CA1152243A - Sizing agents for paper - Google Patents
Sizing agents for paperInfo
- Publication number
- CA1152243A CA1152243A CA000334775A CA334775A CA1152243A CA 1152243 A CA1152243 A CA 1152243A CA 000334775 A CA000334775 A CA 000334775A CA 334775 A CA334775 A CA 334775A CA 1152243 A CA1152243 A CA 1152243A
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- Canada
- Prior art keywords
- sizing agents
- amines
- sizing
- paper
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
SIZING AGENTS FOR PAPER
Abstract of the Disclosure Paper sizing agents in the form of aqueous preparations of on an average dibasic amides having been quaternized with epichlorohydrin of a) fatty acids having melting points above 30°C and b) amines corresponding to the general formula H2N-R-(NH-R')n-NH2 wherein R and R' represent C2-C3 alkylene radicals and n has a value of from 1 to 6 and/or technical mixtures of these amines, which may contain as accompanying substances cyclic and/or branched amines having the same boiling range.
Le A 19 124
Abstract of the Disclosure Paper sizing agents in the form of aqueous preparations of on an average dibasic amides having been quaternized with epichlorohydrin of a) fatty acids having melting points above 30°C and b) amines corresponding to the general formula H2N-R-(NH-R')n-NH2 wherein R and R' represent C2-C3 alkylene radicals and n has a value of from 1 to 6 and/or technical mixtures of these amines, which may contain as accompanying substances cyclic and/or branched amines having the same boiling range.
Le A 19 124
Description
~lSZ243 The present invention relates to sizing agents for paper in the form of aqueous preparations of special quaternization products of basic fatty acid amides derived from fatty acids having melting points above 30C
5 and polyalkylene polyamines and/or technical mixtures thereof.
So-called resin sizes based on abietic acid are normally used as pulp sizing agents for paper. However, since these sizing agents are not entirely satisfactory, 10for example insofar as they require alum as an additive, other pulp sizing agents which do not require the addition of alum, such as for example fatty acid anhydrides or ketenes, isocyanates or chlorocarbonyl derivatives of fatty acids, have been developed. Disadvantages which are 15common to all these known sizing agents are that they are difficult to emulsify, cationic additives generally have to be used to obtain satisfactory sizing, and in addition they can only be stored for limited periods at room temperature in aqueous emulsion because the ketene, 20anhydride or isocyanate groups are sensitive to water.
Stearic acid or reaction products of aliphatic amines with maleic anhydride may also be used as pulp sizing agents, but these are only effective in large quantities or else w$th alum additions.
According to German Offenlegungsschrift No. 1,771, 243, reaction products of polymeric fatty acids and polyamines may also be~used as pulp sizing agents provided that they ar~ reacted with a strictly deine~
quantity of epichlorohydrin. However, substances such 30as these have only a weak pulp sizing effect, although they are eminently suitable for surface sizing.
It has now been found that amides containing on an average two further basi.c amino groups of oligomeric alkylene amines containing more than 2 nitrogen atoms and Le ~ 19 1~4 i`, .
l~SZ243 C10-C26 fatty acids, particularly C12-C18 fatty acids, which are solid at room temperature, such as lauric acid, myristic acid, palmitic acid and preferably stearic acid, in the form of their quaternization products prepared in the presence of water, with (based on the amino groups in the amide) from 0.5 to 2 equivalents of epichlorohydrin, are eminently suitable for use as sizing agents, and above all as pulp sizing agents, particularly when from 0.05 to 5 % by weight (based on solids) of an electrolyte has been added to their aqueous preparations. They are used in the form of aqueous solutions, suspensions or emulsions, optionally in admixture with other sizing agents.
It has been found that the corresponding amide compounds, for example where stearic acid melting at approximately 69C is used, lead to an effect-ive pulp sizing agent, whereas analogous compounds produced with for example oleic acid which is liquid at room temperature are inadequately effective.
An earlier proposal (German Offenlegungsschrift 2~ 19 039 published on November 8, 1979) relates to sizing agents for paper in the form of a preparation of salts and/or quaternization products of basic fatty acid amides derived from fatty acids having melting points above 30C.
The present invention represents a considerable improvement over this earlier proposal because the quaternization in accordance with present invention of on an average dibasic reaction products of crystalline fatty acids with straight chain polyamines o~ the general ~ormula ~12N-(R'NII)n-RN~12 and/or techn~cal m~xtures thereof ~n the presence of waker with approx~mately ;stolchiometric quantities of ep~chlorohydrin surprisingly leads to products having an effectiveness whlch is distinctly improved, i.e. a good sizing effect is obtained with :, .
~ 2 -; .
.., .
~, ,..
~152243 considerably smaller quantities of straight chain amines. Additionally, the use of technical mixtures of the amines has the advantage that the costly separation processes for preparing the pure straight chain amines can be saved. Another advantage lies in the possibility afforded by the present invention of using additions of electrolyte which, surprisingly, lead to a considerable reduction in the viscosity of the aqueous sizing agent preparation without any significant loss of activity and therefore provides for improved handling in given concentrations.
Accordingly, the present invention provides sizing agents for paper comprising an aqueous preparation of quaternized basic fatty acid amides wherein on an average dibasic amides of fatty acids having melting points above 30C and amines corresponding to the general formula H2N-R-(NH-R')n-NH2 and/or technical mixtures thereof are used, wherein R andR' are the same or different and each represents an alkylene radical containing 2 or 3 carbon atoms, and 25 n has a value of from 1 to 6, and the technical amine~
may contain up to 80 % by weight o~ accompanyin~ sub-stances which consist essent.ially of c~clic and/or branched amlnes having approximately the same technical boiling range, such as for example tert. aminoalkyl 30 amines or aminoalkyl piperazines, the amides are quater-nized with from 0.5 to 2 equivalents of epichlorohydxln (based on the amino groups in the basic amide) in the Le A 19 124 ll~Z2~3 presence of water, optionally followed by dilution with more water to a desired solids concentration.
The afore-mentioned accompanying substances of the technical amines contain additionally minor amounts of unidentified by-products which, however, do not impair the production and the efficiency of the sizing agents according to the invention.
According to another embodiment of the present invention, from 0.05 to 5 ~ by weight (based on solids) 10 of an electrolyte is added to the aqueous sizing agent preparation of the present invention.
