flocculant shown in Table XIV and the amount of filler is the difference between 100% and the total amount of latex and fiber, all based on dry matter. Quantities = 5 are also selected such that they provide handmade foils that theoretically weigh 75 grams instead of 100 grams and the dilution water of the paper making material is reduced accordingly. The data are shown in Table XIV.

TABLE · IV

Example No. _ 65 66 62 68 69 70

Latex, art 0 0 P P Q A

Quantity,% (a) 15 7.5 15 7.5 15 7.5

Fiber E, 15 amount,% (a) 6 10 6 10 6 10

Flocculant, E, quantity, kg / ton (a) 3.0 1.8 3.6 2.1 3.4 2.1

Drainage time, sec. 97 59 64 41 122 61

Tensile Strength, R.T.

20 kg / cm2 137 110 131 141 120 110 (a) = On a dry matter basis x = The percentage retention in all of these examples is greater than 92.

Example 71 and Comparative Example 71 C.

25 With a portion of latex R blend 8% (based on the latex solids content) of tetrachloro carbon. The resulting product is centrifuged. The aqueous serum is removed and the remaining solids are washed with water. The resulting moist solids are redispersed in water by discarding the solids and vigorously stirring for 30 minutes to 1 hour. The resulting dispersion is latex R-1 and has a pH of 3.8.

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Except for quantities which are theoretically sufficient to produce one 30 gram film instead of a 100 gram and correspondingly reduce the dilution = water, the standard method of making hand = 5 made films each of latex R and latex is used. Rl in an amount of 15% of the respective latex, 15% fiber E and 75% filler = substance K (based on solids and based on the weight of latex fiber and filler) using 127 ml of a 0.1% aqueous solution of flocculant E. Moist 10 handmade foils are formed with each of latex R1 (Example 71) and latex R (Comparative Example 71-C) with a dewatering time of 20 seconds and 29 seconds, respectively. In Example 71, there is only a barely detectable amount of impurities in the surface of the liquid in the preparation of the material 15 for the papermaking and only a slight adhesion of the film to the Wire when the moist handmade films are dried. During the addition of the flocculant, the flocculation progress is readily observed. In Comparative Example 71-C, however, a large amount of impurities and foams appear on the surface in the preparation of the papermaking material. There is so much adherence to the dried handmade foils to the wire and the absorbent paper that a foil cannot be separated from the wire.

The bound charge of latex R and latex R-1 is the same, because the process for preparing latex R-1 of latex R does not change the existing bound charge (from carboxyl groups). The significant difference is the removal from latex R of water-soluble components, e.g. surface active agents and acrylic acid polymers or copolymers having a sufficiently low mold weight and sufficiently high carboxyl content to be water soluble. These results are consistent with the fact that excessive amounts of water-soluble polymers, including surfactants and ionic polymers, are detrimental to carrying out the present process.

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Examples 72 and 73

An aqueous dispersion of fiber having a consistency of 4% of bleached pine and water is prepared in a Black Clawson hydra pulper. The crude dispersion is pumped to a refining = 5 box and refined to a Canadian standard of 500 ml by recirculation through a Sprout-Waldron double = stream refiner,. High filler foils for Examples 72 and 73 are made from parts of fiber dispersion. the latex and filler, as identified and in the 10 quantities shown in Table XV, using a 78 cm Fourdrinier paper machine with a long phosphor bronze waveguide, four flat suction boxes between the breast roll and a suction roller, a first wet press, a reverse press, a multi-section drying section with a glue press between sections = 15, and a calender stack of 7 rollers. The fiber dispersion, filler, water and latex diluted to 25% solids are added to the machine box in said order, the added amount of water being calculated to give a consistency of 4%. The resulting material is transferred by means of a pump = 20 pe through a valve, then through a blower pump to the main box. The flocculant shown in Table XV is added between the pump and the valve, and some white water from the later stages of the process is returned to the system between the valve and the blower pump such that the consistency 25 of the material in the main box is as shown in Table XV. Material = everything from the main box is carried on the wire, which moves at 6 meters per minute. from which white water is drained to form a wet film,. from which further water is removed by means of the four suction boxes, before the foil springs from the wire 30 by the suction roller. After the two pressing steps have further reduced the water content, the foil is passed through the dryer and calender stack. Data for the method and properties of the strongly filled films are shown in Table XV.

