DK159210B - AFFORDABLE LIMITING MEASURES, PROCEDURE FOR LIMITING PAPER AND IT WITH THE MIDDLE LIMITED PRODUCT - Google Patents

Abstract

Described are sizing compositions in the form of aqueous dispersions comprising a hydrophobic cellulosereactive sizing agent such as a ketene dimer, fortified rosin and a water-soluble, nitrogen-containing cationic dispersing agent. The compositions are highly efficient internal or surface sizing agents for paper and maximize the advantages of each sizing component while minimizing the disadvantages.

Description

DK 159210 B

in

The invention relates to paper sizing compositions and in particular to aqueous compositions containing hydrophobic, cellulose-reactive sizing agents and reinforced rosin.

Aqueous dispersions containing finely divided rosin particles, a water-soluble cationic resin dispersant, and water are disclosed by Aldrich in the specification to U.S. Patent No. 3,966,654. The aqueous dispersions of reinforced rosin are useful as internal sizing agents or surface sizing agents for paper. However, the bonding ability is dependent on both the pH value and the concentration, and in order to achieve a good bonding efficiency it is necessary to use more than approx. 0.1% reinforced rosin based on the dry weight of the fiber mass (the critical level) and performing bonding in acidic systems.

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Also known are sizing compositions which are aqueous emulsions or dispersions of a hydrophobic, cellulose-reactive sizing agent such as a ketene dimer and a nonionic, anionic or cationic dispersant. The cellulose-reactive sizing agents, and especially the ketene dimer sizing agents, have become commercially important as sizing can be carried out under alkaline conditions, which does not adversely affect the paper strength, and a better sizing at a lower critical level than is possible with rosin anti-sizing agents. However, they have a serious disadvantage, since drying is necessary for PC to develop initial bonding and the maximum expected bonding is not developed until after a considerable period of time depending on the conditions of use.

A method that has been proposed to accelerate the sizing evolution with cellulose-reactive sizing agents involves the addition of certain water-soluble, cationic, thermoset resins to the dispersions. Compositions of this type are mentioned e.g. in the specification of GB patent No. 1,533,434 and in the description of US patent 4,240,935. Although these compositions 35 provide a substantial improvement in the rate of adhesive development, complete drying is required to obtain maximum bonding. However, with painted wood pulp and other hard-to-glue fibers, aging is required to achieve maximum bonding.

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With the present invention, aqueous dispersions are now provided which contain both reinforced rosin and cellulose-reactive sizing agents and which surprisingly overcome the disadvantages associated with the use of both components separately. The dispersions of the present invention also provide the advantages of the individual components and further provide greater and faster bonding than would be expected with one or the other component alone.

The aqueous dispersions of the present invention have as the continuous phase an aqueous solution containing at least one of any known dispersing agent for rosin glue of anionic anionic or cationic species, and as the dispersed phase (a) finely divided particles of a hydrophobic, cellulose-reactive 15 sizing agents selected from key additives, organic acid anhydrides, organic isocyanates and mixtures thereof, which sizing dispersion is characterized in that it also contains (b) finely divided rosin particles, the weight ratio of the dispersed phase between (b) and (a) is from 0.1: 1 to 10: 1, and the amount of dispersant is from about. 5 to approx. 140% based on the weight of the dispersed phase.

The reinforced rosin component in the dispersed phase is the adduct reaction product of the rosin reaction with an acidic compound containing the group> C = i-C = 0 and is obtained by reacting rosin with the acidic compound at elevated temperatures of from ca. 150 ° C to approx. 210 ° C.

The amount of acidic compound used will be the amount which will provide amplified rosin containing from ca. 1 to approx.

12% by weight of acidic compound, based on the weight of the reinforced rosin. Methods for preparing reinforced rosin are described in the specification of U.S. Patent Nos. 2,628,918 and 2,684,300, incorporated herein by reference.