Suitable parent fatty acids are fatty acids or fatty acid mixtures each fatty acid containing from 10 to 26 and preferably from 12 to 18 carbon atoms and having 15 melting points above 30~C. Particularly suitable are stearic acid or fatty acid mixtures containing stearic acid. It is, however, also possible to use other fatty acids, such as for example tallow acid, cocinic acid, palmitic acid, abietic acid, arachic acid and behenic acid, 20 hydrogenated oleic acid or other fatty acids which are obtainable by oxosynthesis or similar processes.
Amines or technical amine mixtures suitable for the production of the basic fatty acid amides are, preferably, polyethylene polyamines, for example diethylene triamine, 25 triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine. The corresponding propylene amin~
are also sultable. Technical triethylene tetramine is of particular lnterest.
The by-products occuring because of their similar 30 boiling properties in the technical polyethylene poly-amines are for example aminoethyl piperazine, trisamino-ethyl amine, N,N'-bis-aminoethyl piperazine, aminoethylated Le A 19 124 1~5ZZ43 N-aminoethylpiperazines in the form of different isomers and a number of not identified further impurities, most of them in amounts of less than 10 % by weight. The amount of straight chain compounds according to the formula should be at least 20 %, by weight, and preferably more than 40 % by weight. It is also possible to use mixtures of technical polyalkylene polyamines having different boiling ranges in the process.
For the conversion into quaternization products, epichlorohydrin is used in quantities of from 0.5 to 2 equivalents and pre~erably in quantities of from 0.5 to 1.5 equivalents, based on the amino groups present in the basic amide. ~lthough larger quantitites of epichloro-hydrin may readily be used, they do not produce any significant increase in effect.
Further quaternizing agents such as dimethyl sulphate, diethyl sulphate, propane sultone, benzyl chloride, alkylene oxides or chloroacetic acid amide optionally may also be taken into account they are, however, of minor importance.
Based on the quantity of amine used, the fatty acids required for the production of the preliminary stage amide for the sizing agent according to the present in-vention are used in such quantities that the resulting basic amide contains on average about 2 basic amino groups per molecule, i.e. for example approximatel~ 2 moles of stearlc acid may be react~d per mole of trl-ethylene tetramine, The basic amides may be produced by various methods known to the man skilled in the art, for example by heating stoichiometrically calculated quantities of stearic acid and amine to 180C to 220C, optionally under a nitrogen atmosphere, and slowly distilling off Le A 19 124 ;' ' llS2Z43 the water formed during amide formation. The amidation product should have acid numbers below 20 and preferably below 5. After cooling to a suitable temperature range, for example in the vicinity of the melting points of the amides which normally lie in the range of from about 60C to 130~ the melt of the basic amides formed may then be reacted in water with the quaternization agent and after a reaction time of from 0.5 to 10 hours, preferably while it is still hot, is converted, optionally with the 10 addition of a further quantity of water, into a 5 to 40 ~ by weight, preferably a 10 to 25 % by weight, suspension or emulsion after stirring for another 0.1 to 10 hours at 60 to 130C.
This is generally done by simple stirring, but in 15 some cases the use of mechanical emulsifying aids may be desirable.
In one variant of the process for the preparation of sizing agents according to the present invention, a small quantity of the quaternization agent, i.e. below 20 50 % by weight of the total amount of epichlorohydrin required, is added to the molten basic amide beore the first addition of water. In this way, an emulsifier is prepared in situ which enables the water added immediately before the main quaternization reaction to be more uni-25 formly distributed throughout the reaction medium.
It has proven to be advisable for the amount ofwater present during the quaternization reaction to be smaller than the amount of water subsequently contained in the aqueous sizing agent preparation because in this 30 way, adjustment of the requlred concentration of slzing agent may be optimally combined with the addition of an : 35 Le A 19 124 115:22~3 electrolyte. In many cases, it has proven to be sufficient and favourable in terms of processing to initially add only about 100 to 900 % by weight of water, based on the quantity of basic amide used, during the quaternization 5 reaction. Without the addition of water, however, end pro-ducts of reduced activity are surprisingly obtained.
With a solids content above 10 % by weight, the described aqueous sizing ayent preparations often have a pasty consistency which can lead to handling problems.
10 According to the present invention, it is possible in cases such as these to add from 0.05 to 5 % by weight and preferably from 0.1 to 1 % by weight, based on solids con-tents, of an electrolyte to the preparations. This is best done during the final dilution of the sizing agent 15 preparation by dissolving the required amount of electro-lyte in the water to be used for the final dilution and adding the electrolyte in this way. Although it is also possible to add the electrolyte at the beginning or even during the first or second additions of water, it 20 has been found to be most effective to incorporate the electrolyte at the beginning or even during the first or second additions of water, it has been found to be most effective to incorporate the electrolyte as near as is possible to the end of the dilution process. The pre-25 parations obtained in this way are thinly li~uld for asolids content above 10 ~ by weight and do not sub~qu2ntly thicken.
In additlon to organlc salts, such as ammonium or alkali formates, acetates, benzoates, phosphonates or 30 sulphonates, suitable electrolytes are, preferably, in-organic salts, such as ammonium chloride, potassium chloride, calcium chlorlde, zinc chloride, aluminium Le A 19 124 ll~ZZ43 chloride or, more preferably, sodium chloride, although in principle soluble chlorides, nitrates, sulphates, phosphates, and carbonates of other elements and the acids or bases themselves are also suitable. In many cases even hard or mineral-containing tap water produces adequate electrolyte effects.
The aqueous sizing agent preparations obtained in this way are ready for use and have a solids concentration of from 5 to 40 ~ by weight and preferably of from 10 to 25 % by weight. The preparations are further diluted during their application to the particular concentrations re~uired, for example to concentrations below 0.5 %
by weight of the type normally used in the sizing of paper.
The sizing agents according to the present invention have the advantage that they may be stored indefinitely in the form of their aqueous preparations without any signlficant loss of activity and they do not require any additions of either alum or a cationic or anionic auxiliary.
However, such additions are possible and may well be taken into account, for example the addition of auxiliaries based on cationic starch, quaternize~ poly-amines, ~uaternized polyamide amines, quaternized basic formaldehyde resins, methylcellulose, carboxymethylcellulose, lignine sulfonic acids, starches and polysaccharides of different origin, pullulane, chitosape, polymers or copolymers of (meth)acrylic acid, maleia acid, fumaric acid and itaconic acid or other polymers or copolymer9 having carboxylic acid or sulfonic acid groups, optionally present in the form of salts, collagen, gelatine, 30 alginates and caragenates.