TABLE XV

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Example Example 72 73

Filler Of% (on solids basis) 75 80 5 Latex C,% (on solids basis) 15 -

Latex F,% (on a solids basis) - 15

Bleached conifers,% (on a dry matter basis) 10 5

Flocculant A, kg / ton 10 solids - 0.63

Flocculant B, kg / ton dry matter 5.4

Texture in box,% 4.0 4.0

Consistency in main box,% 3.31 1.22 15 Main box, Canadian standard freedom, ml 603 668

Machine speed, mpm 6 6 Wet pressing, 1st press, pli 20 20 2nd press, pli 70 70 20 Retention,% 99 102 Target, rnm 0.71 0.69

Room weight, kg / m2 936 904 2

Tensile strength, MD, kg / cm 51.6 32.3 CD, kg / cm2 36.4 28.8 25 Hot thread strength, MD, kg / cm2 30.1 13.4 CD, kg / cm2 23.2 6.2 DOP tensile strength, MD, kg / cm2 38.1 9.5

Extension, R.T.,% MD 3.1 2.0 30 CD 7.9 3.8

Elongation, warm,% MD 2.0 1.7 CD 4.0 2.8

Extension, DOP, MD,% 2.3 1.7 TABLE XV continued 46

DK 153575B

Example Example 72 73

Stiffness, MD

5 Loser 119 119 DOP 81 29

Water 20 29

Stiffness, CD

Losing 81 72 10 DOP 46 12

Water 14 19

Elmendorf tear strength, g-cm MC 24.8 16.7 CD 24.7 11.7 2 15 Mullen rupture, kg / cm 1.72 1.08

Water uptake,% 14.1 10.3

Toluene uptake,% 49.9 54.2

Limiting Oxygen Index (L.O.I.) 47 53

Example 74 An aqueous dispersion of fiber is prepared having a consistency of approx. 4% of unbleached Northern State pine trees and water in a Black Clawson hydra pulper. The crude dispersion is pumped to a refiner box and refined to a standard Canadian freedom of 500 ml by recycling through a Sprout-Waldron dob = 25 belt current refiner. High filler sheets for example 74 are made from the fiber dispersion, a latex, a filler as identified and a wet strength additive, which is a 12.8% nitrogen cationic polyamide epichlorohydrin resin and a viscosity at 25 ° C between 40 and 65 centi = 30 poise, all in the amount ratios shown in Table 16, using a Fourdrinier machine with (a) a 90 cm wide plastic wire (b), a main box equipped with a manifold type input, a homogenizer roller and a Neilson dial

DK 153575B

47 (c), a suction tube (d), a flat press with straight through (e), a reverse press (f}, a drying section consisting of 5 and 7 dryers with one-piece shaft die and 2 felt dryers on the bottom and felt at the top of the first section and 5 (g) a calender stack consisting of 8 rollers with the intermediate rollers drilled into steam.The fiber dispersion, the filler, the wet strength additive, the water and the latex diluted to 25% solids are added to the machine box in said order, the added amount of water is calculated to give a constant = 10% of 4% The resulting material is transferred by means of a pump through a valve and then through a fan = pump to the main box. The flocculant shown in Table XVI is added. between the pump and the valve, and some white water from the later stages of the process is sent back to the system between the valve and the blower pump, such that the consistency of the material in the main box is as shown in Table XVI. moves at 12 meters per second. and white water is drained to form a wet film, from which an additional 20. water is removed by suction boxes before the film is removed.

from the wire at the suction roller. After the two pressing steps have further reduced the water content, the foil is fed through the dryer and calender stack. Data for the method and properties of the highly filled films are shown in Table 25 XVI.