II

Examples of acidic compounds containing the group> C = C-C = O which can be used to prepare the enhanced rosin include α- / J-unsaturated organic acids and their available anhydrides, specific examples include fumaric acid, maleic acid, 3

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acrylic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citric acid anhydride. If desired, mixtures of acids can be used to prepare the reinforced rosin.

If desired, mixtures of various reinforced rosin may also be used. Thus, e.g. a mixture of the acrylic acid derivative of rosin and the fumaric acid adduct is used to prepare the novel dispersions of the present invention. Also amplified rosin can be used which has been substantially completely hydrogenated after adduct formation.

The reinforced rosin may, if desired, be stretched by known stretching agents therefor, such as wax (particularly paraffin wax and crocrystalline wax), hydrocarbon resins, including those derived from petroleum hydrocarbons and terpenes, and similar compounds. This is accomplished by mixing the amplified rosin with from approx. 10 to about 100% by weight based on the weight of the reinforced rosin of the stretching agent for the reinforced rosin.

Mixtures of reinforced rosin and rosin as well as mixtures of reinforced rosin, rosin and rosin extender may also be used. Mixtures of reinforced rosin and rosin include from ca. 25 to 95% reinforced rosin and from approx.

75 to 5% rosin. Mixtures of reinforced rosin, rosin-2 sodium and rosin extender comprise from ca. 25 to 45% reinforced rosin, from approx. 5 to 50% rosin and from approx. 5 to 50% rosin extender.

If rosin (i.e., non-reinforced rosin) is used in conjunction with reinforced rosin, it can be any of the commercially available rosin, such as rosin, gum rosin, tall oil rosin, and mixtures of two or more thereof in untreated or treated form. Partially or substantially completely hydrogenated rosin as well as polymerized rosin may be used as well as rosin that has been treated to inhibit crystallization, such as by heat treatment or reaction with formaldehyde.

Aqueous dispersions containing finely divided particles of reinforced 4

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rosin is commercially available. One method of preparing such dispersions is disclosed by Aldrich in the disclosure of U.S. Patent No. 3,966,654 and comprises first dissolving the amplified rosin in a water-immiscible organic solvent therefor, such as e.g. benzene, xylene, chloroform, methylene chloride or 1,2-dichloropropane. If desired, mixtures of 2 or more solvents may be used. The selected solvent will also be non-reactive to the components of the aqueous dispersion to be prepared subsequently. The solution of the organic solvent and enhanced rosin is then mixed with the aqueous solution of a cationic dispersant to produce an emulsion which is substantially unstable and in which the solution of the organic solvent and the rosin constitutes the dispersed phase. The substantially unstable aqueous emulsion is then subjected to extreme shear to produce a substantially stable aqueous emulsion. Extreme displacement is conveniently achieved by a homogenizer. Thus, passing the unstable aqueous emulsion at least once through a homogenizer under pressure of the order of approx. 7000 to ^ approx. 55160 kPa a substantially stable emulsion will be provided. Then, the organic solvent component of the emulsion is removed from the emulsion and a substantially stable aqueous dispersion of reinforced rosin particles is provided. Alternatively, the organic solvent solution and prepackaged rosin may be mixed with an aqueous solution of a cationic dispersant in an amount sufficient to provide a stable water-in-oil emulsion which is then inverted to produce a stable oil. -i-water emulsion by rapid addition of water with vigorous stirring. The organic solvent 30 is then removed, e.g. by distillation under reduced pressure.

The dispersant may be any of the known rosin adhesive dispersants and may be nonionic, anionic or cationic. Particularly preferred are the cationic, thermosetting, water-soluble polyaminopolyamide-epichlorohydrin resins, all kylene-polyamine-epichlorohydrin resins, and poly (di-alkylamino) epichlorohydrin resins. These resins are disclosed in U.S. Patent Nos. 2,926,116, 2,926,154, 3,700,623, and 3,966,954.