Their effectiveness is not affected but rather im-proved by white toners or cationic and particularly i Le ~ 19 1~4 .
~152Z~3 anionic dyestuffs and in addition the aqueous preparations may be prep æed with-out emulsification aids.
me sizing agents according to the present invention are on their own or in combination with other sizing agents particularly suitable for the pulp sizing of paper, although they may of course also be used for surface sizing.
mey may be used not only for chalk-containing or kaolin-containing papers, but also for papers which do not contain fillers or which contain other types of filler, such as for example talcum or gypsum. They are also suitable for sizing oe llulosic materials such as pasteboard, textile materials, cardboard or wood-chip boards and insulating boards and also leather.
The present invention is further illustrated by the following Examplesin which the parts and percentages quoted are based on weight, unless otherwise stated.
EXAMPLE 1 (Gomparison Example):
A sizing agent corresponding to the earlier proposal mentioned in the description is prepared (German Offenlegungsschrift 28 19 039 published on November 8, 1979).
Sizing Agent 2 146 parts of triethylene tetramine and 569 parts of stearic acid are heated under reflux for 5 hours to 180& under a nitrogen atmosphere. All frac-tions which are volatile at that temperature are then distilled off with thorough stirring. After oooling to 95&, a sol~tion oE 90 p æ ts of acetic acid in 5210 parts of watar which has been p~ehea~ed to go& i.s added to the basic amide formed with thorough stirring. This results in the formation of an emLl-sion which is cooled while stirring. It may be directly used as a sizing agent.
Its solids content amounts to approximately 10%.
:
;~
_ g _ ., ~
llSZZ43 --~o--Production of the dibasic amide:
170 parts of stearic acid are melted and stirred with 43.8 parts of triethylene tetramine (molar ratio approximately 2:1). The temperature is then increased under a nitrogen atmosphere to 190C and all the volatile fractions are distilled off. After 6 hours and the acid number of 1.9 is reached. The amide produced has a melting range of from 87 to 107C.
Production of sizing agent A:
480 parts of the basic amide prepared above are melted at 120C and then stirred together with 240 parts of water, resulting in the formation of a pasty mixture under gentle reflux. 86.4 parts of epichloro-hydrin (approximately 0.67 mole/amino group) arethen stirred in as quick as possible, followed by stlrring for 1 hour under gentle reflux. 1080 parts of water are then added, followed by stirring for another hour under gentle reflux. The paste obtained is then allowed to cool to approximately 50C, and this is followed by the addition of a solution of 5.6 parts of NaCl (0.5 ~, based on solids) in 967 parts of water.
An approximately 20% emulsion which is thinly liquid at room temperature is obtained and is then used as a sizing agent.
Sizing Agent ~
201 parts o ~he basic amide prepared according to the procedures set out in Example 2 are stirred for 30 minutes at 120C with 3.7 parts of epichlorohydrin.
1252 parts of water which is preheated to approximately 95C are then added, followed by the addition of 32.3 ... .
Le A 19 124 , . . .
r ,., l~Z243 parts of epichlorohydrin. Stirring for 1.5 hours under gentle reflux gives a thick emulsion having a solids content of 16 % and which is then cooled to approximately 30C. To prepare a thinly liquid emulsion, the thick emulsion thus obtained is diluted to a solids content of 15 ~ with a solution of 2.3 parts of ~aCl in 92 parts of water. The emulsion may then be used as a sizing agent.
Sizing Agent C
201.6 parts of the basic amide prepared according to the procedures set out in Example 2 are stirred for 30 minutes at 120C with 3.7 parts of epichlorohydrin.
70 parts of water and then 32.3 parts of epichlorohydrin are added, followed by stirring for 1 hour at from 100C
to 120C. 1182 parts of water which is preheated to approxlmately 95C are then added, after which the emulsion formed is stirred for about 1 hour under gentle reflux. After cooling to approximately 40C, a solution of 1.2 parts of NaCl in 92 parts of water is added to the pasty emulsion, resultlng in the formation of a thinly liquid sizing agent preparation having a solids content of approximately 15%.
The criterion used for assessing the sizing agents is the so-called ink float test. In this test, a strip of paper slzed with the agent to be tested is placed on the surface of a dlsh Eilled with standard ink according to DI~ 53 126~ and the tlme taken by the ink to penetrate through to that side of the paper which is facing the observer is measured. In standardised form this test is a very effective method of assessing various sizing agents.
Le A 19 124 1~52~43 Compared with conventional reactive sizing agents, the sizing agents according to the present invention can be stored almost indefinitely in the form of aqueous preparations and, in this way, are technically advan-S tageous. The comparison with resin size (sizing agent 1)reveals another technical advantage of the sizing agents according to the present invention, namely their high effectiveness. Another significant advantage arises out of the fact that the sizing agents of the present invention develop their considerable effectiveness on alum-free and chalk-containing and optionally brightener-containing paper on which resin size has very little effect. Accordingly, the sizing agents according to the present invention were also tested for example on alum-free, chalk-containing paper.
5 g of a mixture of 50 g of pine sulphite pulp, 50 g of beech sulphate pulp and 25 g of chalk are suspended in 200 ml of tap water. x % pf the sizing agent (solids content, based on pulp plus filler) are then stirred in. The supension is then made up with water to approximately 1 litre without the addition of a fixing agent and the sheet of paper is produced on a sheet former. The sheet of paper thus prepared is filt-ered under suction, pressed and dried for 5 minutes at 100C on a drying cylinder. Strips (2 cm x 6 cm) are cut from ,the sheet for the ink float test.
Thè lnk float times set ou~ in the following Table were observed. An alum-containing test paper slzed with commercial resin size was used for compaxison:
Le A 19 124 Table 1 Example No. 5 _ 6 7 8 9 10 11 Comparison xx xx xx 00 Sizing Agent 1 1 1 2 A B C
Quantity used 1 0.5 0.3 0.65 0.40 0.50 0.40 Time (mins) 20 9 2 15 15 15 15 The results of the ink float test reflect the distinctly better sizing effect of the sizing agents according to the present invention on chalk-containing paper.
