[0001] This invention relates to a method of sizing paper.
[0002] Conventional high-grade, water-resistant papers are made by adding rosin (a natural
product from pine trees) at the wet-end of the papermaking process. The rosin is barely
water-dispersible, and in the presence of alum, it precipitates in the fibre web as
the paper sheet is being formed. Variations in the composition of the paper-making
furnish can have an adverse effect on the amount of rosin which precipitates on the
papermaking wire. The usual commercial practice to compensate for such variations
is to add an excess amount of rosin to the furnish to ensure sufficient pickup to
make a paper having the desired level of water-resistance.
[0003] There are increasing numbers of paper mills which use recycled paper as part of the
raw material in the wet-end furnish of the papermaking process. As material economy
measures are required, and conditions of pH, surface charge and pulp constituents
in the papermaking machine are changed, the materials which can be used to impart
water-resistance to the paper must meet new requirements without sacrificing paper
quality.
[0004] In some earlier attempts to make a water-resistant paper by adding rosin/alum compounds
at the size press, too much rosin/alum was employed and the excess tended to coagulate
and gum up the size press, causing the resulting paper to be "spotty". To the applicants'
knowledge, there has not yet been a successful commercial method of obtaining water-resistant
paper by means of sizing with a starch derivative at the size press in a papermaking
process.
[0005] United States Patent 3,279,975 describes a method of surface sizing using the reaction
product of an unsaturated acid and petroleum resin. Various other materials are disclosed
in the literature for use as sizing agents for the surface treatment of paper. Such
materials include emulsions of the reaction product of an unsaturated dibasic acid
or anhydride of the acid with, for example, a maleated petroleum resin, alkyl ketene
dimers, alkali-soluble styrene copolymers, chromium complexes of fluorocarbon chemicals,
and others. Such materials have not attained widespread use because of costs, or control
problems, such as the "gum up" phenomena, or drying problems.
[0006] United States Patents, 2,613,206; 2,461,139 and 3,091,567 disclose certain hydrophobic
starch acid-esters and various uses for these starch derivatives. A method of making
these starch acid-esters and their combination with multivalent metal ions such as
aluminium is disclosed in United States Patent 2,613,206, and the hydrophobic character
of the starch is set forth. However, the industrial uses suggested for the resulting
starch derivative do not include paper sizing. The mentioned uses include: anti-offset
spray for preventing ink transfer between freshly printed sheets: insecticide carriers,
delustering agent in the manufacture of cellulose acetate rayons, delustering agent
in lacquer- type paints and coatings; rubber finishing agent; and textile sizing and
finishing agent. This patent makes no mention of any use of the subiect starch derivative
in paper sizing; or of thinning it prior to use. Paper sizing and coating is mentioned
in U.S. Patent 2,661,349, Col. 11, lines 5-10, but only in a general way. There are
no examples illustrating such uses.
[0007] United States Patent 2,461,139 describes a method of making starch ester derivatives
by reacting starch, in the presence of moisture, with organic acid anhydrides to obtain
an inhibited starch having a reduced tendency to gel. The patent states that an alkaline
reaction medium (pH 7-11) is essential to the practice of the inventive method. "An
amazing increase in water absorptive powers" is shown by starch treated with succinic
anhydride. Papermaking is mentioned (Column 3, lines 31-34), but the starch derivative
is only described as a replacement for tuber starches in papermaking for its non-
gelling nature and its superior cohesiveness. Apparently, the application under consideration
was that of a binder in the wet-end, or furhish, of the paper machine. Examples 4
and 5 of the subject patent describe making a so-called "thin-boiling" starch, but
only with maleic and acetic anhydride. Example 6 describes thinning a starch maleate
ester to obtain a thin-boiling starch. Both Example 8 and 9 describe reacting starch
with succinic anhydride, and the general disclosure states that the starch derivatives
of any of the examples may be further converted, as by acid hydrolysis, for example.
There is no mention of sizing paper, however, and the starch derivative obtained using
succinic anhydride is described as a "high water absorptive starch" (column 12, lines
2 and 3 of U.S. Patent 2,461,139).
[0008] United States Patent 3,091,567 is directed to a starch acid-ester encapsulating agent
having controlled water repellency obtained by reacting the starch acid-ester with
a compound containing a polyvalent metallic ion. The starch acid-ester may be obtained
from the reaction of starch with octenyl succinic acid anhydride. General language
in this patent suggests that the starch used to make the described starch acid-ester
"may have been previously modified ... by hydrolysis, oxidation ..." etc. (Column
3, lines 22-24). This patent, however, discloses only one use of the starch derivative.
It is used to encapsulate water-insoluble substances to permit slow, gradual release
of the encapsulated material. There is no mention of possible use in a papermaking
process.
[0009] Recently published French Patent Specification 2370772 describes sizing of paper
or cardboard with a sizing composition comprising 1-20 parts of hydrophobic starch
and 99-80 parts of non- hydrophobic starch. The hydrophobic starch consists of a dicarboxylic
acid starch monoester in which the carboxylic acid groups are on adjacent carbon atoms.