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Another method for preparing aqueous dispersions of reinforced rosin is disclosed by Aldrich in the specification of U.S. Patent No. 3,817,768. This method comprises first preparing an unstable aqueous dispersion containing reinforced rosin and a small amount of a salt of rosin base material as a dispersant, heating the unstable dispersion to from 150 to approx. 195 ° C, and the heated dispersion is then subjected to extreme shear as through passage through a homogenizer under a pressure of from ca. 13800 to approx. 55160 kPa to produce a substantially stable dispersion. Other anionic dispersants, such as the salts of all chylaryl sulphonic acid, salts of the dialkyl esters of sulfuric acid, salts of all chilic half esters of sulfuric acid, and salts of all kylphenoxy (polyethyleneoxy) ethanol semesters of sulfuric acid are disclosed in the patent specification. be suitable by this method.

Yet another suitable method for preparing aqueous dispersions of enhanced rosin is described by Hughes et al. in U.S. Patent No. 4,199,369. This method is an inversion method and involves adding a solution of certain water-soluble anionic dispersants in water to molten, reinforced rosin under continuous stirring to produce a water-in-oil emulsion and then adding hot water with vigorous stirring until the emulsion inverses, the water becoming the continuous phase and the rosin becoming the dispersed phase. The preferred dispersants used in the inversion method described in U.S. Patent No. 4,199,369 are alkali metal or ammonium salts of alkyl phenoxy or higher alkoxy poly (ethyleneoxy) ethanol halves of sulfuric acid.

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The hydrophobic, cellulose-reactive adhesives which have been found to be particularly suitable as the second component of the dispersed phase are ketene dimers, acid anhydrides and organic isocyanates.

Ketene dimers used as cellulose reactive sizing agents are dimers of the general formula: [R "CH = C = O] 2, wherein R" represents a hydrocarbon radical such as an alkyl group having at least 8 carbon atoms, a cycloal cooling group having at least 6 carbon atoms, an aryl, aralkyl and an alkaryl group. In naming chain dimers, the radical is called 6 6

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"R" followed by "chain dimer". Thus, phenylketene dimer is: // n-ch = c = 0 J2 10 and benzylketene dimer is: 15 / ~ \ _ V y - CH2-CH = C = 0 L -h 20 and decylketene dimer is [C 2nd Examples of ketene dimers include octyldecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, Naphthyl and cyclohexyl ketene dimers as well as the ketene dimers produced by from montanoic acid, naphthenic acid, g in 9 10 Δ '-decylenic acid, Δ' -dodecylenic acid, palmitolic acid, oleic acid, ricinoleic acid, linoleic acid and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids, such as the mixtures of fatty acids, , babassu oil, palm-30 core oil, palm oil, olive oil, peanut oil, rapeseed oil, beef tallow, fat (plum) and whale blubber. Mixtures of any of the fatty acids listed above may also be used.

Acid anhydrides suitable as paper cellulose-reactive adhesives 35 are well known in the art and include (A) rosin anhydride, see US Patent No. 3,582,464, (B) anhydrides of the form: 7

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(I) vc °

VCX

Wherein R 1 represents a saturated or unsaturated hydrocarbon radical which is an unbranched or branched alkoxy radical, an aromatically substituted alkoxy radical or an alkoxy substituted aromatic radical, provided that the hydrocarbon radical contains in total from ca. 14 to 36 carbon atoms, and (C) cyclic di carboxylic anhydrides of the formula: (ii) o

II

, / \ 15 R -V. '0 \ /, fr

ISLAND

wherein R 1 represents a dimethylene or trimethylene radical and wherein R "20 represents a hydrocarbon radical having more than 7 carbon atoms and is preferably all alkyl, alkenyl, aralkyl or aralkenyl. Substituted cyclic dicarboxylic anhydrides encompassed by the above formula (II) are substituted succinic and glutaric anhydrides. In the formula (I) above, each R 1 may represent the same carboxylic hydrocarbon radical or each R 2 may be a different hydrocarbon radical.

Specific examples of anhydrides of formula (I) are myristoyl anhydride, palmitoyl anhydride, oleoyl anhydride and stearoyl anhydride.

30

Specific examples of anhydrides of formula (II) are isooctadecyanuric anhydride, n-hexadecenyric anhydride, dodecyric anhydride, decenyl succinic anhydride, and octenyl succinic anhydride.