The test is carried out in the same way as in Example 11, except that the paper used contains kaolin instead of chalk. An ink float time of 10 minutes is measured.
The test is carried out in the same way as in Example 9, except that the paper contains talcum in-stead of chalk. An ink float time of 12 minutes is measured.
-The test is carried out in the same way as in Example 10, except that the paper contains mechanical wood pulp instead of beech sulphate pwlp. An ink float time o 11 mlnutes is measured.
E~AMPLE 15 ~Comparison Example) A basic amide is prepared in the same way as set out in Example 2, except that the molar ratlo o stearic acid to amine amounts to 3:1.
. Le A 19 124 ., 115~243 The processing of this amide in the same way as for the production of sizing agents A, B or C leads to emulsions which, when used in quantities of less than 1% in accordance with Examples 5 to 11, give ink float times of less than 2 minutes and are regarded as unsuitable.
A mixture of 710 parts of stearic acid and 189 parts of tetra-ethylene pentamine (molar ratio approximately 2.5:1) is reacted to form the amide following the procedure as set out in Example 2. Acid number: 3.8,melting range: 65-66C.
Sizing Agent D
240 parts of the above amide are stirred for 1 hour at approximately 100C with 120 parts of water and 65 parts of epichlorohydrin (approximately 1 mole/amino group). 593 parts of water are then added, followed by stirring for another hour under gentle reflux. 305 parts of water are then added and the mixture is cooled with stirring to approximately 45C. To prepaxe a thinly liquid emulsion, the product is then diluted to a solids content of approximately 18~ with a solution of 1.5 parts of NaCl in 203 parts of water.
This emulsion is used as a sizing agent.
A sizing test carried out in accordance with Examples 9 to 11 gives a ink float time o 16 minute~
for 0.45~ o~ the slzing agent.
The ollowing examples are carried out with technical amines.
.:
Le A 19 124 ., ~':
` 115;~Z43 Amine: technical triethylene tetramine straight chain branched piperazine other constituent (%) consti- constituent constituents tuent (%~
E 46.6 24.2 26.0 balance F 67.0 , 12.7 8.7 "
G 70.4 14.4 9.0 "
H 73.4 10.9 7.3 "
Technical tetraethylene pentamine straight chain branched piperazine other constituent(%) consti- constituent(%) consti-tuent (%) tuents I 45.9 16.2 32.2 balance Technlcal diethylene triamine K 97.2 - 1.7 "
Example 17 According to Example 2 uslng the same recipe the basic amides are prepared from the amines E to K. The amides, all having acid numbers below 5, are further processed in the following way:
201.6 parts of the amide are melted at 120C and then stirred wlth 1252 parts of hot water with aooling to 80C. 36 parts of epiahlorohydrln ar~ addod to the resultlng suspension at 80C which is then ~tlrred for 2 hours at 80C thereby orming a fine particle suspension.
The temperature is then decreased to 40C and a solution of 1.15 parts of NaCl in 92 parts of water is added to the pasty material with thorough stirring.
Le A 19 124 "
Thinly liquid fine particle suspensions are formed having a solids content of approximately 15% which may be used as sizing agents E to K.
The ink float times set out in the following table were observed. An alum-containing test paper sized with commercial resin size (sizing agent 1) was used for comparison.
Table 2 Example No. 18 19 20 21 22 23 24 25 _ Comparison xx xx xx Sizing agent 1 1 1 E F G H
Quantity used 1 0.5 0.3 0.4 0.4 0.4 0.4 0.4 (%) Time (mins) 20 9 2 15 16 18 18 15 The results of the ink float reflect the distinctly better sizing effect on chalk-containing paper of the sizing agents according to the present invention pre-pared with technical mixtures of amines.
Example 26 The test is carried out in the same way as in Example 24, except that the paper used contains kaolin instead of chalk. An ink float time of 12 minutes is measured.
Example 27 Th~ text i9 carried out in the same way as in Example 23l except that the paper contalns talcum istead of chalk. An ink float time of 12 minutes is measured.
Le A 19 124 , 1~522~3 Example 28 The test is carried out in the same way as in Example 24, except that the paper contains mechanical wood pulp instead of beech sulphate pulp. An ink float time of 11 minutes is measured.
Example 29 994 parts of stearic acid (3.5 mole) are reacted with 206 parts of technical diethylene triamine (about
5 and polyalkylene polyamines and/or technical mixtures thereof.
So-called resin sizes based on abietic acid are normally used as pulp sizing agents for paper. However, since these sizing agents are not entirely satisfactory, 10for example insofar as they require alum as an additive, other pulp sizing agents which do not require the addition of alum, such as for example fatty acid anhydrides or ketenes, isocyanates or chlorocarbonyl derivatives of fatty acids, have been developed. Disadvantages which are 15common to all these known sizing agents are that they are difficult to emulsify, cationic additives generally have to be used to obtain satisfactory sizing, and in addition they can only be stored for limited periods at room temperature in aqueous emulsion because the ketene, 20anhydride or isocyanate groups are sensitive to water.
Stearic acid or reaction products of aliphatic amines with maleic anhydride may also be used as pulp sizing agents, but these are only effective in large quantities or else w$th alum additions.
According to German Offenlegungsschrift No. 1,771, 243, reaction products of polymeric fatty acids and polyamines may also be~used as pulp sizing agents provided that they ar~ reacted with a strictly deine~
quantity of epichlorohydrin. However, substances such 30as these have only a weak pulp sizing effect, although they are eminently suitable for surface sizing.
It has now been found that amides containing on an average two further basi.c amino groups of oligomeric alkylene amines containing more than 2 nitrogen atoms and Le ~ 19 1~4 i`, .
l~SZ243 C10-C26 fatty acids, particularly C12-C18 fatty acids, which are solid at room temperature, such as lauric acid, myristic acid, palmitic acid and preferably stearic acid, in the form of their quaternization products prepared in the presence of water, with (based on the amino groups in the amide) from 0.5 to 2 equivalents of epichlorohydrin, are eminently suitable for use as sizing agents, and above all as pulp sizing agents, particularly when from 0.05 to 5 % by weight (based on solids) of an electrolyte has been added to their aqueous preparations. They are used in the form of aqueous solutions, suspensions or emulsions, optionally in admixture with other sizing agents.
