[0001] The invention relates to the sizing of cellulosic fibres and to compositions for
use in this, and to their manufacture.
[0002] During the manufacture of paper it is necessary to render the naturally hydrophilic
cellulosic fibres hydrophobic so that penetration of aqueous liquids into the formed
sheets is limited thereby making writing and printing on the sheets possible. This
process, known as sizing, can be carried out by adding a sizing agent to the pulp
slurry (usually termed internal sizing) or the sizing agent can be applied to the
formed paper sheet. This invention is concerned with the internal sizing process.
[0003] There are two types of sizing agent in general use. One of these is based on rosin
which is used in conjunction with alum. The rosin is added as a soap solution or as
an emulsion and alum is added afterwards just prior to sheet formation to precipitate
the rosin as a fine particulate which is retained by the sheet.
[0004] The second type of size is a reactive size, such as a ketene dimer or an anhydride-based
size, which reacts chemically with the cellulosic fibres. Preferably it is applied
in combination with a polyelectrolyte which will help to retain the size in the sheet.
[0005] The reactive size is generally added to the pulp in the form of an aqueous emulsion,
generally a cationic emulsion. The emulsion can be prepared at the mill but this necessitates
the mill having emulsifying equipment and so it would be more convenient if a concentrated
emulsion could be supplied to the mill ready for dilution and use. Unfortunately reactive
sizes tend to react with water so that an aqueous emulsion is liable to be rather
unstable.
[0006] Anhydride based sizes, such as alkenyl succinic anhydride sizes, are so reactive
that their emulsions have to be prepared at the mill just prior to use. These sizes
are normally supplied to the mill with a cationic starch which generally has to be
precooked before emulsification, thus making it even less convenient for the emulsion
to be formed at the mill.
[0007] Ketene dimer sizes often are supplied to the mill in the form of an emulsion but
these emulsions have only limited shelf-life and the maximum concentration of ketene
dimer in the emulsion is rather low, generally below 6%, so that very large volumes
of emulsion have to be supplied to the paper manufacture.
[0008] Emulsification of liquid ketene dimers can be achieved using conventional emulsification
equipment but some of the preferred ketene dimers are solids at ambient temperature.
As described in U.S. Patent Specification 3,046,186, emulsification of these necessitates
initially either melting the solid (so that upon cooling the emulsion is converted
to a dispersion) or dissolving the solid in a solvent, generally benzene. A typical
important ketene dimer is distearyl ketene dimer and this only has relatively low
solubility in organic solvents with the result that the solution of it that is emulsified
must be rather dilute. For instance we have found that this dimer precipitates from
a 40% by weight solution in benzene (weight ratio benzene:dimer of 1:0.67) and so
any solution in benzene must be much more dilute than this. Also this dimer is less
soluble in other organic solvents than it is in benzene.
[0009] As described in Patent Specification 3,046,186 the emulsions are generally prepared
by emulsifying the dimer into an aqueous solution of cationic dispersing agent although
that patent does mention that in certain instances the emulsifying agent may be predispersed
in the ketene dimer. It is stated that the emulsions may be prepared at any convenient
solids content but are used at 1 to 5% solids by weight.
[0010] In each of the examples in U.S. Patent Specification 3,046,186 the initial composition
that was prepared and that contained both size and polyelectrolyte was very dilute.
For instance in Example 1 the initial concentration is about 9% by weight size based
on the total composition.
[0011] As mentioned above, it is preferred to provide a polyelectrolyte with the reactive
size and it might be thought that some of the disadvantages associated with providing
emulsions of reactive size and polyelectrolyte could be minimised if the reactive
size and the polyelectrolyte were supplied separately. However this incurs other disadvantages.
[0012] It would therefore be very desirable if it was possible to supply a stable concentrated
composition that contained both reactive size and polyelectrolyte and which was readily
dilutable with water at the mill.