35

Hydrophobic organic isocyanates used as paper sizing agents are well known in the art. The best results are obtained when the hydrocarbon chains of the isocyanates contain at least 12 carbon atoms, preferably from 14 to 36 carbon atoms. Such isocyanates 8

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includes rosin isocyanate, dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicosyl isocyanate, dococyl isocyanate, 6-ethyldecyl isocyanate, 6-phenyldecyl isocyanate, and 2 isocyanate radicals and impart hydrophobic properties to the molecule in its entirety.

Aqueous dispersions or emulsions containing finely divided particles of hydrophobic, cellulose-reactive adhesives are commercially available. Such dispersions are traditionally prepared by stirring the cellulose-reactive sizing agent in an aqueous solution of one emulsifier and passing the mixture through a homogenizer. Emulsifiers traditionally used in the preparation of 1® emulsions of cellulose-reactive adhesives are suitable. Such emulsifiers include cationic starches, which are water-soluble starches containing sufficient amino groups, quaternary ammonium groups or other cationic groups to make the starch in its entirety cellulose substrate. Examples of such cationic starches are the cationic amine modified starches disclosed in the specification of US Patent No. 3,130,118 and the known cationic starch graft copolymers. Other emulsifiers are the water-soluble cationic thermosetting resins obtained by reacting epichlorohydrin with a water-soluble aminopolyamide 25 prepared from a dibasic carboxylic acid having from 3 to 10 carbon atoms and a polyalkylene polyamine containing from 2 to 8 alkylene groups ( U.S. Patent Nos. 2,926,116 and 2,926,154), with a water-soluble polydiallylamine (see U.S. Patent No. 3,966,654), with condensates of dicyandiamide or cyanamide and a polyalkylene polyamine on (see U.S. Patent No. 3,403,113 ), with bis-aminopropylpiperazine or condensates thereof with dicyandiamide or cyanamide (see U.S. Patent No. 4,243,481) and the like.

The dispersed phase of the cationic aqueous dispersions of the present invention contains both finely divided particles of a hydrophobic, cellulose-reactive sizing agent and finely divided particles of reinforced rosin, and it is found that the dispersed phase should comprise at least 10% by weight of each. one must obtain the advantages of the invention. The weight ratio of the reinforced

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Thus, 9 rosin and the cellulose reactive adhesive will range from 0.1: 1 to 10: 1. However, the most convenient range is from 0.2: 1 to 5: 1, which is the preferred range.

The aqueous dispersions of the present invention also contain, as previously stated, a water-soluble nitrogen-containing cationic dispersant. Any cationic, nitrogen-containing dispersant which is water-soluble and which imparts a positive surface charge to the particles in the dispersed phase of the dispersion is suitable. Nitrogen-containing dispersants of this type are well known in the art and are commercially available. Typical dispersants are quaternary ammonium compounds, homopolymers or copolymers of ethylenically unsaturated amines; the resinous reaction products of the reactions between epihalohydrin and polyaminopolyamides, al chylene polyamines, poly (diallylamines), b -aminopropylpipe-razin condensates and cationic starches, especially starch ethers containing amino groups or quaternary amino groups. Particularly preferred are cationic starches and the resinous reaction products from the reaction between epichlorohydrin and an aminopolyamide, an alkylene polyamine, a poly (diallylamine) or a dicyandiamide-polyalkylene polyamine condensate. The dispersants can be used singly, in combination with each other or in combination with anionic or nonionic dispersants.

The least amount of cationic dispersant used should be

OA

of course, be sufficient to make the dispersion cationic.

The amount used will, of course, vary depending on the water solubility, the anionic or cationic strength of the dispersions used initially, and the cationic strength of the agent used. The amount will usually range from approx. 5 to approx. 140% by weight, preferably from 20 to 120 and more preferably from 40 to 100% by weight, based on the dispersed phase. Quantities of less than approx. Generally, 5% is not sufficient to make the dispersion cationic, and larger amounts than about 5%. 140% have not been found to provide additional benefits and are therefore not required.