It has been found that the corresponding amide compounds, for example where stearic acid melting at approximately 69C is used, lead to an effect-ive pulp sizing agent, whereas analogous compounds produced with for example oleic acid which is liquid at room temperature are inadequately effective.
An earlier proposal (German Offenlegungsschrift 2~ 19 039 published on November 8, 1979) relates to sizing agents for paper in the form of a preparation of salts and/or quaternization products of basic fatty acid amides derived from fatty acids having melting points above 30C.
The present invention represents a considerable improvement over this earlier proposal because the quaternization in accordance with present invention of on an average dibasic reaction products of crystalline fatty acids with straight chain polyamines o~ the general ~ormula ~12N-(R'NII)n-RN~12 and/or techn~cal m~xtures thereof ~n the presence of waker with approx~mately ;stolchiometric quantities of ep~chlorohydrin surprisingly leads to products having an effectiveness whlch is distinctly improved, i.e. a good sizing effect is obtained with :, .
~ 2 -; .
.., .
~, ,..
~152243 considerably smaller quantities of straight chain amines. Additionally, the use of technical mixtures of the amines has the advantage that the costly separation processes for preparing the pure straight chain amines can be saved. Another advantage lies in the possibility afforded by the present invention of using additions of electrolyte which, surprisingly, lead to a considerable reduction in the viscosity of the aqueous sizing agent preparation without any significant loss of activity and therefore provides for improved handling in given concentrations.
Accordingly, the present invention provides sizing agents for paper comprising an aqueous preparation of quaternized basic fatty acid amides wherein on an average dibasic amides of fatty acids having melting points above 30C and amines corresponding to the general formula H2N-R-(NH-R')n-NH2 and/or technical mixtures thereof are used, wherein R andR' are the same or different and each represents an alkylene radical containing 2 or 3 carbon atoms, and 25 n has a value of from 1 to 6, and the technical amine~
may contain up to 80 % by weight o~ accompanyin~ sub-stances which consist essent.ially of c~clic and/or branched amlnes having approximately the same technical boiling range, such as for example tert. aminoalkyl 30 amines or aminoalkyl piperazines, the amides are quater-nized with from 0.5 to 2 equivalents of epichlorohydxln (based on the amino groups in the basic amide) in the Le A 19 124 ll~Z2~3 presence of water, optionally followed by dilution with more water to a desired solids concentration.
The afore-mentioned accompanying substances of the technical amines contain additionally minor amounts of unidentified by-products which, however, do not impair the production and the efficiency of the sizing agents according to the invention.
According to another embodiment of the present invention, from 0.05 to 5 ~ by weight (based on solids) 10 of an electrolyte is added to the aqueous sizing agent preparation of the present invention.
Suitable parent fatty acids are fatty acids or fatty acid mixtures each fatty acid containing from 10 to 26 and preferably from 12 to 18 carbon atoms and having 15 melting points above 30~C. Particularly suitable are stearic acid or fatty acid mixtures containing stearic acid. It is, however, also possible to use other fatty acids, such as for example tallow acid, cocinic acid, palmitic acid, abietic acid, arachic acid and behenic acid, 20 hydrogenated oleic acid or other fatty acids which are obtainable by oxosynthesis or similar processes.
Amines or technical amine mixtures suitable for the production of the basic fatty acid amides are, preferably, polyethylene polyamines, for example diethylene triamine, 25 triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine. The corresponding propylene amin~
are also sultable. Technical triethylene tetramine is of particular lnterest.
The by-products occuring because of their similar 30 boiling properties in the technical polyethylene poly-amines are for example aminoethyl piperazine, trisamino-ethyl amine, N,N'-bis-aminoethyl piperazine, aminoethylated Le A 19 124 1~5ZZ43 N-aminoethylpiperazines in the form of different isomers and a number of not identified further impurities, most of them in amounts of less than 10 % by weight. The amount of straight chain compounds according to the formula should be at least 20 %, by weight, and preferably more than 40 % by weight. It is also possible to use mixtures of technical polyalkylene polyamines having different boiling ranges in the process.
For the conversion into quaternization products, epichlorohydrin is used in quantities of from 0.5 to 2 equivalents and pre~erably in quantities of from 0.5 to 1.5 equivalents, based on the amino groups present in the basic amide. ~lthough larger quantitites of epichloro-hydrin may readily be used, they do not produce any significant increase in effect.
Further quaternizing agents such as dimethyl sulphate, diethyl sulphate, propane sultone, benzyl chloride, alkylene oxides or chloroacetic acid amide optionally may also be taken into account they are, however, of minor importance.
Based on the quantity of amine used, the fatty acids required for the production of the preliminary stage amide for the sizing agent according to the present in-vention are used in such quantities that the resulting basic amide contains on average about 2 basic amino groups per molecule, i.e. for example approximatel~ 2 moles of stearlc acid may be react~d per mole of trl-ethylene tetramine, The basic amides may be produced by various methods known to the man skilled in the art, for example by heating stoichiometrically calculated quantities of stearic acid and amine to 180C to 220C, optionally under a nitrogen atmosphere, and slowly distilling off Le A 19 124 ;' ' llS2Z43 the water formed during amide formation. The amidation product should have acid numbers below 20 and preferably below 5. After cooling to a suitable temperature range, for example in the vicinity of the melting points of the amides which normally lie in the range of from about 60C to 130~ the melt of the basic amides formed may then be reacted in water with the quaternization agent and after a reaction time of from 0.5 to 10 hours, preferably while it is still hot, is converted, optionally with the 10 addition of a further quantity of water, into a 5 to 40 ~ by weight, preferably a 10 to 25 % by weight, suspension or emulsion after stirring for another 0.1 to 10 hours at 60 to 130C.
This is generally done by simple stirring, but in 15 some cases the use of mechanical emulsifying aids may be desirable.
In one variant of the process for the preparation of sizing agents according to the present invention, a small quantity of the quaternization agent, i.e. below 20 50 % by weight of the total amount of epichlorohydrin required, is added to the molten basic amide beore the first addition of water. In this way, an emulsifier is prepared in situ which enables the water added immediately before the main quaternization reaction to be more uni-25 formly distributed throughout the reaction medium.