The dicarboxylic acid may have 8-22 carbon atoms, and may have alkyl or halogen substituent
groups. Included in Example 2 of the subject French Specification is 1-octenylsuccinic
anhydride as an esterification agent for making Starch "C". The method of Example
1 was followed to make Starch "C", and the level of substitution was reported to be
0.027 d.s.
[0010] A starch derivative like the above Starch "C" was used to size a paper web made from
bleached kraft pulp containing about 1% alum, based on the pulp dry weight. The dispersed
sizing composition contained 5% of a hydrophobic starch (like Starch "C", but with
a d.s. of 0.032) and 95% of a non- hydrophobic cationic starch (having about 0.24%
by wt. nitrogen content). The dispersion had a solids level of about 4-5%. Sixty pounds
of the size dispersion per ton of paper was applied. Rosin was also used in the sample
runs (at 12 and 6 kg/metric tonne respectively).
[0011] The above derivatized starch sizing agent and sizing method differs from the subject
sizing composition and method in at least the following important ways:
[0012] It is not clear from the disclosure of the subject French specification that some
alum must be present in the paper web as it enters the size press. In addition, it
is believed that the overall expenses and materials cost to practice the method of
the subject French patent specification would be too high for use as a competitive
method of sizing paper. The purpose of the present invention is to cut down on the
excessive use of rosin. The method described in the French patent specification does
not substantially reduce the amount of rosin used, and it is believed that the same
sizing effect is obtainable using the stated amounts of rosin without the highly substituted
octenyl succinic acid starch ester. The results of the present invention are much
superior to the results reported in the subject French specification, and applicants
use a starch derivative having a much lower level of substitution with only enough
rosin present to control pick-up (1-2 kg rosin/tonne of paper).
[0013] The present invention provides a method of externally sizing a cellulosic web, which
contains a multivalent metal ion but not more than 2 kg/tonne rosin, to impart increased
water resistance to the web which comprises applying to the web at a temperature of
50°C to 80°C a starch containing aqueous sizing composition having a pH of 4 to 7.5
and a Brookfield viscosity in the range of 10 to 1 50 cps (No. 1 spindle; 20 rpm;
66°C) so that the starch is applied to the cellulosic web at a rate of 10 to 100 kg
tonne, the aqueous sizing composition containing 2 to 15% by weight based on the sizing
composition of a dicarboxylic acid starch ester obtained by reacting starch with a
dicarboxylic acid anhydride having 8 to 22 carbon atoms which an aliphatic, aromatic,
alicyclic, or bicyclic aliphatic dicarboxylic acid anhydride, the starch ester having
a degree of substitution of the dicarboxylic acid anhydride in the range from 0.005
to 0.023. Preferably the starch ester is obtained by reacting starch with 1-octenyl
succinic acid anhydride.
[0014] Thus the starch ester may be a 1-octenylsuccinic acid half ester of cornstarch, the
degree of substitution of which is in the range of 0.008 to 0.016, e.g. a 1-octenylsuccinic
acid half ester of cornstarch which is slightly oxidized so that the amount of protein
remaining in said half ester is less than 0.1 % by weight based on the weight of the
starch.
[0015] Preferably the multivalent metal ion which may be aluminium, calcium, magnesium,
manganese or barium is in the form of a slightly water-soluble salt, and is added
to the aqueous furnish from which the cellulosic web is formed. Preferably the multivalent
metal ion is aluminium and is obtained from aluminium chloride, aluminium sulphate
or sodium aluminate. Thus the multivalent metal salt may be aluminium sulphate which
is present in the cellulosic web in an amount of at least 5 kg aluminium sulphate
per tonne of fibre in the cellulosic web, or sodium aluminate which is present in
the cellulosic web in an amount of at least 1.5 kg per tonne of fibre in the cellulosic
web.
[0016] Preferably the reduced viscosity of the starch ester is obtained by acid hydrolysis
of the starch ester or by thermal chemical treatment of the starch ester. Alternatively,
the substituted starch may have been slightly oxidized, and the reduced viscosity
obtained by high temperature thermal treatment, e.g. at 107 to 163°C. Preferably the
paper web is free of rosin.
[0017] Thus the invention relates to a method of making a water resistant paper by sizing
the paper web at the size press with an aqueous solution of a viscosity thinned, hydrophobic
starch derivative. The preferred starch derivative is the starch acid-ester of octenyl
succinic anhydride. Alum present in the web from the wet-end of the papermaking process
reacts with the starch derivative to produce a water-resistant sheet. When this starch
derivative is applied from a solution at the size press of the papermaking machine,
it apparently combined with the alum in a unique way to produce a high level of water
resistance concentrated at the surface of the paper. The multivalent metal ion (aluminium)
is supplied from the sheet passing through the size press from the wet-end (furnish)
of the papermaking machine, or if the wet-end composition does not contain alum, aluminium
sulphate may be added to the furnish at the wet-end of the papermaking machine so
that it is present in the web at the size press where the thin viscosity octenyl succinate
starch acid-ester is applied.
