FI56419C - PAPPERSPRODUKT BESTAOENDE AV PAPPERSMASSA OCH ETT PIGMENTFYLLMEDEL - Google Patents

Description

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M ("» UTLAOONINOSSKMFT 56419 C (Mjtentti raySr.r.rtty 10 01 1900

Patent raeddelit V v / (51) K ».ik. * / Int.ci. * D 21 H 3/48 FINLAND —FINLAND (21) P» t »nttlh» k * mui— Ptuntimöknlnj 6 ^ / 71 (22) Htk «ml» pllvl - Antöknlngtdtf 12.01.71 (Fl) (23) AI kupu vl - Giltighttsdag 12.01.71 (41) Tullut Julkisaksi - Bllvlt offantilg 13 · 07 · 71

National Board of Patents and Registration (44 \ Nlhttvlkiipanon ja kuL |

Patent and registration authorities Antökan utlagd och utl. * KrMt «n publicarad 20.09.79 (32) (33) (31) Privilege requested — Begird priorltet 12.01.70 29.10.70 usa (us) 2U27, 85273 (71) Cabot Corporation, 125 High Street, Boston, Mass., USA

Ciba-Geigy AG, IL, Klybeckstrasse, Basel, Switzerland-Switzerland (CH) (72) Peter Economou, Bedford, Mass., John F. Hardy, Andover, Mass., USA Alfred Renner, Muenchenstein, Evald Forster, Allschvil, Hermann Diet-helm, Aesch, Switzerland-Schveiz (CH) (7 * 0 Oy Kolster Ab (54) Paper product consisting of pulp and pigment filler -Pappersprodukt best & ende av pappersmas och ett pigmentfyllmedel

The present invention relates to a paper product consisting of a pulp and a pigment filler which is an insoluble, indigestible, non-porous, finely divided urea-formaldehyde polymer having a molar ratio of urea to formaldehyde of between 1: 1.3 2 and 1: 1.0 and a BET specific surface area. area of about 5 to 100 m / g.

The invention is characterized in that the amount of pigment filler is 0.5 to Θ0% by weight, based on the amount of dry paper pulp.

The finely divided insoluble polymer, alone or in combination with additives, imparts a number of excellent physical properties to the base paper or board. These properties, which include brightness, opacity and retention, can be achieved with a single substance or combination depending on the base paper with which the blends are used. As will be shown later, the additive mixtures further avoid the normal decrease in strength caused by the addition of fillers to the papermaking materials.

2 56419

The paper industry uses large amounts of inorganic pigments such as talc, kaolin, calcium carbonate, zinc sulfide, clay, titanium dioxide and the like as fillers in the manufacture of paper products. Typically, such inorganic pigments are effective in the manufacture of paper products having improved properties such as brightness, opacity, basis weight, softness, finished surface, and / or ink absorbency. In addition, in the paper industry, an acceptable chemical additive for pepper must be such that it does not migrate from the base paper to a nearby absorbent. The additive must not cause "jamming" or sticking of the paper together when the paper is rolled or stacked on top of the sheet. Although conventional pigments meet most of the requirements of conventional papermaking techniques, the pigments are not entirely satisfactory because the use of such additives has a detrimental effect on paper strength and pigment retention. Inorganic pigments, when used as paper fillers, are believed to lower pulp sizing and reduce strength properties, mainly due to fiber-to-fiber bonds. It is therefore clear that it would be advantageous for the paper industry to have an optically effective filler available as such or in a mixture that does not affect the strength and printing properties of paper products when the filler is added to the paper in normal amounts.

It is an object of the present invention to provide improved paper products which do not have the disadvantages associated with the prior art.

The objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.

