DK147859B - PROCEDURE FOR THE MANUFACTURE OF LIMITED PAPER OR CARTON AND LIMITED APPLICATION BY EXERCISE OF THE PROCEDURE - Google Patents

Description

147859

The invention relates to a process for the production of glued paper or cardboard of cellulose fibers, using an adhesive in the form of an aqueous emulsion which comprises: (A) a hydrophobic, cellulose-reactive adhesive such as a ketene dimer, an acid anhydride or an organic isocyanate , (B) a nitrogen-containing adhesive accelerator, (C) an emulsifier, and optionally (D) a smaller amount of sodium lignin sulfonate.

From the disclosure of English Patent No. 1,373,788, the use of a dicyandiamide-formaldehyde condensate in combination with a ketene dimer-containing adhesive for providing glued paper and a higher sizing board is known than is obtained by using the same amount of ketene dimer. containing glue alone.

Further, from U.S. Patent No. 3,666,512, it is known to produce sizing paper with acid anhydride type adhesive, in connection with which is used a sizing accelerator which may be an aminopolyamide-epichlorohydrin resin. In relation to this, it has now become possible to obtain even better sizing results with the method according to the invention.

This is achieved by the process set forth in the preamble being characterized in that the nitrogen-containing adhesive accelerator (B) used is made by reacting an epihalohydrin with a condensate obtained by condensing dicyan diamide or cyanamide with a polyalkylene polyamine.

The invention also relates to an adhesive for making paper or cardboard from cellulose fibers in the form of an aqueous emulsion, comprising: (A) a hydrophobic, cellulose-reactive adhesive such as a ketene dimer, an acid anhydride or organic isocyanate, (B) a nitrogen-containing sizing accelerator, (C) an emulsifier, and optionally (D) a smaller amount of sodium lignin sulfonate, the adhesive being characterized in that the nitrogenous sizing accelerator (B) is produced by reacting an epihalohydrin with a condensate produced by the condensation of dicyandiamide or cyanamide with a polyalkylene polyamine.

The term "emulsion" is used herein, as is customary in the art, in the sense either a liquid-in-liquid type dispersion or of a solid-in-liquid type.

To prepare the new adhesives according to the invention, a sufficient amount of sizing accelerator is thoroughly mixed into the emulsion to increase the sizing effect of the adhesive. It has been found that from 0.25 to 8 parts by weight for each part by weight of the cellulose-reactive, hydrophobic adhesive, so * 11 car present in the emulsion, gives the best results.

The amount of emulsifier used will be the amount sufficient to provide and maintain an emulsion which is stable for a long period of time and may be determined by one skilled in the art.

The emulsifier used may be selected from the emulsifiers commonly used in the preparation of emulsions of cellulosic reactive adhesives. Such emulsifiers are well known in the art and include cationic starches, which are water-soluble starches containing enough cationic amino groups, quaternary ammonium groups or other cationic groups to render the starch as a whole cellulose emulsifier. An example of such a cationic starch is that of cationic amine modified starch known from U.S. Pat. No. 903,416.

Another emulsifier which can be used is the water-soluble cationic thermosetting resin which is obtained by reacting epichlorohydrin with a water-soluble aminopolyamide obtained from a dicarboxylic acid and a polyalkylene polyamine. Resins of this type are disclosed in the specification to English Patent No. 865,727.

The nitrogenous condensation products used in the invention are obtained by reacting an epihalohydrin with a poly-condensate provided by condensing dicyandiamide or cyanamide with a polyalkylene polyamine, both reactions being carried out at elevated temperatures.

Nitrogen-containing condensation products suitable for use in the present invention are described in the disclosure to English Patent No. 1,125,486.

The epihalohydrin may be epibromohydrin, but epichlorohydrin is preferred. The epihalohydrin can be prepared in situ, if desired, using a glycerol dihalohydrin such as glycerol dichlorohydrin.

The polyalkylene polyamine used in the preparation of the polycondensate has the formula:

R

in H2NCnH2n (HCnH2n> x, IB2 where R is hydrogen or C1 -C4 alkyl, n is an integer of 2-6 and x is an integer of 1-4. Examples of C1 -C2 - alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and t-butyl.

Particular examples of the polyalkylene polyamines of the above formula are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropyltriamine, dihexamethylenetriamine, pentaethylenehexamine and methyl bis (3-aminopropyl) amine.