[0018] The invention is illustrated by the following examples.
Example 1
[0019] The starch acid-ester used in the method of the invention may be made as follows:
Pearl starch (100 parts, as is) is adjusted with water to a slurry of about 21-22°
B6 (at 16°C). About 2.9 parts of 60° B6 sulfuric acid which has been diluted with
2.9 parts of water is then added to the above starch slurry, and the temperature is
adjusted to 53°C.
[0020] The acid is allowed to convert the starch at 53°C for approximately five hours to
reach a target alkali fluidity value of 56 ml, using a 10 g sample of starch in 90
ml of 0.375N NaOH for determining alkali fluidity value. When the target alkali fluidity
has been reached, the pH of the thinned starch slurry is adjusted to 4.5-5.0 with
18° B6 soda ash (sodium carbonate). About 2.8 parts soda ash is required. The slurry
is then screened, filtered, and the filter cake washed. The washed filter cake is
then reslurried in water to 21-22° Be (at 16°C) and the temperature is adjusted to
32-35°C. The slurry is then agitated vigorously throughout the remaining steps of
the process.
[0021] Two parts of 1-octenyl succinic anhydride is then added to the slurry. Immediately
thereafter, 5% NaOH solution is aded to adjust the slurry pH to 6.5-7.5. The pH is
maintained in this range (6.5-7.5) with 5% NaOH until the slurry pH remains constant.
Approximately 2t hours is required to reach pH equilibrium, with a total addition
of about 0.5 parts NaOH.
[0022] The slurry is then adjusted to 6.0-6.5 pH with 30° Bé sulphuric acid (about 0.5 parts
of 60° Be H
2SO
4 required). The reacted starch is then screened and filtered. The filter cake is thoroughly
washed with water at 43°C maximum. The washed starch derivative is then dried and
screened. The moisture content of the dried product should be in the range of 10-13%,
and at least 1% by weight, dry solids basis, of 1-octenyl succinic anhydride should
have been reacted with the starch. The above starch derivative is then ready to use
in the method of the invention and its various embodiments described herein.
Example 2
[0023] The starch derivative made according to the above Example 1 has been successfully
used as a water resistant size press starch to impart a high degree of water resistance
to paper when applied to a paper sheet during the papermaking process. The sheet should
contain sufficient alum (sodium aluminate) from the wet-end of the Fourdrinier-type
papermaking machine. The addition of this starch derivative at the size press also
develops the internal strength properties as efficiently as any conventional size
press starches.
[0024] A trial was conducted at a paper mill which normally includes alum (sodium aluminate)
in the wet-end of the papermaking machine. This mill also normally used a fortified
rosin in the wet-end and another starch (enzyme converted) at the size press to obtain
borderline sizing. Various trial runs were made as described below. The tests indicated
that a significant improvement in water resistance can be obtained through application
of the subject starch derivative at the size press of a paper-making machine.
[0025] A number of runs were made on a commercial paper-making machine using the starch
derivative of Example 1, added at the size press. A control run was made on the same
papermaking machine using an enzyme converted pearl starch at the size press at the
same solids level. Hercules H.S.T.
#2 INK tests were performed, and the results recorded. In another series of tests,
pearl starch and the starch derivative of Example 1 were applied at the size press.
In both of the above cases, the starch solids at the size press was about 7.8%. The
results of the subject test runs are reported below in Table I:
[0026] Table I shows that definite and effective sizing was obtained using the subject starch
derivative, applied at the size press. Only borderline sizing was obtained when an
enzyme converted pearl starch was used at the size press in combination with a fortified
rosin in the wet-end. However, Table I shows that the subject starch derivative not
only gave excellent water-resistance size effect to the paper, but the internal fortified
rosin size was also reduced by 25%. In addition, the subject starch derivative had
no adverse effect on other physical properties of the sheet, such as mullen, tear,
wax, pick, opacity and brightness. The pH of the size press dispersion was maintained
at about 6 during the tests. The level of alum in the newly formed sheet was about
7.5 to 10 kg per metric tonne expressed as alum. The amount of alum in the sheet was
determined by the method set forth below following Example 3.
Example 3
[0027] Another paper mill test was also conducted which further demonstrated the effectiveness
of the subject starch derivative to produce a water-resistant sheet when the subject
starch is applied at the size press of a paper machine as described below.
[0028] Table II below is a report of the second series of tests conducted at the same paper
mill as Example 2 on the same commercial papermaking machine. The subject starch derivative
was again applied at the size press in the various combinations described in Table
II:
[0029] As seen in Table II, the percent starch solids at the size press was about 7.5%,
the particular starches comprising the total starch solids were changed as noted from
a 50/50 blend of the starch of Example 1 and an enzyme-converted pearl starch to 100%
enzyme converted pearl starch and then back to a 50/50 blend of the above starch derivatives.
The effect on the H.S.T. #2 INK test results caused by removing the starch derivative
of the subject invention from the size press starch blend was dramatic and clear.