It has now been found that the above object is achieved by adding to the pulp a pigment filler which is an insoluble, insoluble, non-porous, finely divided urea-formaldehyde polymer having a molar ratio of urea to formaldehyde of between 2 1: 1.3 and 1: 1.8. and a BET specific surface area of about 5 to 100 m / g (Brunauer-Emmet - Te 1ler method is described in the Journal of the American Chemical Society, 1938, Vol. 60, p. 309), and the concentration of volatile components of the pigment filler is preferably about 10 to 25% by weight based on the amount of dry urea-formaldehyde polymer. Soluble polymeric materials suitable for improving the dry strength of 3,564,194 paper as a filler with urea-formaldehyde polymers include soluble cationic and anionic urea-formaldehyde resins, cationic and nonionic melamine-formaldehyde resins, soluble nonionic, anionic, anionic cimethylcellulose, alginates or similar water-soluble polymers. Paper with a filler according to the invention has good properties compared to papers with commonly used inorganic pigments, thus substantially alleviating the two difficult problems encountered in using conventional fillers in the paper industry, namely reduced paper strength properties and difficulty in pigment retention. The numerical values describing these properties of the filler-containing paper depend on the choice of the base paper treated in accordance with the present invention.

The amount of pigment filler is generally 0.5 to Θ0% by weight based on the amount of dry pulp. In a preferred embodiment, this amount is about 0.5 to 30% by weight based on the amount of dry pulp. In the most preferred embodiment of the invention, the pigment filler is used at about 1 to 15% by weight based on the amount of dry pulp. The additive blends of this invention comprise from about 75% to about 99.9% by weight of insoluble urea-formaldehyde polymer based on the amount of blend and from about 0.1% to about 25% by weight based on the amount of soluble polymeric blend mixture suitable to improve dry strength. However, it is preferred to use additive blends in an amount of about 85 to 99.8% by weight of soluble urea-formaldehyde polymer based on the amount of blend, and about 0.2 to 15% by weight based on the amount of soluble polymer blend suitable to improve the dry strength properties of the paper.

Any grade commonly used in the manufacture of pulp can be used in the manufacture of paper products in accordance with this invention. As the raw material for the paper, a chemical pulp such as sulfite, soda, or sulfate pulp, semi-chemical pulp, groundwood, or mixtures thereof can be used. In addition, pulps made from plants and rags are suitable pulp components in the manufacture of paper products. Thus, it is not necessary or desirable to use fresh pulp as a pulp component, so that waste paper and the like obtained during papermaking, alone or in combination with fresh pulp, can be used. Waste called scrap paper can be added to fresh pulp either as dry or aqueous slurry.

4,56419

By volatile components of a pigment filler are meant substances which leave the urea-formaldehyde polymer product when the polymer product is heated at a temperature of about 135 ° C for about 2 hours in a vacuum drying oven at a pressure of 0.01 mm Hg.

The urea-formaldehyde polymer products used in accordance with the invention can be readily prepared by any suitable method, one of which is disclosed in U.S. Application Θ07,926. For example, insoluble, indigestible products can be obtained by a one-step or two-step process in which the polymers are prepared by the molar ratio between is 1: 1.3 and 1: 1.8. In a two-step process, urea is first reacted with formaldehyde in aqueous solution to form a soluble and meltable precondensate, and then an insoluble and indigestible product, which may be a gel or precipitate, is prepared at elevated temperature in the presence of a suitable curing catalyst. When using a one-step process, all reaction components and additives are added initially and the reaction proceeds directly until a crosslinked, insoluble and unmeltable urea-formaldehyde polymer is formed. In either case, the final urea-formaldehyde polymer gel is neutralized and recovered by filtration and centrifugation and dried by any conventional technique such as spray-drying, air-drying, azeotropic distillation, or other means to achieve contact and convection drying. Depending on the reaction conditions used, insoluble and indigestible reaction products can be prepared directly in a finely divided form such as powder or granulate, 3% of the reaction product is not obtained in such a form, so that the product can be ground using, for example, a ball mill, roller mill, impact mill or air mill.