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The cationic dispersions of the present invention can be prepared at any convenient concentration. Particularly useful are dispersions in which the dispersed phase is from ca. 5 to 70%, preferably from 10 to 55%, the dispersant from 1 to 15%, 5 preferably from 2 to 10%, and the remainder up to 100% being water. The dispersions of the present invention may also contain other sizing ingredients or non-sizing ingredients provided that their presence does not destroy the advantages obtained by the invention. Particularly useful in this regard are alum which is traditionally used to cure rosin adhesives. Generally, alum cannot be added to reinforced rosin until used as a paper timing agent and must be added separately to an aqueous suspension of papermaking fibers at various stages prior to sheet forming for internal bonding or applied to the sheet formed before, 1® simultaneously or after use of rosin for the external bonding. It has now been found that alum can be present in any amount in the aqueous cationic dispersions of the present invention without destroying the bonding efficiency, and that the presence of alum provides a unique advantage, making the dispersion more convenient, which advantage has not been achieved in the past. When alum is present, quantity will generally be in the range of approx. 25 to approx. 200% based on the weight of reinforced rosin particles. However, the most practical range is between 75 and 150% and this is the preferred range.

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Other additives, such as preservatives, may also be present in small amounts.

The novel dispersions of the present invention can be prepared by mixing a pre-made dispersion on the particles of reinforced rosin with a pre-made cationic dispersion of the hydrophobic, cellulose-reactive sizing agent. They can also be prepared by mixing a melt or an organic solution of reinforced rosin and the cellulose-reactive sizing agent in aqueous medium containing the cationic dispersant and subjecting the mixture to extreme shear conditions as stated above. Modifications to the above mentioned methods are also suitable and can be made by one of ordinary skill in the art relevant to the invention.

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The dispersions according to the invention are particularly suitable for internal sizing or surface sizing of paper and maximize the advantages of the individual sizing components while minimizing the disadvantages. The dispersions provide improved bonding 5 under conditions which are not practical for cellulose-reactive bonding dispersions alone or for reinforced rosin dispersions alone, and they also provide the fast cure rate typical of reinforced rosin adhesive and the high bonding rate typical of cellulose reactive. sizers. Thus, with the present invention, it is possible to achieve easy control of the sizing rate and / or degree under normal paper mills. ebeti ngel sees where alum is usually present, as well as using pH levels which provide paper with excellent durability. The aqueous dispersions may be added to the fiber pulp suspension at any time after refining is complete and before sheet formation or may be applied to the sheet on the paper machine by e.g. size press. For none of these applications, it is necessary to prepare the aqueous dispersion in advance, and similar advantages can be obtained from an in situ formation of the dispersion, ie. by separately adding a pre-prepared cationic dispersion of reinforced rosin and a pre-prepared cationic dispersion of the cellulose-reactive sizing agent to the fiber pulp suspension at the same site or at different sites, and thoroughly mixing the dispersions with the fiber pulp prior to sheet formation. The aqueous dispersions of the present invention may also be prepared in situ by the glue press by simultaneous or separate addition of the individual cationic components in dispersion form and mixture.

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The amount of dispersion added to the aqueous fiber pulp suspension (internal bonding) or to the prepared paper sheet (outer bonding) shall be such that a retained amount of from about 50 to about 100 is obtained. 0.01 to approx. 1% by weight and preferably from ca. 0.01 to 0.5% by weight of the combination of cellulose-reactive glue and reinforced rosin, based on the dry weight of the fibers.

Following the general outline of embodiments of the present invention, are examples which specifically illustrate 12

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invention. Unless otherwise indicated, all parts and percentages are in parts by weight and percentages by weight.

Example A 5

A ketene dimer dispersion having a total solids content of 15% and containing 5.4% ketene dimer solids, 1.4% cationic starch and 8.2% of a cationic resin prepared by condensing 1 mole of dicyandiamide with 1 mole of diethylenetriamine and reacting the condensate 10 with 1 , 2 moles of epichlorohydrin, was prepared as follows.