It has proven to be advisable for the amount ofwater present during the quaternization reaction to be smaller than the amount of water subsequently contained in the aqueous sizing agent preparation because in this 30 way, adjustment of the requlred concentration of slzing agent may be optimally combined with the addition of an : 35 Le A 19 124 115:22~3 electrolyte. In many cases, it has proven to be sufficient and favourable in terms of processing to initially add only about 100 to 900 % by weight of water, based on the quantity of basic amide used, during the quaternization 5 reaction. Without the addition of water, however, end pro-ducts of reduced activity are surprisingly obtained.
With a solids content above 10 % by weight, the described aqueous sizing ayent preparations often have a pasty consistency which can lead to handling problems.
10 According to the present invention, it is possible in cases such as these to add from 0.05 to 5 % by weight and preferably from 0.1 to 1 % by weight, based on solids con-tents, of an electrolyte to the preparations. This is best done during the final dilution of the sizing agent 15 preparation by dissolving the required amount of electro-lyte in the water to be used for the final dilution and adding the electrolyte in this way. Although it is also possible to add the electrolyte at the beginning or even during the first or second additions of water, it 20 has been found to be most effective to incorporate the electrolyte at the beginning or even during the first or second additions of water, it has been found to be most effective to incorporate the electrolyte as near as is possible to the end of the dilution process. The pre-25 parations obtained in this way are thinly li~uld for asolids content above 10 ~ by weight and do not sub~qu2ntly thicken.
In additlon to organlc salts, such as ammonium or alkali formates, acetates, benzoates, phosphonates or 30 sulphonates, suitable electrolytes are, preferably, in-organic salts, such as ammonium chloride, potassium chloride, calcium chlorlde, zinc chloride, aluminium Le A 19 124 ll~ZZ43 chloride or, more preferably, sodium chloride, although in principle soluble chlorides, nitrates, sulphates, phosphates, and carbonates of other elements and the acids or bases themselves are also suitable. In many cases even hard or mineral-containing tap water produces adequate electrolyte effects.
The aqueous sizing agent preparations obtained in this way are ready for use and have a solids concentration of from 5 to 40 ~ by weight and preferably of from 10 to 25 % by weight. The preparations are further diluted during their application to the particular concentrations re~uired, for example to concentrations below 0.5 %
by weight of the type normally used in the sizing of paper.
The sizing agents according to the present invention have the advantage that they may be stored indefinitely in the form of their aqueous preparations without any signlficant loss of activity and they do not require any additions of either alum or a cationic or anionic auxiliary.
However, such additions are possible and may well be taken into account, for example the addition of auxiliaries based on cationic starch, quaternize~ poly-amines, ~uaternized polyamide amines, quaternized basic formaldehyde resins, methylcellulose, carboxymethylcellulose, lignine sulfonic acids, starches and polysaccharides of different origin, pullulane, chitosape, polymers or copolymers of (meth)acrylic acid, maleia acid, fumaric acid and itaconic acid or other polymers or copolymer9 having carboxylic acid or sulfonic acid groups, optionally present in the form of salts, collagen, gelatine, 30 alginates and caragenates.
Their effectiveness is not affected but rather im-proved by white toners or cationic and particularly i Le ~ 19 1~4 .
~152Z~3 anionic dyestuffs and in addition the aqueous preparations may be prep æed with-out emulsification aids.
me sizing agents according to the present invention are on their own or in combination with other sizing agents particularly suitable for the pulp sizing of paper, although they may of course also be used for surface sizing.
mey may be used not only for chalk-containing or kaolin-containing papers, but also for papers which do not contain fillers or which contain other types of filler, such as for example talcum or gypsum. They are also suitable for sizing oe llulosic materials such as pasteboard, textile materials, cardboard or wood-chip boards and insulating boards and also leather.
The present invention is further illustrated by the following Examplesin which the parts and percentages quoted are based on weight, unless otherwise stated.
EXAMPLE 1 (Gomparison Example):
A sizing agent corresponding to the earlier proposal mentioned in the description is prepared (German Offenlegungsschrift 28 19 039 published on November 8, 1979).
Sizing Agent 2 146 parts of triethylene tetramine and 569 parts of stearic acid are heated under reflux for 5 hours to 180& under a nitrogen atmosphere. All frac-tions which are volatile at that temperature are then distilled off with thorough stirring. After oooling to 95&, a sol~tion oE 90 p æ ts of acetic acid in 5210 parts of watar which has been p~ehea~ed to go& i.s added to the basic amide formed with thorough stirring. This results in the formation of an emLl-sion which is cooled while stirring. It may be directly used as a sizing agent.
Its solids content amounts to approximately 10%.
:
;~
_ g _ ., ~
llSZZ43 --~o--Production of the dibasic amide:
170 parts of stearic acid are melted and stirred with 43.8 parts of triethylene tetramine (molar ratio approximately 2:1). The temperature is then increased under a nitrogen atmosphere to 190C and all the volatile fractions are distilled off. After 6 hours and the acid number of 1.9 is reached. The amide produced has a melting range of from 87 to 107C.
Production of sizing agent A:
480 parts of the basic amide prepared above are melted at 120C and then stirred together with 240 parts of water, resulting in the formation of a pasty mixture under gentle reflux. 86.4 parts of epichloro-hydrin (approximately 0.67 mole/amino group) arethen stirred in as quick as possible, followed by stlrring for 1 hour under gentle reflux. 1080 parts of water are then added, followed by stirring for another hour under gentle reflux. The paste obtained is then allowed to cool to approximately 50C, and this is followed by the addition of a solution of 5.6 parts of NaCl (0.5 ~, based on solids) in 967 parts of water.
An approximately 20% emulsion which is thinly liquid at room temperature is obtained and is then used as a sizing agent.
Sizing Agent ~
201 parts o ~he basic amide prepared according to the procedures set out in Example 2 are stirred for 30 minutes at 120C with 3.7 parts of epichlorohydrin.
1252 parts of water which is preheated to approximately 95C are then added, followed by the addition of 32.3 ... .
Le A 19 124 , . . .
r ,., l~Z243 parts of epichlorohydrin. Stirring for 1.5 hours under gentle reflux gives a thick emulsion having a solids content of 16 % and which is then cooled to approximately 30C. To prepare a thinly liquid emulsion, the thick emulsion thus obtained is diluted to a solids content of 15 ~ with a solution of 2.3 parts of ~aCl in 92 parts of water. The emulsion may then be used as a sizing agent.