Suitable acid hardener catalysts for use in the preparation of insoluble, insoluble, fully crosslinked urea-formaldehyde polymers in accordance with this invention include any conventional acid catalysts such as sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid; medium organic acids with a pK value of less than 4, such as formic, oxalic, maleic, succinic and chloroacetic acid and the like. However, it is preferred to use sulfamic acid or water-soluble ammonium hydrogen sulfate of the formula RNH 2 SO 2 H, wherein R is hydrogen, alkyl, cycloalkyl, hydroxyalkyl, aralkyl or aryl, as the acid hardener catalyst. Examples of water-soluble ammonium hydrogen sulfates include ammonium hydrogen sulfate, methyl ammonium hydrogen sulfate, ethyl ammonium hydrogen sulfate, hydroxyethyl ammonium hydrogen sulfate, phenyl ammonium hydrogen sulfate, benzyl ammonium hydrogen sulfate, and the like.

According to a preferred embodiment of the present invention, water-soluble macromolecular organic substances which greatly represent and increase the viscosity of aqueous solutions, hereinafter referred to as protective colloids, may be present in the reaction mass during the precipitation of urea-formaldehyde condensation products. Typical examples of such protective colloids are natural substances such as starch, gelatin, glue, tragacanth and acacia; modified natural materials such as karboksimetyylisel-cellulose, karboksimetyylisellusoosan alkali metal salts, especially the sodium salt of carboxymethylcellulose, methyl cellulose, ethyl cellulose, betahydroksietyyliselluloosa, aikaiimetailialgi-tops and the like, synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, water soluble polymers and aryl-lithium or methacrylic acid copolymers and their alkali metal salts , copolymers containing salts of maleic acid, copolymers of styrene-maleic anhydride, polyhydrochlorides of homopolymers and copolymers of vinylpyridine and the like. The amounts of protective colloids used depend on the type, chemical structure and and molecular weight. Protective lloids are generally used in amounts of about 0.1 to 10% by weight based on the amount of the urea and formaldehyde component. Preferably, the amount of protective colloid is about 0.5 to 5% by weight based on the amount of urea and formaldehyde reaction component used. In the preparation of urea-formaldehyde polymers by a one-step process, the protective acid can be added to the urea and formaldehyde precondensate at any wet end of the manufacturing process. With similarly advantageous results, the protective acid can be added after the formation of the urea-formaldehyde precondensate in the preparation of insoluble, insoluble urea-formaldehyde polymers by a two-step process.

In a particularly preferred embodiment of this invention, the urea-formaldehyde polymers used as the pigment filler are prepared using sulfamic acid or water-soluble ammonium hydrogen sulfate as a hardener catalyst together with a protective colloid to convert the urea and formaldehyde precondensate to a bound gel. A urea-formaldehyde precondensate having a molar ratio of 6,56419 urea to formaldehyde between 1: 1.3 and 1: 1.0 is formed at a temperature of about 40-100 ° C and a pH in the range of about 6-9 and for a time sufficient to bring the bulk of the formaldehyde react with urea. The protective colloid, called the sodium salt of carboxymethylcellulose, is added to the precondensate at any stage of the preparation or separately as a solution to the precondensate prepared in advance. A solution of sulfamic acid or water-soluble ammonium sulfate is then added to the resulting precondensate with stirring at a temperature between room temperature and about 100 ° C until a crosslinked gel is formed. The gel is then comminuted in an extruder or shear mill and the precipitate is separated by filtration or centrifugation. The resulting reaction product, which is a solid, insoluble and insoluble urea-formaldehyde polymer condensation product, is neutralized and dried by a conventional technique such as air drying and then deagglomerated using an impact mill, an air jet mill or a ball mill.