An emulsion of a ketene dimer prepared from a mixture of palmitic acid and stearic acid was prepared by mixing 880 parts of water, 50 parts of cationic corn starch of 10 parts of sodium in igninsulfo-1® night. The pH of the mixture was adjusted to approx. 3.5 with 98% sulfuric acid and the mixture was heated at 90-95 ° C for approx. 1 hour. Then water was added to the mixture in an amount sufficient to provide a mixture of 1760 parts (total weight). Then 240 parts of the ketene dimer were stirred in the mixture and the mixture (at 65 ° C) was homogenized by passing it once through a homogenizer at 27600 kPa. The homogenized product (at 15% total solids and 12% ketene dimer solids, 136.4 parts) was then mixed with 136.4 parts of an 18% aqueous solution of the cationic resin and 27.2 parts of water and the pH of the mixture was adjusted to from 4.0 to 4.5.

25

Example B

A cationic dispersion on reinforced rosin with a total solids content of 34.1% and containing 28.4% rosin solids 30 and 5.7% of a cationic resinous reaction product obtained by reacting 1.25 moles of epichlorohydrin with an aminopolyamide derived from 1 mole adipic acid and 0.97 moles of diethylenetriamine were prepared as follows.

35

A solution was prepared by dissolving 300 parts of reinforced rosin in 200 parts of methylene chloride over a period of 20 minutes. The reinforced rosin contained 7.5% fumaric acid, substantially all of which was in the combined or induced form. The reinforced rosin was prepared by adding 22.5 13

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parts of fumaric acid with 277.5 parts of formaldehyde treated oil resin at a temperature of approx. 205 ° C until substantially all of the fumaric acid had reacted and the amplified rosin was then cooled to room temperature. The amplified rosin solution was mixed admixture with a premixed mixture of 480 parts of aminopolyamide / epichlorohydrin resin with 12.5% solids and 260 parts of water, and the mixture was homogenized twice at 20700 kPa. The methylene chloride was then removed by distillation under reduced pressure at 60 ° C. The product was cooled and filtered through a 149 µm sieve, thereby

ISLAND

10, 750 parts of a dispersion having a viscosity of 51 x 10 Ns / m 2 were produced.

EXAMPLES 1-8 15 When mixed in a container equipped with a magnetic stirrer, various compositions were prepared from 50 parts of the cationic dispersion prepared in Example A and from ca. 9 to approx. 59 parts of the cationic dispersion prepared in Example B. Details of these examples as well as the resulting cationic dispersions 20 are set forth in subsequent Table I.

o 25 30 35

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S ^ OLO CM co CO Γ »CD CM CO SrXJ

lu m co · - <i »iricM p <β Φ * Λ cor» «* _ LO 3s- 'co co · * o i-ι o cn c W e. # 1 ft« L ^ »I 1— <* * o oo o co co oo σι. — i .. cn lu m cm i — i "00 LOCM σι +3 ^ '-P S' ** * i— * f- '® <e J2 * r» com i - <· * r »oo co w ~ v] - - -" s / i, • 2 ^ o oo in CM CD n «t · - <m ..r_r ~ lu mmi — in cm ca" φ s - J2 ΟΙ Λ co oo oo mr »* σι o <*.-I oo co co * a- -2> c ο om« * - <oO · - * cm co «we 1— LU in 1-1 00 σΐι -ι ™ o 03 t Lrt C -i =

-Q C O -M

to φ χ; * ® I- ^ 00 o * a- „lo ε To * cn c \ j σ» vo r ^ r-i ooo> c \ / ^ Λ · Λ ** Λ · * Λ # »~. \ ο (Ο co oj r ^. νο oo See lu m * d- ι — ι t "- ^ cm vi ~ * =

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* 1—1 CO.-Η CO LOCO CM h- JZ. -r- C