Excellent water resistance (149 sec) was obtained when a 50/50 blend was used which
included the starch derivative of the subject invention. The H.S.T. #2 INK test fell
in value by a factor greater than two to a value less than one-half the initial value
(61 sec). When the 50/50 blend of enzyme converted pearl starch and the starch derivative
of Example 1 herein was again restored in the Size press, the H.S.T. #2 INK test more
than tripled in value when compared to 100% enzyme-converted
Jearl starch applied at the size press. This example clearly establishes that the increased
sizing is attributable to the starch derivative of Example 1 and not to some other
cause. The percent starch pick- up was also measured in this trial and was about 3%.
The test shows that a 50/50 blend of an enzyme converted pearl starch with the subject
starch derivative of Example 1 proved very adequate to obtain excellent water resistance
when applied at the size press.
[0030] Apparently, the level of octenyl succinate groups on the paper web in the range of
substitution described is what determines the level of water resistance in the resulting
paper, not the amount of starch used, although the starch per se does contribute internal
strength to the paper web. In other words, a starch derivative having a d.s. of 0.016
can be used in a smaller quantity to obtain the same level of water resistance obtainable
from a larger quantity of a starch derivative having a lower level of octenyl succinate
groups therein. When the substitution level of octenyl succinate groups is 0.016 or
lower, it appears to be unnecessary to add any other starch, because enough of the
subject starch is then present to provide both water resistance and internal strength
to the paper. The lower d.s. levels, therefore, greatly simplify the preparation of
the sizing composition, since only one starch derivative is needed.
[0031] Table III below shows the relationship between the percent pick-up of octenyl succinate
starch and the effect on sizing that the percent pick-up has.
Table III above clearly shows a dramatic increase of water resistance when the amount
of pickup of the subject starch derivative is increased. Tripling of the pick-up of
the subject starch derivative causes a substantial increase in water resistance of
the sheet, as evidenced by the Hercules Sizing Test results (122 seconds). The above
sizing effect was obtained without the use of any rosin in the wet-end, but in some
applications, it may be desirable to include a small amount (1-1.5 kg rosin/tonne
of paper furnish) in the wet-end to aid in controlling size press pick-up.
[0032] As pointed out earlier, to obtain effective sizing, it is a requirement of the method
of the present invention that some alum (aluminium sulphate) or sodium aluminate be
added at the wet-end, so that there is actually a minimum amount of aluminium ion
in the paper web as it enters the size press. At the present time, it has been found
that about 5 kg alum/tonne of fibre in the paper web is the minimum required to obtain
effective water-resistant sizing in the finished paper sheet.
[0033] The subject starch derivative is cooked prior to application to the sheet, either
by batch methods, or by a continuous cooking methods, such as jet cooking. The subject
starch derivative can be combined with a conventional size press starch (e.g. pearl
cornstarch) to increase the strength of the sheet. The application temperature should
not fall below 51 °C, and is preferably in the range of 76-82°C. For best pick-up
and sizing at the size press using the subject starch derivative, a pH in the wet-end
of about 4-6 has been found to be desirable.
[0034] The subject starch derivative is most useful when added at the size press to develop
a high degree of water resistance in a paper web which contains alum, sodium aluminate,
or other multivalent metal ion introduced at the wet-end of the papermaking machine.
The starch derivative also develops internal strength equivalent to the most efficient
of the conventional size press starches. It is also contemplated that the subject
starch derivative can be applied to a cellulosic sheet from a kalender stack to efficiently
obtain a higher level of water resistance in such sheets.
[0035] The viscosity characteristics of this starch are described below. As the concentration
increases from a 2% dsb starch to 12% dsb starch, the Brookfield viscosity increases.
For example, at 52°C, the Brookfield viscosity of a 2% dsb aqueous starch sample was
about 13 cps. When the concentration was increased to 8%, the Brookfield viscosity
was about 45 cps., at 10% concentration, the Brookfield viscosity was about 69 cps
and at 12% starch concentration, the Brookfield viscosity was about 97 cps. As the
temperature is increased, the viscosity increases with increased solids levels are
not as large as they are at lower temperatures. For direct comparison of the temperature
effect see the table below:
The above Brookfield viscosities are obtained using a #1 spindle at 100 rpm.
[0036] The above viscosity/solids/temperature characteristics are typical of size press
starches. It is considered desirable that the subject starch have such viscosity characteristics
for convenience of application, particularly when it is applied from the size press
in combination with other conventional starches.
[0037] Although the exact reason is not known with certainty, the subject starch derivative
is not effective when subjected to viscosity thinning by means of enzyme conversion.
It is possible that the enzyme separates the octenyl groups from the starch ester,
so that the hydrophobic properties are lost.