The filler-containing paper products of the invention are readily prepared by forming a slurry from the pulp component, homogeneously mixing the pigment filler pulp with the slurry, and forming water-insoluble materials into a paper web on a conventional paper machine such as a Fourdrinier wire, dewatering, drying and calendering. The pigment fillers of this invention may be added to the pulp at some convenient stage during the manufacture of the paper product prior to sheet formation in the pulp. The pigment filler can be added, for example, to a pulper, a Dutcher or other pulp cleaning and manufacturing device, and in particular as a wet head additive for a vacuum pump or headbox. It is desirable that the pigment filler be homogeneously dispersed in the pulp to achieve optimum dispersion, in which case any conventional method can be used for grinding, dispersing and mixing. Pulps containing fully dispersed fillers are ground to the desired Canadian Standard Freeness degree of grinding (C.S.F.). When the desired degree of grinding is achieved, the excess water is removed and the web is formed on a conventional Fourdrinier paper machine wire or a cylinder paper machine.

For many purposes, it may be desirable to add other common paper additives or modifiers to the pulp system containing fillers. For example, in the manufacture of paper products, it is common practice to add common neutral flavoring agents such as ketene dimers or succinic anhydride derivatives and acidic adhesives such as resin adhesive, e.g. sodium resinate and adhesive precipitate such as alumina In addition, the properties of paper products can be modified by mixing neutral and synthetic adhesives and glues, dyes, cleaning agents, wetting agents, wet and dry strength resins, and the like with the pulp system.

It is known that the addition of inorganic pigments such as titanium dioxide, zinc sulfide, kaolin, lime and the like in the manufacture of paper products generally reduces the mechanical strength of the paper product and especially the dry strength. In addition, it is known that the mechanical strength of the paper products modified with the urea-formaldehyde polymers according to the invention decreases to some extent. However, it has been found that this disadvantage can be well avoided by the addition of certain soluble polymeric substances suitable for improving and promoting the dry and / or wet strength properties of paper products to which insoluble, finely divided urea-formaldehyde resins, anionic urea-formaldehyde resin , nonionic starches, anionic starches, cationic starches, carboxymethylcellulose, alginates, carboxylated polyacrylamides, and poly-salt complexes of carboxylated polyacrylamides and polyamines.

The present invention will become more apparent from the following examples.

Example A

A suitable stainless steel reaction vessel equipped with heat addition and removal devices, stirring devices and temperature recording devices 11a was charged with 15.75 parts by weight of water and 22.5 parts by weight of a 30% aqueous formaldehyde solution.

This mixture was heated to about 70 ° C and the pH was adjusted to 7 with sodium hydroxide solution. 9 parts by weight of urea were then added with stirring. After complete addition of urea, the temperature of the reaction mixture was maintained at about 70 ° C and pH 7 for about 2 hours. The resulting precondensate reaction mixture was cooled to about 50 ° C and rapidly stirred with a solution containing a hardener catalyst comprising 0.465 parts of sulfamic acid dissolved in 15.75 parts of water and maintained at 50 ° C.

and 66419

The gel began to form after 12 seconds, when the temperature of the reaction mixture rose to about 60-65 ° C. The resulting gel was then maintained under adiabatic conditions at about 65 ° C for about 2 hours. The resulting gel was then ground to a particle size of about 1-2 mm in a standard shear grinder, slurried with an appropriate amount of water and neutralized to pH 7.5 with sodium carbonate solution. The solid product was collected by filtration, dried at 110 ° C in a hot air jet for 5 hours and cooled to room temperature. The resulting product was then deagglomerated by conveying through a high speed (e.g. 20,000 rpm) rod mill. 13.6 parts by weight of a fine, white, powdery, non-porous, insoluble urea-formaldehyde polymer with a specific BET surface area of about 26.1 m / g, a molar ratio of urea to formaldehyde of 1 * 1.6 and a volatile matter content of 15 .6% by weight based on the amount of polymer. The volatile matter content of the fine polymer was determined in a drying oven at 135 ° C at a pressure of 0.01 mm Hg for 2 hours. The product obtained is hereinafter referred to as U / F-B,