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15

Example 9

The sizing effect of each of the aqueous cationic dispersions prepared in Examples 1-5 was tested in the preparation of hand sheets using varying amounts of glue solids. To make the hand sheets, a mixture of 50 parts of Rayonier bleached hardwood pulp and 50 parts of Weyerhaeuser was suspended in its own hardwood pulp in standard hard water and ground to a Canadian standard grade of 500 in a "Noble and Wood" cycle unpainted. The pulse pop slurry 10 was diluted to a consistency of 0.25% in the distributor. A 2-1 it portion of the slurry was treated with enough of the cationic dispersion to produce different adhesive percentages and enough alum for papermaking to produce 0.5% alum, based on the pulp weight, and diluted to a consistency of 0.05 to 25% to produce of a sheet having a weight of 65 (g / m2) at a pH of 6.5 using a "Noble and Wood" sheet making machine. The molded sheets were wet pressed to a dry matter content of 33% and then dried at 105 ° C for 45 seconds on a steam drum dryer to a moisture content of 3-4%. The glue properties of the sheets 20 were tested using Hercules glue sample with test solution # 2 to 80% reflection. The "off-machine data" results were obtained within 2 minutes of drying and the results from natural aging were obtained after 7 days storage at room temperature and 50% relative humidity. Gluing results from 2 of these experiments as well as from 7 controls prepared in the same manner, but with the exception that the dispersion from Example A or Example B was added to the slurry portion, is given in Table II below.

30 35 16

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Table II

Glue composition Glue level Hercules glue sample (seconds) from example (%) "Off machine" Naturally aged 1 0.25 393 537 5 2 0.30 317 434 3 0.30 540 739 4 0.275 185 175 5 0.35 514 694 A 0.075 (1} 1 1 10 A 0.10 (1) 10 12 A 0.15 (1) 247 320 A 0.20 ^) 428 579

B 0.10 O O

B 0.20 3 2 15 B 0.40 "62 64 (1) Paper making alum was omitted.

Example 10 20

The aqueous dispersions of Examples 6 to 8 were used to make inner glued paper on a pilot paper making machine. The paper was prepared from a mixture of 50 parts softwood kraft pulp and 50 parts hardwood pulp milled to a Canadian standard grade of 500 and 25 molded into sheets having a weight of 65 (g / m2) at a pH of 6.4 to 6.6. Each dispersion was added to the thick stock solution immediately before dilution at the fan pump. If papermaking alum was used, it was added at the same time as the dispersion. The glued sheets were dried to a moisture content of 3% before the glue press and to a moisture content of 4% at the coil. The glue press contained a 6% solution of oxidized corn starch. The sizing was measured by the Hercules glue sample with test solution # 2 to 80% reflection on samples taken before the glue press, at the coil (from the machine) and after 7 days storage at room temperature and 50% relative humidity. Bonding results for these 35 samples and for 6 controls prepared in the same way except that the dispersion from Example A or Example B was added to the thick stock solution is given in Table III below.

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4- »Φ Ό _υ ^ · ιη <Μΐ ^ .οο <ηοιοιη ΐ, Η ^ ο ^ σιιοαι lo .Ji h n o \ cn φ => -a £ g i φ (Λ _

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O) <U

> £

s C

S_ “TcJOCO · - • 'd'OOOVOLO

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DK 159210 B

It is clear from the foregoing table that a considerable improvement in bonding is achieved with the compositions of the present invention under conditions which are not practical for ketene dimer dispersions alone (control experiments 7) or for dispersions with reinforced rosin alone (control experiments 8 and 9 ). The results further show that the compositions of the invention provide the fast cure rate typical of rosin glue and the high degree of sizing typical of ketene dimer glue, and that the sizing rate and degree can be easily controlled under normal grinding conditions where alum is usually used. are present and at pH levels which provide paper of excellent durability.

Example C

A dispersion having a total solids content of 51 ° and containing by weight 21.2% reinforced rosin, 4.3% of the cationic resin-like reaction product of Example B and 25.5% alum was prepared by mixing 50 parts of the dispersion of Example B with 17.1 parts of alum (Al2 (SO4) 3 * 181 ^ 0).