TABLE XVI

Example 74

Filler B,% (on solids basis) 82.5 Latex N,% (on solids basis) 7.5

Fiber E,% (on a solids basis) 10.0

Flocculant E, kg / ton dry matter 0.4

Texture in box,% 4.0

Consistency in main box,% 1.7 35 Main box Canadian standard freedom, ml 568 TABLE XVI continued

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Example 74

Machine speed, mpm 12 5 Wet pressing, 1st press, pli 100 2nd press, pli

Withholding,%> 90 Dimensions, mm 0.58

Room weight, kg / m ^ 802 2 10 Tensile strength, MD, kg / cm 112 CD, kg / cm ^ 45.7

Stiffness, CD

Losing 48

Elmendorf tear strength, g-cm 15 MD 136 CD 160 2

Mullen burst, kg / cm 2.6

Petroleum uptake,% 64.4

The various tests are performed as described below with the 20 changes shown in the individual examples.

Canadian Standard Freedom (CSF) The value in milliliters is determined according to TAPPI standard T 227-M-58 on a sample containing 3 g of solid diluted = that of water to 1000 milliliters.

25 Elmendorf tear strength

The test is performed according to TAPPI method T414-ts-65. Results = ne are shown as an average of at least 3 samples.

Extension percent

The extension at room temperature, the extension at 177 ° C

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49 (warm), the extension DOP and the extension water are determined over a 15 cm span at the same time as the respective tensile strength tests - see description below.

Limiting Oxygen Index (L.O.I.) 5 L.O.I. determined according to method ASTM D 2863-74. The grinding TAPPI method D 403-OS-76 is followed except that the sample is applied to thicker films. The results shown are an average of 4 or 5 samples.

10 Withholding, percent

The materials for the handmade films are added in quantities sufficient to give 100 grams of film. Thus, the dry weight of the product also represents the percent retention of dry matter in the film.

15 Por foils made. on the Fourdrinier machine, the percent retention relates to the amount of filler retained in the foil. Incineration of samples is carried out under such conditions that the rest of the filler = fat (calculated as percent ash) is retained, but so that the other 20 components are removed. The ash percentage is multiplied by an appropriate factor for changes in the filler caused by combustion (e.g., Mg (0H> 2 MgO) to determine the percentage amount of filler in the foil. From the found percentage of filler in the foil and ·, the added percentage percent = 25 the fillers (on a dry matter basis) calculate the percentage amount retained in the foil, with an average of three samples.

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Stiffness loses

Loss of stiffness (g-cm) is determined according to TAPPI standard method T 489-os-76, except that the results of three tests are used to form an average, unless otherwise stated. The resulting value is corrected to a value for a thickness of 0.75 mm by multiplying by the factor: (30) 3 _ (Thickness of sample in mm)

To distinguish from modified loser stiffness tests (DOP 10 and water - as described below), the TAPPI method is sometimes referred to as "losing stiffness, Reg."

Stiffness, DOP

The DOP stiffness (grams-cm) is determined in the same way as the stiffness loss except that the sample is soaked in dioctyl = 15 phthalate for 18-24 hours before testing and the value indicated is an average of two samples.

Stiffness, water

The water stiffness is determined in the same way as the loser stiffness except that the sample is soaked in water for 18 to 24 hours 20 before testing and the values given are the average of two samples.

Tensile strength, room temperature (R.T.)

The sheets are cut into strips with dimensions of 2.5 cm x 20 cm and the minimum thickness over the test area determined. Strip = 25 flour being tested is placed in an instron machine with a 15 cm span. While instron machine is driven at a head height of 2.5 cm per head. minute, elongation = late and breaking strength are noted.

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The fracture strength is calculated by dividing the tensile strength of fracture by the thickness of the sample. The results are reproduced as an average of three samples.