Example B

A suitable reaction vessel with heat addition and removal equipment, means for measuring the temperature of the reaction mass and means for stirring the reaction mass was charged with a solution containing 0.315 parts by weight of the sodium salt of high molecular weight carboxymethylcellulose, type 7 HP, sold by Hercules, Inc. .75 parts by weight of water. To this solution was added 22.5 parts by weight of 30 aqueous formaldehyde solution, and then the resulting mixture was heated to about 70 ° C and the pH was adjusted to about 7 with sodium hydroxide solution. 9 parts by weight of urea were then added with stirring. Upon completion of the urea addition, the condensation reaction was allowed to proceed for 2 hours while stirring and maintaining the temperature of the reaction mixture at about 70 ° C and the pH at about 7. The resulting precondensate reaction product was cooled to about 50 ° C and stirred rapidly with a crosslinking solution comprising 0.441 parts. sulfuric acid dissolved in 15.75 parts of water heated to about 50 ° C. Gel formation occurred after 7 seconds, during which time the temperature of the reaction mixture rose to about 65 ° C. The gel is kept under adiabatic conditions for 2 hours at a temperature of 56419 g at 65 ° C. The gel was then ground to a particle size of about 1-2 mm in shear grinders, soaked with an appropriate volume of water and neutralized to pH 7.5 with sodium carbonate solution. The resulting solid was filtered off, dried for 5 hours at 110 ° C with an air jet, cooled to room temperature and deagglomerated by passing through a rod mill operating at 20,000 rpm. This gave 13.6 parts by weight of a fine, white, powdery, non-porous, insoluble and insoluble urea-formaldehyde polymer with a BET specific surface area of about 2 31.8 m / g, a molar ratio of urea to formaldehyde of 1: 1.5 and volatile the content of substances is 7.9% by weight, based on the amount of polymer, as previously described. The resulting polymer is hereinafter referred to as U / F 11.

Examples C - 0

By proceeding as in Example 2 and using a mlaar ratio of 1 mole of urea / 1.5 moles of formaldehyde, the following insoluble, insoluble, non-porous, urea-formaldehyde polymers were prepared having the physical properties shown in Table A.

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The physical properties of paper products containing indigestible, insoluble, non-porous urea-formaldehyde polymers as fillers and mixtures thereof with soluble polymeric substances which improve dry strength have been shown under various experimental conditions in the following detailed examples, which show preferred and expected results. The following test methods, which are TAPPI (Technical Association of Paper and Pulp Industry) standard measurement methods, were used to evaluate the physical properties of filler-containing products. The paper samples were conditioned prior to testing by maintaining them in an atmosphere maintained at 23 ° C and 50% relative humidity according to TAPPI T402 m-49. The values describing the physical characteristics have been corrected to correspond to the values obtained with paper samples with a basis weight of 23 kg per 500 sheets of rice and a size of 63.5 x 101 cm.

Surface weight - PIN T410 os-61

Thickness - PIN T411 m-44

Opacity - Using a Bausch and Lomb Opacimeter with a white body and an absolute reflectance ratio of 0.69, the percentage opacity adjusted to the value of paper with a basis weight of 23 kg was determined using a TAPPI T425 m standard. 60 according to.

The scattering coefficient per 0.454 kg of paper was determined according to TAPPI Standard T 425 m-60 using the Kubelka-Munk equations and adjusting the white base so that its absolute reflection was 0.69. This measurement describes the essential quality of a paper pigment that eliminates opacity and brightness differences and other variables due to pulp quality variations.

Brightness - Percent brightness was determined using a reflectance meter TAPPI Standard T 425 m-56. A "Coloreye" tristimulus colorimeter, manufactured by Instrument Development Laboratories, Inc. of Attleboro, Massachusetts, was used.

Pigment Retention - The percentage of pigment retention was determined by dividing the weight of pigment remaining in a given amount of paper by the weight of pigment added to the same amount of pulp.

Puncture resistance (Mullen) - PIN T403 ts-63

Tensile strength - Paper samples were taken from the machine direction (M.D.) and the tensile strength of the paper was determined according to TAPPI Standard T404 os-61 12 56419 2 and is expressed in units of kp / cm.

Ash - The ash content of the paper as a percentage was calculated according to TAPPI T413 m-58.