Sizing Agent C
201.6 parts of the basic amide prepared according to the procedures set out in Example 2 are stirred for 30 minutes at 120C with 3.7 parts of epichlorohydrin.
70 parts of water and then 32.3 parts of epichlorohydrin are added, followed by stirring for 1 hour at from 100C
to 120C. 1182 parts of water which is preheated to approxlmately 95C are then added, after which the emulsion formed is stirred for about 1 hour under gentle reflux. After cooling to approximately 40C, a solution of 1.2 parts of NaCl in 92 parts of water is added to the pasty emulsion, resultlng in the formation of a thinly liquid sizing agent preparation having a solids content of approximately 15%.
The criterion used for assessing the sizing agents is the so-called ink float test. In this test, a strip of paper slzed with the agent to be tested is placed on the surface of a dlsh Eilled with standard ink according to DI~ 53 126~ and the tlme taken by the ink to penetrate through to that side of the paper which is facing the observer is measured. In standardised form this test is a very effective method of assessing various sizing agents.
Le A 19 124 1~52~43 Compared with conventional reactive sizing agents, the sizing agents according to the present invention can be stored almost indefinitely in the form of aqueous preparations and, in this way, are technically advan-S tageous. The comparison with resin size (sizing agent 1)reveals another technical advantage of the sizing agents according to the present invention, namely their high effectiveness. Another significant advantage arises out of the fact that the sizing agents of the present invention develop their considerable effectiveness on alum-free and chalk-containing and optionally brightener-containing paper on which resin size has very little effect. Accordingly, the sizing agents according to the present invention were also tested for example on alum-free, chalk-containing paper.
5 g of a mixture of 50 g of pine sulphite pulp, 50 g of beech sulphate pulp and 25 g of chalk are suspended in 200 ml of tap water. x % pf the sizing agent (solids content, based on pulp plus filler) are then stirred in. The supension is then made up with water to approximately 1 litre without the addition of a fixing agent and the sheet of paper is produced on a sheet former. The sheet of paper thus prepared is filt-ered under suction, pressed and dried for 5 minutes at 100C on a drying cylinder. Strips (2 cm x 6 cm) are cut from ,the sheet for the ink float test.
Thè lnk float times set ou~ in the following Table were observed. An alum-containing test paper slzed with commercial resin size was used for compaxison:
Le A 19 124 Table 1 Example No. 5 _ 6 7 8 9 10 11 Comparison xx xx xx 00 Sizing Agent 1 1 1 2 A B C
Quantity used 1 0.5 0.3 0.65 0.40 0.50 0.40 Time (mins) 20 9 2 15 15 15 15 The results of the ink float test reflect the distinctly better sizing effect of the sizing agents according to the present invention on chalk-containing paper.
The test is carried out in the same way as in Example 11, except that the paper used contains kaolin instead of chalk. An ink float time of 10 minutes is measured.
The test is carried out in the same way as in Example 9, except that the paper contains talcum in-stead of chalk. An ink float time of 12 minutes is measured.
-The test is carried out in the same way as in Example 10, except that the paper contains mechanical wood pulp instead of beech sulphate pwlp. An ink float time o 11 mlnutes is measured.
E~AMPLE 15 ~Comparison Example) A basic amide is prepared in the same way as set out in Example 2, except that the molar ratlo o stearic acid to amine amounts to 3:1.
. Le A 19 124 ., 115~243 The processing of this amide in the same way as for the production of sizing agents A, B or C leads to emulsions which, when used in quantities of less than 1% in accordance with Examples 5 to 11, give ink float times of less than 2 minutes and are regarded as unsuitable.
A mixture of 710 parts of stearic acid and 189 parts of tetra-ethylene pentamine (molar ratio approximately 2.5:1) is reacted to form the amide following the procedure as set out in Example 2. Acid number: 3.8,melting range: 65-66C.
Sizing Agent D
240 parts of the above amide are stirred for 1 hour at approximately 100C with 120 parts of water and 65 parts of epichlorohydrin (approximately 1 mole/amino group). 593 parts of water are then added, followed by stirring for another hour under gentle reflux. 305 parts of water are then added and the mixture is cooled with stirring to approximately 45C. To prepaxe a thinly liquid emulsion, the product is then diluted to a solids content of approximately 18~ with a solution of 1.5 parts of NaCl in 203 parts of water.
This emulsion is used as a sizing agent.
A sizing test carried out in accordance with Examples 9 to 11 gives a ink float time o 16 minute~
for 0.45~ o~ the slzing agent.
The ollowing examples are carried out with technical amines.
.:
Le A 19 124 ., ~':
` 115;~Z43 Amine: technical triethylene tetramine straight chain branched piperazine other constituent (%) consti- constituent constituents tuent (%~
E 46.6 24.2 26.0 balance F 67.0 , 12.7 8.7 "
G 70.4 14.4 9.0 "
H 73.4 10.9 7.3 "
Technical tetraethylene pentamine straight chain branched piperazine other constituent(%) consti- constituent(%) consti-tuent (%) tuents I 45.9 16.2 32.2 balance Technlcal diethylene triamine K 97.2 - 1.7 "
Example 17 According to Example 2 uslng the same recipe the basic amides are prepared from the amines E to K. The amides, all having acid numbers below 5, are further processed in the following way:
201.6 parts of the amide are melted at 120C and then stirred wlth 1252 parts of hot water with aooling to 80C. 36 parts of epiahlorohydrln ar~ addod to the resultlng suspension at 80C which is then ~tlrred for 2 hours at 80C thereby orming a fine particle suspension.
The temperature is then decreased to 40C and a solution of 1.15 parts of NaCl in 92 parts of water is added to the pasty material with thorough stirring.
Le A 19 124 "
Thinly liquid fine particle suspensions are formed having a solids content of approximately 15% which may be used as sizing agents E to K.
The ink float times set out in the following table were observed. An alum-containing test paper sized with commercial resin size (sizing agent 1) was used for comparison.
Table 2 Example No. 18 19 20 21 22 23 24 25 _ Comparison xx xx xx Sizing agent 1 1 1 E F G H
Quantity used 1 0.5 0.3 0.4 0.4 0.4 0.4 0.4 (%) Time (mins) 20 9 2 15 16 18 18 15 The results of the ink float reflect the distinctly better sizing effect on chalk-containing paper of the sizing agents according to the present invention pre-pared with technical mixtures of amines.