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The nitrogenous condensation products are provided by first condensing at elevated temperature dicyandiamide or cyanamide with a polyalkylene polyamine as described above to form a polycondensate. For each primary amino group in the polyalkylene polyamine, from 0.1 to 1 mole is preferably used, from 0.4 to 0.6 mole of dicyandiamide. When cyanamide is used, it is used in an amount of from 0.2 mole to 2 mole, preferably from 0.8 mole to 1.2 mole, for each primary amino group of the polyalkylene polyamine. The resulting polycondensate is preferably reacted at elevated temperature with an epihalohydrin using from 0.3 mol to 5.5 mol, preferably from 1 mol to 1.5 mol, epihalohydrin for each secondary or tertiary amino group of the polyalkylene polyamine used. in the preparation of the polycondensate.

In preparing the polycondensates, dicyandiamide or cyanamide is heated with the polyalkylene polyamine at a temperature of from ca. 100 ° C to approx. 200 ° C, preferably from ca. 150 ° C to approx. 170 ° C. During the reaction, 2 moles of ammonia are formed for each mole of dicyandiamide and 1 mole of ammonia for each mole of cyanamide.

As a rule, it is not necessary to conduct the condensation in the presence of a solvent as the reactants dissolve at each other at the reaction temperatures used. If desired, an inert solvent such as ethylene glycol monoalkyl ether or dialkyl ether or diethylene glycol monoalkyl ether or dialkyl ether can be used.

The reaction of the polycondensate with epihalohydrin is preferably carried out in aqueous solution or dispersion. If desired, another medium, e.g. acetone or an alcohol such as methanol or ethanol, or mixtures thereof with water, is used. The reaction with epihalohydrin is carried out at elevated temperature, preferably at from 60 ° C to 100 ° C. As soon as the reaction mixture shows signs of imminent gelling, the reaction is stopped by the addition of an acid or by dilution with water or both.

Depending on the polyalkylene polyamine used and the ratio of polyalkylene polyamine to dicyandiamide or cyanamide to epichlorohydrin selected, the nitrogenous condensation products are readily soluble or dispersible only in water.

The stability of the aqueous solutions can be greatly enhanced by setting them to an acidic pH. Furthermore, improved stability is also obtained by diluting the aqueous solutions, such that e.g. with a 20% solution at a pH of 4.8 to 5 at room temperature, a stability of 3-4 months is ensured.

The percentages in the examples below are weight percentages.

Example 1 252 grams (3 moles) of dicyandiamide are added to 309 grams (3 moles) of diethylenetriamine in a reaction vessel equipped with a thermometer, stirrer and reflux. The resulting mixture is heated to 120-140 ° C and the reaction product ammonia is released. The reaction proceeds exothermically as the temperature rises to approx. 160 ° C. This temperature is kept for approx.

1 hour. The amount of ammonia eliminated during the reaction is 5-6 moles. The reaction mass is then cooled by the addition of water in sufficient quantity to give a solids content of approx. 25%. 358.8 grams (3.9 moles) of epichlorohydrin are then added slowly so that the temperature of this reaction mass rises to 55 - 60 ° C. This temperature is maintained until the viscosity of the reaction mass reaches H on the Gardner-Holt scale. The reaction is terminated by adding water in sufficient quantity to give a dry matter content of 20%. The resulting solution is adjusted to pH 5 by the addition of formic acid.

Example 2 252 grams (3 moles) of dicyandiamide are added to 438 grams (3 moles) of triethylenetetramine in a reaction vessel equipped with a thermometer, stirrer and reflux. The resulting mixture is heated to 120-140 ° C and the reaction product ammonia is released. The reaction proceeds exothermically as the temperature rises to approx. 160 ° C. This temperature is kept for approx.

1 hour. The amount of ammonia eliminated during the reaction is 4-5 moles. The reaction mass is then diluted by adding 400 grams of water. The resulting solution has a solids content of 59.5%. Dilute 336 grams of the solution to a dry matter content of 25% by adding 464 grams of water. 110 grams (1.2 moles) of epichlorohydrin are then added slowly over a period of 15 minutes, during which time the temperature of the reaction mass rises to 70 ° C. This temperature is kept for 44 minutes while the viscosity of the reaction mass rises to N on the Gardner-Holt scale. The reaction is terminated by adding 680 grams of water at once and the pH of the solution is adjusted to 4.5 by the addition of 22 grams of concentrated formic acid. The resulting solution has a dry matter content of 21.1%.