[0038] Other starch ester derivatives are also believed to be useful in the method of sizing
paper at the size press to obtain high levels of water resistance. These additional
starch derivatives may be made from substituted cyclic dicarboxylic acid anhydrides
and mixed anhydrides which attach to the starch molecule through the ester group,
have hydrophobic properties, and are capable of reacting with the multivalent metal
ion (aluminium ion) in the paper web as it passes through the size press. It is contemplated
that hydrocarbon chain extensions obtainable from CB-Cz4 cyclic dicarboxylic anhydrides
are useful for this purpose with the necessary adjustments in concentration of the
respective starch derivatives in the size press dispersion. For extremely hydrophobic
starch derivatives, less will be required to obtain water resistance, and in those
instances a more conventional size press starch is used to obtain internal strength
in the paper sheet.
Example 4
[0039] One hundred parts of cornstarch is slurried in water in about 22.5 Be at 16°C. The
slurry temperature is then raised to about 32-35°C, and the pH is adjusted to about
6.5-7.0 with 5% (7.0-7.4° Bé) sodium hydroxide solution. Then about 2% by weight based
on the starch weight, of 1- octenylsuccinic anhydride is added to the slurry with
agitation (as rapidly as possible). As soon as all the anhydride is in, the addition
of 5% (7.0-7.4° Be) sodium hydroxide is begun, and the pH of the slurry is adjusted
to 6.5-7.5. The addition of sodium hydroxide is continued with agitation for about
2f hours with constant agitation while the pH of the slurry is maintained at about
6.5-7.5 with 5% sodium hydroxide. The reaction is continued until the pH remains constant.
The degree of substitution at completion of the reaction should be in the range of
0.008 to 0,016.
[0040] The pH of the derivatized starch slurry is then adjusted to 5.5--6.0 and temperature
is adjusted to 43°C. The resulting product is then screened, filtered, washed and
dried. The resulting product should have the following characteristics:
[0041] The above starch derivative is not thinned, but should be, prior to use. It can be
thinned at the paper mill at the time of use by thermal-chemical cooking as described
in Example 6 below.
Example 5
[0042] One hundred parts of cornstarch is slurried in water to a solids level of about 22.5°
Be at 16°C. The slurry pH is adjusted to about 7.5 with anhydrous sodium carbonate,
and the slurry temperature is adjusted to 49-52°C. The slurry is then subjected to
alkaline bleaching for about two hours using about 1.7% by weight of NaOCI, or about
0.5% by weight chlorine (based on the weight of the starch). The alkali fluidity of
the bleached starch should be at least 65 ml using a 2.5 g sample, 0.375N and the
test procedure described following the examples. The bleaching step is terminated
by adding 0.13% by weight, based on the total starch weight, of sodium bisulphite.
[0043] The slurry temperature is adjusted to about 32-35°C and the pH is maintained in the
range of 6.5-7.0. Then about 2% by weight 1-octenylsuccinic anhydride is added while
the slurry is vigorously agitated. Then sodium hydroxide is immediately added to adjust
the pH to 6.5, and thereafter maintain the pH in the range of 6.5-7.5, and the esterification
reaction is continued for about 2t hours to the end point, during which the pH is
adjusted with NaOH as needed to maintain the pH in the range of 6.5-7.0. The amount
of 1-octenyl succinic anhydride is limited to a total of 3% based on the dry substance
weight of the starch. The slurry temperature is then adjusted to 43°C, followed by
screening, filtering and drying. The dry product should have the following properties:
alkali fluidity: 75 ml minimum (2.5 g sample, 0.375N)
d.s. of octenyl succinate groups : 0.008-0.016
(range 1-3% by weight octenyl succinate groups, based on starch).
The preferred degree of substitution level is 0.008-0.016 of octenyl succinate groups.
However, the level of substitution may be as low as 0.005 or as high as 0.023, and
still provide the benefits of increased sizing to some papers.
[0044] The starch half ester of Example 5 is also thinned prior to use, as described in
Example 4, by thermal-chemical cooking, jet cooking, high temperature pressure cooking,
acid hydrolysis, or by any conventional method, except enzyme thinning, to produce
a thinned viscosity starch having a Brookfield viscosity in the range of 10-150 cps
(2-15% solids level; 66°C; No. 1 spindle at 100 rpm). When the starch derivative has
been bleached, as in Example 5, then chemical conversion at the mill is unnecessary.
The bleached product produces better colour in the coated paper, also.
[0045] The viscosity of the starch composition is adjusted to effect the most desirable
pick-up of materials from the size press. There are viscosity differences dictated
by particular paper machine apparatus, and also by the particular grade of paper being
manufactured. For certain hard-to-size papers, it is believed that it would be desirable
to increase the substitution level above the normal upper limit of 0.023, up to about
0.039. Such a starch derivative is then thinned, and can be used alone at the size
press without a second, or supplementary, starch sizing agent. The pH range at the
wet end may be up to 6, and, at the size press, the pH may range from 4 to 7.5.
[0046] The subject starch derivatives can be used without any rosin present in the wet end.
However, it may be desirable to use about 1-1.5 kg of rosin/tonne of paper in the
wet end furnish of the paper making machine to help control size press pick-up and
to improve runability of the paper making process.