20

Examples 11.oa 12

Two compositions were prepared by mixing in a container equipped with a magnetic stirrer 50 parts of the 25 cationic dispersion prepared in Example A and 30 parts (Example 11) or 60 parts (Example 12) of the dispersion prepared from Example C. The cationic dispersion of Example 11 contained, by weight, of the total composition 7.95% reinforced rosin, 3.41% ketene dimer, 7.58% of the mixed cationic dispersant, and 9.56% alum and had a total solids content of 28.5 %. The cationic dispersion of Example 12 contained by weight of the total composition 11.56% reinforced rosin, 2.48 ketene dimer, 6.68% of the mixed dispersant and 13.90% alum and had a total solids content of 34.6% .

35

The efficiency of the aqueous dispersions prepared in these examples for surface sizing of paper was assessed using non-bonded 2 bleached kraft paper (65 g / m) made at a pH of 6.5.

The sheets were processed using a small horizontal

DK 159210 B

19 laboratory presses by sampling the aqueous dispersions to the glue press slot and passing the sheets of paper through the dispersion before being pressed by the glue press rollers. Under these conditions, the sheets collected approx. 70% of the glue depression dispersion relative to their 5 weight. The glued sheets were dried for approx. 20 seconds at 93 ° C to a moisture content of approx. 5%. Bonding was determined by the Hercules glue test using Test Solution # 2 for a reflection of 80% within 2 minutes of drying ("from the machine") and after 7 days storage at room temperature and 50% relative humidity (naturally aged 10). The gluing results for these examples and controls where the paper was treated in the same way except that the dispersions from Examples A, B or C were used are given in Table IV below.

Table IV 15

Glue joint - Additive Hercules glue sample (seconds) Sample level from example (% 1 "From the machine" Naturally aged 11 0.21 23 320 20 12 0.175 8 35 A 0.035 0 5 A 0.07 4 160 B 0.07 0 0 B 0.07 ^ 7 15 25 C 0.14 8 14 1 35

Alum, in an amount of 0.07% based on the weight of the dry pulp, was added to the glue press slot as an aqueous solution simultaneously with the dispersion of Example B.

30

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Claims (11)

Sizing dispersions having as the continuous phase an aqueous solution containing at least one of any known dispersing agent for rosin adhesives of a nonionic, anionic or cationic nature, and as the dispersed phase (a) finely divided particles of a hydrophobic cellulose reactive sizing agent selected from ketene dimers, organic acid anhydrides, organic isocyanates, and mixtures thereof, characterized in that they also contain (b) finely divided particles of "rosin", the weight ratio of the dispersed phase between (b) and (a) being from 0 , 1: 1 to 10: 1, and wherein the amount of dispersant is from about 5 to about 140% based on the weight of the dispersed phase. The sizing dispersion according to claim 1, characterized in that the aqueous dispersion also contains from approx. 25 to approx. 200% alum based on the weight of the reinforced rosin particles. Glue dispersion according to claim 1, characterized in that the cellulose-reactive glue is a ketene dimer. Glue dispersion according to claim 1, characterized in that the dispersant is a water-soluble nitrogen-containing cationic dispersant. 25 Sizing dispersion according to claim 3, characterized in that the dispersant is selected from cationic starches and the resinous reaction products from the reaction between epichlorohydrin and an aminopolyamide, an alkylene polyamine, a poly (diallylamine) 30 or a dicyandiamide polyalkylene polyamine condensate. Method for gluing paper or cardboard from cellulose solids, characterized in that the sizing dispersion according to claim 1 is used as glue in a sizing process in a papermaking machine. Process according to claim 6, characterized in that the sizing process is an internal sizing process. DK 159210 B Method according to claim 6, characterized in that the bonding process is a surface bonding process. A paper or cardboard product comprising sheet-laid cellulose fibers 5 bonded with the bonding dispersion of claim 1. Product according to claim 9, characterized in that the cellulose fibers are the inner glue. Product according to claim 9, characterized in that the cellulose fibers are surface-glued. 15 20 25 30 35