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Example 3 168 grams (2 moles) of dicyandiamide are added to 290 grams (2 moles) of methyl bis (3-aminopropyl) amine contained in a reaction vessel equipped with a thermometer, stirrer and reflux. The resulting mixture is heated to 220 ° C and kept at this temperature for 1 hour. Then 350 grams of water is added to provide a solution with a dry matter content of 44.9%. 768 grams (345 grams of dry matter, 2 equivalents) of this solution are diluted to a dry matter content of 20% with 957 grams of water. 966 grams (10.5 mol) of epichlorohydrin is then added slowly. The temperature of the reaction mass is maintained at 80 ° C until its viscosity reaches N on the Gardner-Holt scale. The reaction is terminated by the addition of 3862 grams of water and the solution is adjusted to pH 5 by the addition of 61 grams of concentrated formic acid. The resulting solution has a solids content of 17%.

Acid anhydrides useful as for cellulose-reactive adhesives for paper are well known in the art and include (A) resin anhydride, see the specification for U.S. Patent No. 3,582,464, (B) Anhydrides having the structure: "> <> Wherein R 1 is a saturated or unsaturated hydrocarbon radical, which hydrocarbon radical is a straight or branched alkyl radical, an aromatic, substituted alkyl radical or an alkyl substituted aromatic radical, as long as the hydrocarbon radical contains in total from ca. 14 to approx. 36 carbon atoms, and (C) cyclic dicarboxylic anhydrides having the structure:

ISLAND

H

Rn-R 'O (II),

C

II

wherein R 'is a dimethyl or trimethylene radical and wherein R "is a hydrocarbon radical containing over 7 carbon atoms selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl. Substituted cyclic dicarboxylic anhydrides which fall under the above formula (XI), are substituted succinic and glutaric anhydrides. In the above formula (I), the two R 1 may be the same hydrocarbon radical or different hydrocarbon radicals.

Particular examples of anhydrides of formula (I) are myristyl anhydride, palmityl anhydride, oleyl anhydride and stearyl anhydride.

Particular examples of anhydrides of formula (II) are isooctacetacenyl succinic anhydride, n-hexadecenyl succinic anhydride, dodecyl succinic anhydride, decenyl succinic anhydride, octenyl succinic anhydride and heptyl glutaric acid.

Hydrophobic organic isocyanates used as adhesives for paper 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 include resin isocyanate, dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicosyl isocyanate, docosylisocyanate, 6-ethyl decyl isocyanate, 6 long chain alkyl group belongs to two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole.

Ketene dimers used as for cellulose reactive adhesives are dimers of the formula: [r '"ch = c = o] 2, wherein R"' is a hydrocarbon radical such as alkyl, having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms , aryl, aralkyl and alkaryl. In naming the ketene dimers, the R '' radical is followed by "ketene dimer." Phenyl ketene dimer is thus: - <^^> - CH = C = 0, - * 2 benzyl ketene dimer: ^ 7 ^> - ch2-ch = c = o - - * 2 8 147859 and decyl ketene dimers are [Ο10Η21-ΟΗ = Ο = Ο] 2- Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl and cyclohexylketene dimers, as well as the ketene dimers made of montanoic acid, naphthenic acid, Δ9,10-decylene acid, Δ9,10 dodecylenic acid, palmitolic acid , castoric acid, linoleic acid, linolenic acid and eleostearic acid, as well as ketene dimers made from naturally occurring fatty acid mixtures such as those found in coconut oil, bab ssuo onion, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed oil, beef tallow, lard, and whale oil. Mixtures of several of the above fatty acids may also be used.

Example 4

An emulsion of a ketene dimer made from a mixture of palmitic and stearic acid is prepared by mixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignin sulfonate. The mixture is adjusted to a pH of approx. 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90 - 95 ° C for approx. 1 hour. Water is then added to the mixture in sufficient quantity to give a mixture of 1750 parts (total weight). Ca. 240 parts of the ketene dimer are stirred into the mixture together with 2.4 parts of thiadiazine. Thiadiazine is used as a preservative. The resulting premix (at 65 ° C) is homogenized 2 by one passage through a homogenizer at 280 kg / cm. The homogenized product is diluted with water to a ketene dimer content of approx. 6%.

Example 5

Example 4 is repeated except that the ketene dimer of oleic acid is used in place of the ketene dimer made from a mixture of palmitic and stearic acid.