[0047] Sizing efficiency has been observed to fall off as the alum dosage in the wet end
is lowered, and as the wet end pH is increased. Although, alum (aluminium sulphate)
is presently preferred, it is also contemplated that other compounds can be substituted.
Sodium aluminate, for example can be used to provide multivalent aluminium ion in
the paper web as it enters the size press. In addition, it is expected that CaCl
z' MgCl
z, MnCI
2., or BaCl
z could be used in the wet end furnish to provide a multivalent metal ion in the web
of the paper entering the size press. At the present time, it appears that 5 kg alum/tonne
of fibre in the paper web is the minimum required to obtain effective sizing.
[0048] As pointed out above, it has been found that enzyme thinning of the octenyl succinate
ester of starch is not an effective or desirable mode of thinning the starch derivative.
Apparently, the octenyl succinate groups are cleaved away from the starch molecules
by the enzyme action, and the starch derivative loses its effectiveness for sizing.
Example 6
[0049] The starch ester derivative made according to Example 4 was tested under laboratory
conditions to simulate application to a paper web at the size press of a paper making
machine. Six hundred grams of the Example 4 starch derivative was slurried in sufficient
water with 0.2% ammonium persulphate based on the starch (dry substance weight) to
make a total weight of 4000 g. The above slurry was then cooked at about 157-160°C
through a loop type cooker similar to that described in U.S. Patent 3,661,640. The
solids level of the cooked starch paste was 13% at a pH of 4.9. The pH was then adjusted
to 5.7 with 5% NaOH solution. The solids of the cooked starch paste was adjusted to
10%. The Brookfield viscosity, using a No. 1 spindle at 20 rpm and 66°C was 35 cps.
[0050] A base sheet containing no rosin and 10 kg alum/tonne of paper was sized with the
above starch derivative paste at 10% solids level and a pH of 5.7. The pick-up of
sizing calculated to 6.2%, which was considered excellent. The Hercules Size Test
for the above sized paper was 49.5, indicating excellent sizing was obtained.
Example 7
[0051] The starch ester derivative of Example 5 was also tested in the laboratory as described
above in Example 6. The lightly oxidized starch derivative was first subject to thermal
cooking (without added ammonium persulphate). A 15% solids slurry of the Example 5
starch derivative was jet cooked at a temperature of about 160°C in a jet cooker (without
a loop tube). The solids level of the cooked starch derivative was adjusted to 10%
by adding hot water. The Brookfield viscosity was 23 cps (No. 1 spindle; 20 rpm; 66°C).
The pick-up of the cooked starch paste was 6.2%. The Hercules Sizing Test value was
85.6, showing unexpectedly superior sizing. Several additional runs were made and,
although the Hercules Sizing Test for these runs were not as high as the initial run
reported above, they were significantly better than tests made with a similarly substituted
starch which had not been first slightly oxidized. A possible explanation for the
superior performance of the starch derivative of Example 5 is that the light bleaching
further reduces the protein content of the starch to less than about 0.1%. Lower protein
levels and the carboxyl groups added by bleaching enhance film-forming properties
of the starch. However, the carboxyl content is kept below 0.3% because excessive
carboxyl groups from recycled broke act as a dispersant in the wet end of the paper
machine and thereby interfere with filler retention. Wet end problems are avoided
by limiting the amount of carboxyl groups on the starch derivative used at the size
press.
Test procedures
Determination of degree of substitution
[0052] The d.s. of octenyl succinate may be measured by determining the carboxyl level of
the unsubstituted starch, and subtracting this value from the carboxyl level determined
on the reacted and filtered starch. The determination may be made by titrating known
samples with standard (0.100N) sodium hydroxide to pH 7.5. The respective samples
are thoroughly washed prior to the test, to remove any unreacted reagent from the
product test sample, and to subject the control to all the same conditions as the
test sample.
Alkali fluidity
[0053] The alkali fluidity or "inhibition index" test is substantially as described in United
States Patent 3,876,629, column 7, lines 33-67 and column 8, lines 1-10.
Hercules Sizing Test
[0054] This test is described in Hercules Sizing Tester Instruction Manual HST-lA using
Model KA Hercules Sizing Tester sold by Hercules, Inc. of Wilmington, Delaware, U.S.A.
The results are all obtained using a Hercules No. 2 ink and 80% reflectance.
Mullen strength test
[0055] This test is described in TAPPI Standard T403 os-76 (Technical Association of the
Pulp and Paper Industry).
1. A method of externally sizing a cellulosic web, which contains a multivalent metal
ion but not more than 2 kg/tonne rosin, to impart increased water resistance to the
web which comprises applying to the web at a temperature of 50°C to 80°C a starch
containing aqueous sizing composition having a pH of 4 to 7.5 and a Brookfield viscosity
in the range of 10 to 150 cps (No. 1 spindle; 20 rpm; 66°C) so that the starch is
applied to the cellulosic web at a rate of 10 to 100 kg/tonne, the aqueous sizing
composition containing 2 to 15% by weight based on the sizing composition of a dicarboxylic
acid starch ester obtained by reacting starch with a dicarboxylic acid anhydride having
8 to 22 carbon atoms which is an aliphatic, aromatic, alicyclic, or bicyclic aliphatic
dicarboxylic acid anhydride, the starch ester having a degree of substitution of the
dicarboxylic acid anhydride in the range from 0.005 to 0.023.