Tensile strength, warm 5 The hot tensile strength is tested in the same way as the tensile strength at room temperature except that the specimen is heated just before the test to a temperature of 177 ° C for one minute while clamped in the jaws of the test machine.

Pull s Turkish, DOP

The DOP tensile strength is examined in the same way as the tensile strength at room temperature except that the sample is soaked in dioctyl phthalate for 24 hours prior to testing.

Tensile strength, water

The tensile strength of water is determined in the same way as DOP tensile strength = 15, except that the wetting takes place in water.

Toluoloptagelse

A suitable sample (2.5 x 5 cm) is wetted for 15 seconds in toluene, the weight uptake noted and the uptake in weight% calculated.

Petroleum uptake 20 Petroleum uptake is measured in the same way as the toluene uptake, except that wetting takes place in petroleum.

water absorption

Water uptake is determined in the same way as Feoluene uptake, except that wetting occurs in water for 24 hours =

Claims (10)

A process for preparing a high filler tavine film by the following steps: I Preparation of an aqueous dispersion of water dispersible taverns, II Mixing this dispersion with: (A) a finely divided, essentially water-insoluble, non-fibrous non-fibrous Rk - Fvl rice court. and DK 153575B (B) a binder containing a film-forming, water-insoluble organic polymer in the form of an ionically stabilized latex, III Colloidal destabilization of the resulting mixture to form a tavern agglomerate in aqueous suspension, A method according to claim 1, characterized in that the colloidal destabilization step forms a tavern agglomerate in aqueous suspension with the feature that the suspension, with a concentration of 100 g of solid in 13,500 ml, drains over a period of approx. 4 seconds to approx. 120 seconds in a 25.4 x 30.5 cm Williams standard foil mold with a 5.1 cm exit opening 25 and a 76.2 cm water reservoir provided with a 0.149 mm stainless steel screen with a wire diameter of 0.0114 mm, thus that, after dewatering after step IV, at least 85% of the total solids in the tavern agglomerate containing at least 60% of the fillers are left in the moist web. 30 3. A process according to claim 1, characterized in that the organic polymer of the latex has a bound charge of less than 0.7 milliequivalents per minute. g polymer. Process according to claim 3, characterized in that the organic polymer in the latex has a bonded charge of 0.3 DK 153575B Process according to claim 2, characterized in that the aqueous dispersion of the taverns has a consistency of 0.1 to 6%, the taverns are cellulose taverns and the tavern agglomerate has a dewatering time of 15 to 60 seconds. 5 5 IV Distribution and dewatering of the aqueous suspension on porous beaks to form a moist web, and V Drying the web, characterized in that the mixture obtained after step II contains: 10 1-30% tavern 60 - 95% filler 2 - 30% latex as the percentages are based on the dry weight and on the total dry weight and the ionically stabilized latex does not contain enough non-ionic stabilization to interfere with the formation of a silica agglomerate. Process according to Claim 1, characterized in that the tapping rate is 5 to 15%, the filler amount is 70 to 90% and the latex contains copolymerized styrene and butadiene. Process according to claim 1, characterized in that the latex is a mixture of at least two different latex compositions and at least one of the latexes contains a copolymer of an ethylenically unsaturated carboxylic acid. Process according to claim 1, characterized in that the destabilization step is carried out by mixing the product of steps I and II with a sufficient amount of a water-soluble or water-dispersible ionic compound or a polymer which has one with respect to the ionic stabilization of the latex. directed charge. 20 A wet-formed self-supporting film made by the method of claim 1, consisting essentially of a mixture of (A) water dispersible taverns, (B) a film-forming, water-insoluble organic polymer, and (C) water-insoluble, non-fibrous, inorganic fillers , characterized in that it contains 1 - 30% tavern, 60 - 95% filler and 2- 30% organic polymer. A wet-formed film according to claim 9, characterized in that the organic polymer is obtained by emulsion polymerization of an ethylenically unsaturated monomer and in its latex form has a bonded charge of 0.03 to 0.4 milliequivalents per unit weight. g polymer. 35. .