As is well known in the art, cellulose-reactive, hydrophobic adhesives are used for internal and external bonding of paper. The accelerator according to the invention can be used in combination with the adhesive in both methods.

Example 6

The product of Example 4 is diluted with water to a content of ketene dimer of 0.10%.

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Example 7

The product of Example 5 is diluted with water to a content of ketene dimer of 0.10%.

Example 8

The products of Example 4 and Example 1 are combined with the addition of water as needed to provide an aqueous adhesive comprising 0.10% ketene dimer of Example 4 and 0.20% of the nitrogenous condensation product of Example 1.

Example 9

The products of Example 4 and Example 1 are combined with the addition of water as needed to provide an aqueous adhesive comprising 0.10% ketene dimer of Example 4 and 0.10% of the nitrogenous condensation product of Example 1.

Example 10

The products of Example 4 and Example 2 are combined with the addition of water as needed to provide an aqueous lira comprising 0.10% ketene dimer of Example 4 and 0.10% of the nitrogenous condensation product of Example 2.

*

Example 11

The products of Example 4 and Example 3 are combined with the addition of water as needed to provide an aqueous adhesive comprising 0.10% ketene dimer of Example 4 and 0.10% of the nitrogenous condensation product of Example 3.

Example 12

The products of Example 5 and Example 1 are combined with the addition of water as needed to provide an aqueous adhesive comprising 0.10% ketene dimer of Example 5 and 0.10% of the nitrogenous condensation product of Example 1.

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The above glue was applied to the surface of a sheet of 65/2 g / m of unlabeled paper. The sheet was made from a 50:50 blend of hardwood and softwood pulp on a pilot plant paper machine.

Each glue was set to pH 7 before being applied to the sheet in the squeeze area by a horizontal glue press. The glue press was running at 12.3 m / min and the moisture absorption was 70%. The retention of the ketene dimer was the same in all experiments. The glued sheets were dried at 107 ° C for 20 seconds on a laboratory drum dryer to 4% humidity. The sizing was measured by the Hercules sizing test with sample solution # 2 to the specified reflectance. The test results after the machine are obtained 2 minutes after drying and the test results after natural maturation are obtained after at least 3 days storage at room temperature. It is well known in the art that ketene dimer bonding develops virtually all the bonding properties of the paper in 3 days. After this time, the paper's bonding properties remain largely the same.

The bonding results are given in Table I below.

TABLE I

_Hercules Glue Test ____

Glue After machine for Naturally matured according to example 80% reflectance to 85% reflectance 6 0 330 7 0 450 8 180 300 9 (1st attempt) 335 500 9 (2nd attempt) 200 536 9 (3rd attempt) 160 600 10 202 455 11 125 460 12 250 500

Example 13

An emulsion of stearic anhydride is prepared by first mixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium equation sulfonate. The mixture is adjusted to pH approx. 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90 - 95 ° C for approx. one hour. Water is then added to the mixture in sufficient quantity to give a mixture of 1750 parts (total weight). The temperature of the mixture is adjusted to 70 ° C. Ca. 240 parts of stearic anhydride are stirred in the mixture together with 2.4 parts of thiadiazine. Thiadiazine is used as a preservative. The resulting premix (at 70 ° C) is homogenized at one pass 2 through a homogenizer at 281 kg / cm. The homogenized product is diluted with water to a stearic anhydride solids content of approx. 6%.

Example 14

An emulsion of iso-octadecenyl succinic anhydride is prepared by first mixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignin sulfonate. The mixture is adjusted to pH approx. 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90 - 95 ° C for approx.

1 hour. Water is then added to the mixture in sufficient quantity to give a mixture of 1750 parts (total weight). Ca. 240 parts of isooctadecenyl succinic anhydride are stirred into the mixture together with 2.4 parts of thiadiazine. Thiadiazine is used as a preservative. The resulting premix is homogenized at room temperature, one passage through a homogenizer at 281 kg / cm. The homogenized product is diluted with water to an anhydride solids content of approx. 6%.

Example 15

An emulsion of octadecyl isocyanate is prepared by first mixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignin sulfonate. The resulting mixture is heated to 90 - 95 ° C for approx.