2. A method as claimed in Claim 1, wherein the starch ester is obtained by reacting
starch with 1- octenyl succinic acid anhydride.
3. A method as claimed in Claim 2, wherein the starch ester is a 1 octenyisuccinic
acid half esterof cornstarch, the degree of substitution of which is in the range
of 0.008 to 0.016.
4. A method of Claim 3, wherein the 1-octenylsuccinic acid half ester of cornstarch
is slightly oxidized so that the amount of protein remaining in the half ester is
less than 0.1 % by weight based on the weight of the starch.
5. A method as claimed in any of Claims 1 to 4, wherein the multivalent metal ion
is aluminium, calcium, magnesium, manganese or barium.
6. A method as claimed in Claim 5, wherein the multivalent metal ion is in the form
of a slightly water-soluble salt, and is added to the aqueous furnish from which the
cellulosic web is formed.
7. A method as claimed in Claim 6, wherein the multivalent metal ion is aluminium
and is obtained from aluminium chloride, aluminium sulphate or sodium aluminate.
8. A method as claimed in Claim 7, wherein the multivalent metal salt is aluminium
sulphate which is present in the cellulosic web in an amount of at least 5 kg aluminium
sulphate per tonne of fibre in the cellulosic web, or the multivalent metal salt is
sodium aluminate which is present in the cellulosic web in an amount of at least 1.5
kg per tonne of fibre in the cellulosic web.
9. A method in any of Claims 1 to 8 wherein the reduced viscosity of the starch ester
is obtained by acid hydrolysis of the starch ester of by thermal-chemical treatment
of the starch ester.
10. A method as claimed in any of Claims 1 to 8, wherein the substituted starch has
been slightly oxidized, and the reduced viscosity is obtained by high temperature
thermal treatment.
11. A method as claimed in Claim 10, wherein the temperature of the thermal treatment
is in the range 107 to 163°C.
12. A method as claimed in any of Claims 1 to 11, wherein the paper web is free of
rosin.
1. Verfahren zum äußeren Leimen eines Zellulosegewebes zur Erhöhung der Wasserfestigkeit
desselben, wobei das Gewebe das ion eines mehrwertigen Metalles und Rosinharz, jedoch
in einer Menge von nicht mehr als 2 kg/Tonne Rosinharz enthält, dadurch gekennzeichnet,
daß dem Gewebe bei einer Temperatur im Bereich von 50-80°C ein stärkehaltiges wässriges
Verleimungsprodukt mit einem pH von 4-7,5 und einer Viskosität nach Brookfield im
Bereich vc n 10 bis 150 cps (Spindel Nr. 1, 20 U/min bei 66°C) mit einer Zugabe-Menge
von 10-100 kg/Tonne Zellulosegewebe zugegeben wird, wobei das wässrige Verleimungsprodukt
2-15 Gew.-% (auf der Basis des Gewichts der Verleimungsproduktes) eines Dicarbonsäurestärkeesters
enthält, der durch Umsetzung von Stärke mit einem Dicarbonsäureanhydrid mit 8-22 Kohlenstoffatomen
erhalten wurde, wobei das Dicarbonsäureanhydrid ein aliphatisches, aromatisches, alicyclisches
oder bicyclisch-aliphatisches Dicarbonsäureanhydrid ist und der Stärkeester einen
Grad der Substitution mit dem Dicarbonsäureanhydrid im Bereich von 0,005-0,023 hat.
2. Verfahren gemäß Anspruch 1, dadurch gekennziechnet, daß der Stärkeester durch Umsetzung
von Stärke mit dem Anhydrid der 1-Octenylbernsteinsäure erhalten wurde.
3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß der Stärkeester der 1-Octenylbernsteinsäurehalbester
von Maisstärke ist, bei dem der Substitutionsgrad im Bereich von 0,008-0,016 liegt.
4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß der 1-Octenylbernsteinsäurehalbester
der Maisstärke in geringem Umfange oxydiert ist, so daß die im Halbester verbliebene
Menge Protein weniger als 0,1 Gew.-% auf der Basis der Stärke beträgt.
5. Verfahren gemäß irgendeinem der Ansprüche 1-4, dadurch gekennzeichnet, daß das
lon des mehrwertigen Metalles von Aluminium, Calcium, Magnesium, Mangan oder Barium
ist.