Example 26 The test is carried out in the same way as in Example 24, except that the paper used contains kaolin instead of chalk. An ink float time of 12 minutes is measured.
Example 27 Th~ text i9 carried out in the same way as in Example 23l except that the paper contalns talcum istead of chalk. An ink float time of 12 minutes is measured.
Le A 19 124 , 1~522~3 Example 28 The test is carried out in the same way as in Example 24, except that the paper contains mechanical wood pulp instead of beech sulphate pulp. An ink float time of 11 minutes is measured.
Example 29 994 parts of stearic acid (3.5 mole) are reacted with 206 parts of technical diethylene triamine (about
2 mole) under a nitrogen atmosphere for 6 hours at 200C with stirring and destilling off the water formed by the reaction. About 1115 parts of the amide are obtained having a melting range of from 87 to 98C and an acid number of 1.5.
201.6 parts of the basic amide are heated to 120C, then 1250 parts of hot water having a temperature of 80C are added and the mixture is stirred for 30 minutes at 80C. After addition of 36 parts of epi-chlorohydrin quaternisation is carried out for 2 hours at 80C. After cooling to 35C a solution of 1.15 parts of NaCl in 92 parts of water are added. The resulting thinly liquid emulsion is then used as a sizing agent.
The s:Lzing test is carried out according to Examples 21 to 25 and an ink float time of 18.5 minutes is observed.
Le A 19 124
201.6 parts of the basic amide are heated to 120C, then 1250 parts of hot water having a temperature of 80C are added and the mixture is stirred for 30 minutes at 80C. After addition of 36 parts of epi-chlorohydrin quaternisation is carried out for 2 hours at 80C. After cooling to 35C a solution of 1.15 parts of NaCl in 92 parts of water are added. The resulting thinly liquid emulsion is then used as a sizing agent.
The s:Lzing test is carried out according to Examples 21 to 25 and an ink float time of 18.5 minutes is observed.
Le A 19 124
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Sizing agents for paper consisting essentially of an aqueous prepara-tion of quaternised basic fatty acid amides, wherein on an average dibasic amides are used of a) a fatty acid or a mixture of fatty acids having melting points above 30°C and b) one or more amines corresponding to the general formula H2N-R-(NH-R')n-NH2 and/or technical mixtures thereof wherein R and R' are the same or different and each represents an alkylene radical containing 2 or 3 carbon atoms, n has a value of from 1 to 6, and the technical mixtures of the amines may contain up to 80% by weight, of accompanying substances which consist essentially of cyclic and/or branched amines having approximately the same technical boiling range, the amides are quaternised with from 0.5 to 2 equivalents of epichlorohydrin (based on the amino groups in the basic amide) in the presence of water, optionally followed by dilution with more water to a desired solids concen-tration.
2. Sizing agents as claimed in Claim 1, further comprise 0.05 to 5 %
by weight, based on solids content, of an electrolyte.
by weight, based on solids content, of an electrolyte.
3. Sizing agents as claimed in Claims 1 or 2, wherein stearic acid or a fatty acid mixture containing stearic acid is used as the fatty acid or fatty acid mixture.
4. Sizing agents as claimed in Claim 1 or 2 wherein a polyethylene polyamine is used as the amine.
5. Sizing agents as claimed in Claims 1 or 2, wherein technical mixtures of polyethylene polyamines containing branched and/or cyclic amines besides the straight chain major constituents are used as the amine.
6. Sizing agents as claimed in Claims 1 or 2, wherein technical triethylene tetramine is used as the amine.
7. Sizing agents as claimed in Claim 2, wherein sodium chloride is used as the electrolyte.
8. Paper which has been sized with a sizing agent, optionally containing a brightener, as claimed in claims 1, 2 or 7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2838270.9 | 1978-09-01 | ||
| DE19782838270 DE2838270A1 (en) | 1978-09-01 | 1978-09-01 | SIZE FOR PAPER |
| DE19782856858 DE2856858A1 (en) | 1978-12-30 | 1978-12-30 | Aq. paper sizing agents - by quaternising a basic amide of a fatty acid and a poly:alkylene poly:amine with epichlorohydrin |
| DEP2856858.3 | 1978-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1152243A true CA1152243A (en) | 1983-08-16 |
Family
ID=25775609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000334775A Expired CA1152243A (en) | 1978-09-01 | 1979-08-30 | Sizing agents for paper |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0008761B1 (en) |
| CA (1) | CA1152243A (en) |
| DE (1) | DE2961254D1 (en) |
| ES (1) | ES483786A1 (en) |
| FI (1) | FI792701A (en) |
| NO (1) | NO792679L (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530945A (en) * | 1982-09-30 | 1985-07-23 | Ppg Industries, Inc. | Pigment grinding vehicle |
| DE3663701D1 (en) * | 1985-04-30 | 1989-07-06 | Bayer Ag | Use of basic amides for increasing the porosity in paper or paper-like materials |
| DE3672564D1 (en) * | 1985-11-08 | 1990-08-16 | Ciba Geigy Ag | DIQUATERAL AMMONIUM SALTS AND THEIR PRODUCTION AND USE AS A TEXTILE FINISHING AGENT. |
| DE3620033A1 (en) * | 1986-06-13 | 1987-12-17 | Bayer Ag | HYDROPHOBIC AND OLEOPHOBIC EQUIPMENT |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB711404A (en) * | 1951-04-18 | 1954-06-30 | American Cyanamid Co | Improvements relating to the production of sized paper |
-
1979
- 1979-08-16 NO NO792679A patent/NO792679L/en unknown
- 1979-08-27 EP EP79103153A patent/EP0008761B1/en not_active Expired
- 1979-08-27 DE DE7979103153T patent/DE2961254D1/en not_active Expired
- 1979-08-30 CA CA000334775A patent/CA1152243A/en not_active Expired
- 1979-08-30 FI FI792701A patent/FI792701A/en not_active Application Discontinuation
- 1979-08-31 ES ES483786A patent/ES483786A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES483786A1 (en) | 1980-05-16 |
| NO792679L (en) | 1980-03-04 |
| FI792701A (en) | 1980-03-02 |
| DE2961254D1 (en) | 1982-01-14 |
| EP0008761A1 (en) | 1980-03-19 |
| EP0008761B1 (en) | 1981-11-04 |
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