Note: Descriptions are shown in the official language in which they were submitted.
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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
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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
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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
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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
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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
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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
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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
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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
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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%.
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EXAMPLE 2
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.
EXAMPLE 3
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
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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.
EXAMPLE 4
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.
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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:
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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.
EXAMPLE 12
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.
EXAMPLE 13
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.
EXAMPLE 14
-
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.
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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.
EXAMPLE 16
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.
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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.
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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.
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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.
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