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß das lon des mehrwertigen
Metalles in Form eines wenig wasserlöslichen Salzes vorliegt und dem wässrigen Ausgangsprodukt
zugegeben wird, aus dem das Zellulosegewebe Gebildet wird.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß das ion des mehrwerigen
Metalles ein Aluminiumion ist und aus Aluminiumchlorid, Aluminiumsulphat oder Natriumaluminat
erhalten worden ist.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß das Salz des mehrwertigen
Metalles Aluminiumsulphat ist, das in dem Zellulosegewebe in einer Menge von mindestens
5 kg Aluminiumsulphat pro Tonne Fasern Im Zellulosegewebe anwesend ist, oder das Salz
des mehrwertigen Metalles Natriumaluminat ist. das im Zellulosegewebe in einer Menge
von mindestens 1,5 kg pro Tonne Faserb un Zellulosegewebe anwesend ist.
9. Verfahren nach irgendeinem der Ansprüche 1-8, dadurch gekennzeichnet, daß die verminderte
Viskosität des Stärkeesters durch Hydrolyse des Stärkeesters durch thermisch-chemische
Behandlung desselben erreicht worden ist.
10. Verfahren nach irgendeinem der Ansprüche 1-8, dadurch gekennzeichnet, daß die
substituierte Stärke in geringem Maß oxydiert wurde und die verringerte Viskosität
durch thermische Behandlung bei hohen Temperaturen erreicht worden ist.
11. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, daß die thermische Behandlung
bei einer Temperatur im Bereich von 107-163°C durchgeführt wurde.
12. Verfahren nach irgendeinem der Ansprüche 1-11, dadurch gekennzeichnet, daß von
einem solchen Papierausgangsprodukt ausgegangen wird, daß das Papiergewebe frei von
Rosinharz ist.
1. Un procédé pour coller extérieurement une feuille continue cellulosique, qui contient
un ion de métal polyvalent, mais pas plus de 2 kg de colophane par tonne, de façon
à donner à la feuille continue une meilleure résistance à l'eau, selon lequel on applique
à la feuille continue à une température de 50°C à 80°C une composition aqueuse de
collage contenant de l'amidon qui a un pH de 4 à 7,5 et une viscosité Brookfield compirse
entre 10 et 150 cPo (rotor N° 1; 20 tpm; 66°C) de manière que l'amidon soit appliqué
à la feuille continue cellulosique à raison de 10 à 100 kg par tonne, la composition
aqueuse de collage contenant de 2 à 15% en poids, par rapport à la composition de
collage, d'un ester d'amidon d'acide dicarboxylique obtenu en faisant réagir de l'amidon
avec un anhydride d'acide dicarboxylique ayant de 8 à 22 atomes de carbone qui est
un anhydride d'acide dicarboxylique aliphatique, aromatique, alicyclique ou aliphatique
bicyclique, l'ester d'amidon ayant un degré de substitution de l'anhydride d'acide
dicarboxylique compris entre 0,005 et 0,023.
2. Un procédé selon la revendication 1, caractérisé en ce que l'ester d'amidon est
obtenu par réaction d'amidon avec l'anhydride d'acide 1-octényl succinique.
3. Un procédé selon la revendication 2, caractérisé en ce que l'ester d'amidon est
un semi-ester d'acide 1-octénylsuccinique d'amidon de maïs, dont de degré de substitution
est compris entre 0,008 et 0,016.
4. Un procédé selon la revendication 3, caractérisé en ce que le semi-ester d'acide
1- octénylsuccinique d'amidon de maïs est légèrement oxydé de manière que la quantité
de protéine restant dans le semi-ester soit inférieure à 0,1 % en poids par rapport
au poids de l'amidon.
5. Un procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que
l'ion de métal polyvalent est un ion d'aluminium, de calcium, de magnésium, de manganèse
ou de baryum.
6. Un procédé selon la revendication 5, caractérisé en ce que l'ion de métal polyvalent
est sous la forme d'un sel légèrement soluble dans l'eau, et est ajouté à la composition
aqueuse de fabrication à partie de laquelle la feuille continue cellulosique est formée.
7. Un procédé selon la revendication 6, caractérisé en ce que l'ion de métal polyvalent
est de l'aluminium et est obtenu à partir de chlorure d'aluminium, de sulfate d'aluminium
ou d'aluminate de sodium.
8. Un procédé selon la revendication 7, caractérsé en ce que le sel de métal polyvalent
est du sulfate d'aluminium qui est présent dans le feuille continue cellulosique à
raison d'au moins 5 kg de sulfate d'aluminium par tonne de fibre dans la feuille continue
cellulosique et le sel de métal polyvalent est de l'aluminate de sodium qui est présent
dans la feuille continue cellulosique à raison d'au moins 1,5 kg par tonne de fibre
dans la feuille continue cellulosique.
9. Un procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que
la viscosité réduite de l'ester d'amidon est obtenue par hydrolyse acide de l'ester
d'amidon ou par traitement chimique de l'ester d'amidon.
10. Un procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce
que l'amidon substitué a été légèrement oxydé, et la viscosité réduite est obtenue
par traitement thermique à température élevée.
11. Un procédé selon la revendication 10, caractérisé en ce que la température du
traitment thermique est comprise entre 107 et 163°C.
12. Un procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce
que la feuille continue de papier est exempte de colophane.