Flexural strength, M.I.T. - Paper samples were taken with a long dimension in the machine direction (M.D.) and the number of double bends required to tear the paper was measured according to TAPPI Standard T423 m-50.

Bonding - PIN According to T433 m-44 (modified), the bonding of paper and board was determined by measuring the resistance of paper to water penetration. Durability was measured with a KBB Sizing Tester (Model No. TMI 58-5-1) sold by Testing Machines Inc. of Mineola, New York. The time in seconds that water penetrates through a sheet of paper is a measure of the degree of sizing of the sample.

Examples 1-10

The paper products shown in Table I, which contained various amounts of the pigment fillers of the invention, were prepared on a Noble and Wood paper machine. The Niagara Hollander was fed a pulp slurry having a concentration of about 2% and containing 400 g of oven-dried bleached sulfite fibers and 19.6 kg of water. The resulting slurry was ground to a Canadian Standard Freeness degree of grinding (C.S.F.) of about 400 ml and further diluted with 37 liters of water to give an aqueous pulp slurry containing 0.7% by weight of pulp. 7.14 l of a mass with a concentration of 0.7% were mixed vigorously with an aqueous dispersion containing the desired amount of pigment. One liter of pigmented pulp was diluted with 10 liters of water on a Noble and Wood machine and the resulting wet web was dried on a Noble and Wood paper machine for one minute at 116 ° C. The size of the sheets formed was 30.5 x 30.5 cm and per rice (63.5 x 101.6 cm to 500 sheets). The various properties of the paper were determined and the results obtained are shown in Table I below.

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Examples 11-36

The paper to be examined was produced in a pilot mill on a Fourdrinier paper machine with a width of 30.48 cm and a speed of 366 m / min. A pulp slurry having a consistency of about 3% and containing about 9 kg of bleached sulfite fibers was charged to a Johnson Hollander and the slurry was ground to a Canadian Standard Freeness (C.S.F.) Grinding degree of about 400 ml. The desired amount of pigment filler U / F-7, anatase titanium dioxide or Ultrawhite 90 clay was added as either a dry or aqueous slurry to the pulp slurry. The resulting slurry was stirred vigorously and passed to a tank in which sufficient water was added to obtain an aqueous pulp slurry having a concentration of about 1%. At this stage, other additives such as resin glue and alum can be added to the pulp slurry if desired. Alum is added 10 minutes after the addition of the resin adhesive and 30 minutes before the preparation of the paper sheets. The pigmented pulp slurry was passed through a pulp pan, diluted with water to a consistency of about 0.15 to 0.21% by weight, and continuously pumped into a main box from where it was fed to a 30.48 cm Fourdrinier paper machine wire. Water and excess pigment filler were allowed to drain off and the wet paper web was pressed, dried and possibly calendered to obtain a smooth surface. The paper products thus prepared were tested for various physical properties and the results obtained are shown in the following Tables II and III. It should be noted that the values shown in Table II have been obtained with calendered paper samples, while the results shown in Table III have been obtained with non-calendered paper samples.

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The series of experiments summarized in Tables II and III are mainly intended to describe the paper reinforcement properties of the urea-formaldehyde fillers of the invention compared to conventional titanium dioxide and clay fillers. The systems used to evaluate the effectiveness of fillers comprise a pulp slurry alone, a pulp slurry containing alum, and a pulp slurry containing alum together with a resin adhesive, i.e., a conventionally glued paper system. From the above values, it can be seen that paper made from a pulp slurry modified only with urea-formaldehyde filler has a particularly high pigment retention, while the paper strength properties such as dry strength, (Mullen) puncture and M.I.T. the flexural strengths have remained at the values obtained with paper made from a similar pulp slurry without any filler at all. In both cases, when the resin adhesive and alum, i.e., the adhesive system, have been used in the paper system, and when alum alone has been added to the paper system, the strength properties of the filler-containing paper have deteriorated. However, it should be noted that the detrimental effects of the presence of alum and / or resin adhesive additives in the pigment-filled paper are much smaller when the urea-formaldehyde filler is used, compared to titanium dioxide and clay, despite the fact that more urea-formaldehyde remains in the product. As a result of this comparison, it can be said that the order in which the filler, alum and / or resin adhesive is added to the pulp slurry does not provide any clear differences in the final properties of the paper produced. In addition, it has been found that calendering does not affect the strength properties of the paper and the amount of sizing decreases with increasing amount of retained filler when the filler is present as a urea-formaldehyde polymer or some other conventional filler.