1 hour. Water is then added to the mixture in sufficient quantity to give a mixture of 1750 parts (total weight). Ca. 240 parts of octadecyl isocyanate are stirred into the mixture together with 2.4 parts of thiadiazine. Thiadiazine is used as a preservative. The resulting premix is homogenized at room temperature by one passage through a homogenizer 2 tor at 281 kg / cm. The homogenized product is diluted with water to an octadecyl isocyanate solids content of approx. 6%.

Example 16

The product of 13 is diluted with water to a stearic anhydride content of 0.20%.

Example 17

The product of Example 14 is diluted with water to an iso-octadecenyl succinic anhydride content of 0.20%.

147359

Example 18 12

The product of Example 15 is diluted with water to an octa-decyl isocyanate content of 0.20%.

Example 19

The product of Example 13 and a nitrogenous condensation product made according to Example 1 are combined with the addition of water as needed to provide an aqueous glue. containing 0.20% stearic anhydride and 0.20% of the nitrogen-containing condensation product.

Example 20

The product of Example 14 and a nitrogen-containing condensation product prepared according to Example 1 are combined with the addition of water as needed to provide an aqueous glue. containing 0.20% isooctadecenyl succinic anhydride and 0.20 of the nitrogen-containing condensation product.

Example 21

The product of Example 15 and a nitrogen-containing condensation product prepared according to Example 1 are combined with the addition of water as needed to provide an aqueous glue containing 0.20% octadecyl isocyanate and 0.20% nitrogen-containing condensation product.

The above glue according to Examples 16-21 was applied to the surface 2 of a sheet of 65.2 g / m of unlabeled paper. The sheet was made from a 50:50 blend of hardwood pulp and softwood pulp on a pilot-plant paper machine. Each glue was adjusted to pH 7 prior to application to the sheet in the squeeze area by a horizontal glue press. The glue press was running at 12.3 m / min and the moisture absorption was 70%. The adhesive retention was the same in all these experiments. The glued sheets were dried at 107 ° C for 20 seconds on a laboratory drum dryer to 4% humidity. The sizing was measured by the Hercules sizing test with sample solution # 2 to the reflectance indicated. The results after the machine were obtained 2 minutes after drying and the results for natural ripening after 3 days storage at room temperature.

The bonding results are given in Table II below.

TABLE II

13 147859. Hercules sizing test for 80% reflectance according to example After the machine Natural maturation 16 0 451 19 460 882 17 0 602 20 732 920 18 0 620 21 325 930

It is well known in the art that the hydrophobic, cellulose-reactive adhesives provide only little, if any, bonding to the machine. The above examples relating to surface sizing show that the adhesive according to the invention provides a significant improvement of the sizing after the machine.

The adhesive according to the invention can be used for internal sizing of paper to obtain improved sizing results.

Although it is preferred to use the adhesive according to the invention for internal sizing of paper, it should be noted that the hydrophobic, cellulose-reactive adhesive and the sizing accelerator, if desired, can be added separately.

Claims (7)

147859 Patent Claims. A process for making glued paper or cardboard from cellulose fibers using an aqueous emulsion adhesive comprising: (A) a hydrophobic, cellulose reactive adhesive such as a ketene dimer, an acid anhydride or organic isocyanate, (B) a nitrogen-containing adhesive accelerator, (C) an emulsifier, and optionally (D) a smaller amount of sodium lignin sulfonate, characterized in that the nitrogen-containing adhesive accelerator (B) used is prepared by reacting an epihalohydrin with a condensate obtained by condensation of dicyandiamide or cyanamide with a polyalkylene polyamine. Process according to claim 1, characterized in that the epihalohydrine is epichlorohydrin. Process according to claims 1 and 2, characterized in that the polyalkylene polyamine used to prepare the nitrogen condensation product (B) is diethylenetriamine. Process according to claims 1-3, characterized in that the polyalkylene polyamine used to prepare the nitrogen condensation product (B) is triethylenetetramine. Process according to claims 1-4, characterized in that the polyalkylene polyamine used to prepare the nitrogen condensation product (B) is methyl bis (3-aminopropyl) amine. Process according to one of the preceding claims, characterized in that the emulsifier (C) is a cationic emulsifier. An adhesive for use in the preparation of cellulose fiber paper or cardboard in the form of an aqueous emulsion, comprising: (A) a hydrophobic, cellulose-reactive adhesive such as a ketene dimer, anhydride or organic isocyanate, (B) a nitrogen-containing bonding accelerator, (C) an emulsifier, and optionally (D) a smaller amount of sodium lignin sulfonate,