Examples 37 to 90

The paper products shown in Examples 11 to 36 in Tables IV, V and VI were prepared. In each experiment, a 5 kg batch sample was prepared by grinding a bleached sulfite pulp charge to a Canadian Standard Freeness (CSF) grade of 390 to 410 ml, preferably 400 ml, and adding 10% by weight based on dry pulp to . The resulting filler-containing pulp slurry was passed to a tank, which was optionally chemically treated with alum and / or resin glue. The resulting pulp slurry was then pumped through a headbox to a Fourdrinier machine where the pulp was formed into a paper web as described above. The results obtained on the sheets of paper are shown in the following Tables IV-VI.

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Several observations can be easily made from the values obtained from Examples 37 to 90. For example, it can be concluded that the percentage retention of the urea-formaldehyde fillers of the invention in the paper product increases as the BET specific surface area of the finely divided filler increases at about 05-95% and the specific surface area at about 33 m / g. Higher retention with increasing surface area is also observed in Table I, which used hand sheets made on a Noble and Wood paper machine. The detrimental effect of alum and / or resin adhesive on the strength properties of fine filler-containing paper products can also be seen in this series of examples. It is important to note that in many cases, when the filler is highly self-retaining, paper products are characterized in that the opacity and coefficient of dispersion approach the corresponding values of titanium dioxide and the brightness is equal to or better than the corresponding value of titanium dioxide.

As in the previous examples, the pigment fillers U / F -1 to U / F-15 were added to a pulp component containing 50% bleached softwood sulfate pulp and 50% bleached hardwood sulfate pulp to make a paper product. The resulting filler-containing paper products are characterized by better brightness and opacity, excellent pigment retention and only slightly lower strength properties.

Examples 91-95

The paper products shown in Table VII, which contain varying amounts of the additive blends of the invention, were prepared on a Noble and Wood paper machine. A pulp slurry having a consistency of about 2% and containing 400 g of oven-dried sulfite fibers and 19.6 kg of water was then fed to the Niagara Hollander. The resulting slurry was ground to a Canadian Standard Freeness Grinding Degree (C.S.F.) of about 400 ml and then further diluted with 37 liters of water to give an aqueous pulp slurry containing 0.7% by weight of pulp. 7.14 l of a mass with a consistency of 0.7% were mixed vigorously with an aqueous dispersion containing the desired amount of additive mixtures. One liter of the filler-containing pulp was diluted with 10 liters of water on a Noble and Wood machine, and the resulting wet web was dried on a Noble and Wood paper machine for 1 minute at 116 ° C. 23 kg TAPPI per rice (63.5 x 101.6 cm - 500 sheets). The paper was tested for various properties and the results obtained are shown in Table VII below.

23 56419

Table VII

(90% by weight of bleached sulphite and 10% by weight of filler, calculated on the dry weight)

Example No. 91 92 93 94 95% U / F - 8 - 10 9 - -% U / F -11 - - - 10 9% soluble polymeric dry strength modifier * - - 1 - 1% resin adhesive * * 11111% alum 22222 opacity% *** 75.2 85.9 86.0 85.5 84.7 scattering coefficient / 0.454 kg TAPPI rice 0.0395 0.672 0.0666 0.0656 0.0626 brightness% 85.2 90, 3 89.6 90.4 89.3 burst (Mullen)% 50.9 35.3 44.7 39.8 44.9 dry strength kp / cm2 *** 20.6 15.7 20.5 17.3 20 , 1 gluing, (water) s 102 31 92 39 83

jd

Parez 615 is a trademark of cationic water-soluble urea-formaldehyde resin and is sold by American Cyanamid Co.

** Pexol is a trademark of reinforced resin adhesive and is sold by Hercules, Inc., ** # Corrected to match paper with a basis weight of approximately 23 kg per TAPPI rice (63.5 x 101.6 cm - 500 sheets).

Examination of the values in the table above shows that blends comprising an insoluble finely divided urea-formaldehyde polymer and a cationic water-soluble urea-formaldehyde wet strength resin have several advantages that cannot be achieved when using insoluble urea-formaldehyde fillers alone. It can be seen from Table VII that in the presence of resin adhesive and alum, the reduction in strength properties of paper products made using insoluble urea-formaldehyde polymer is avoided by replacing 10% by weight of insoluble urea-formaldehyde polymer with cationic water-soluble urea-formaldehyde. In particular, it should be noted that the dry strength and the percentage of puncture properties are considerably improved and the loss of normal paint in sizing due to the presence of pigments in the paper is minimal.

Examples 96-101

The paper to be examined was produced in a pilot plant on a Fourdrinier paper machine with a width of 30.40 cm and a wire speed of 7.6 m / min. The Johnson Hollander was fed a pulp having a consistency of about 2.5% and containing about 5 kg of bleached sulfate fibers comprising 50% softwood fibers and 50% hardwood fibers and the slurry was ground to a Canadian Standard Freeness degree (C.S.F.) of about 400 ml. The desired amount of filler was added to the pulp slurry as either a dry or aqueous slurry. The resulting slurry was stirred vigorously and then the slurry was passed to a vat where sufficient water was added to obtain an aqueous pulp slurry having a consistency of about 1%. At this stage, other additives such as resin glue and alum can be added to the pulp slurry if desired. Alum is usually added 30 minutes after the addition of the resin adhesive and 30 minutes before the preparation of the paper sheets. The filler-containing pulp slurry was passed through a pulp tank, diluted with water to a consistency of about 0.15 to 0.3% by weight and continuously pumped to the batch. cm for a Fourdrinier paper machine wire. Water and excess filler were allowed to drain and the wet paper web was compressed, dried and optionally calendered to obtain a smooth surface. The prepared paper products were tested for different physical properties and the results are summarized in the following table Vili.

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56419 26

Looking at the values in Table VIII, it can be seen that the reduction in strength properties of paper products containing insoluble fine urea-formaldehyde polymers prepared in the presence of alum and resin adhesive is significantly less when water-soluble wood formaldehyde type is added. Since the opacity and brightness do not change, it is clear that replacing 10 to 15% of insoluble urea-formaldehyde resin with a water-soluble urea-formaldehyde polymer provides a significant improvement in the strength and sizing properties of paper products.

Examples 102 to 115

The paper products shown in Tables IX and X were prepared as in Example 91. Bleached sulfite pulp slurry having a consistency of about 1% was fed into a suitable container. The slurry was ground to a Canadian Standard Freeness Grinding Degree (C.S.F.) of about 420 ml. An aqueous dispersion containing the desired amount of excipient was added to the ground slurry with stirring. The resulting filler-containing pulp slurry was chemically treated with resin glue and alum. From the resulting pulp slurry, sheets of paper were formed in the usual manner, and the sheets were dried in a hot cylinder at 136 ° C for 2 minutes. The basis weight of the sheets was about 32.3 kg / TAPPI rice (30.48 x 101.6 cm -500 sheets). The paper sheets were tested for dry strength properties and the results obtained are shown in the following Tables IX and X.

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From the values in Tables IX and X, it is found that paper products containing insoluble finely divided urea-formaldehyde polymers have better dry strength properties in the presence of a soluble polymeric material. It is further found that an optimum result is obtained when the soluble polymeric substance is used in the form of either modified nonionic starch or carboxymethylcellulose.