[0013] A concentrate composition according to the invention comprises a substantially anhydrous
dispersion of a polyelectrolyte in an organic liquid comprising a solution of a reactive
size in a hydrophobic solvent.
[0014] The concentrate composition generally has a reactive size concentration above 20%
and preferably at least 28.6%. The concentration of reactive size is often in the
range 30 to 60%. The amount may be higher, for instance up to 80% or 85%. All these
amounts are by weight of the total composition.
[0015] The weight ratio, on a dry basis, of polyelectrolyte:reactive size is generally from
1:1 to 1:10, preferably 1:1.5 or 2 up to 1:4 or 1:5.
[0016] In order that the concentrate can conveniently have an appropriately high active
content it is necessary for the weight of reactive size to be at least 0.67 parts
per part by weight organic solvent (i.e. 40% solution). The weight ratio organic solvent:
reactive size is generally from 1:10 to 1:0.67 preferably 1:1 to 1:3.
[0017] With the most dilute solution of reactive size in solvent that is generally used
in the invention (40 parts size to 60 parts solvent) the amount of polyelectrolyte
is generally between 4 parts and 40 parts, giving sizing compositions having a reactive
size content of from 38.4 to 28.6%. A composition having 83.3% reactive size can be
formed from, for instance, 100 parts reactive size, 10 parts solvent and 10 parts
polyelectrolyte.
[0018] Preferred compositions have, per part solvent, about 1 to 3 parts (preferably about
2 parts) reactive size and about 0.5 to 2 parts (preferably about 1 part) polyelectrolyte.
[0019] The concentrate composition must be substantially anhydrous in order that the composition
is stable, and in practice this means that if water is present its amount will be
not more than 10% and preferably not more than 5% by weight of the composition. Preferably
the water content is not more than 1% or, at the most, 2% by weight of the composition.
The amount of water is generally insufficient to form a solution of the polyelectrolyte
and preferably is not significantly more than, and most preferably is the same as
or less than, the equilibrium moisture content of the polyelectrolyte (i.e. the water
content of the electrolyte if it is exposed in the form of dry powder to the ambient
atmosphere).
[0020] The organic liquid in which the polyelectrolyte is dispersed is a solution of the
reactive size in a hydrophobic solvent. Suitable solvents are water immiscible organic
hydrocarbon liquids such as benzene, xylene, toluene, mineral oils, kerosene, and
vegetable oils. In addition to being substantially free of water the composition is
preferably also substantially free of any highly polar liquids with which the reactive
size might tend to react. Preferably the liquid phase of the composition consists
essentially only of hydrophobic solvent and dissolved size.
[0021] Any type of reactive size may be used in the invention but the size preferably is
a ketene dimer reactive size or an anhydride reactive size.
[0022] Suitable ketene dimer reactive sizes that may be used include the dimers derived
from readily available commercial fatty acids such as palmitic, stearic, oleic or
myristic acids or mixtures thereof. Naturally the ketene dimer must be soluble in
the organic liquid chosen for the polymer-in-oil dispersion. Suitable materials are
well known and are described in, for example, U.S. Patent Specification No. 3,046,186.
The ketene dimer may be solid or liquid, but generally the most concentrated products
are obtainable when the dimer is liquid.
[0023] Suitable anhydride reactive sizes that may be used include alkenyl succinic anhydride
sizes. Suitable materials are described in U.S. Patent No. 3,102,064.
[0024] The polyelectrolyte will generally be water soluble and an advantage of the invention
is that it can have a any desired molecular weight and in particular can have a molecular
weight that is higher than is conveniently possible with existing compositions. For
instance the intrinsic viscosity can typically be between 1 and 20, generally 3 to
9.
[0025] The polyelectrolytes may be cationic, anionic or non-ionic, the cationic polyelectrolytes
generally being preferred.
[0026] Preferred cationic electrolytes include homopolymers or copolymers of diallyl dialkyl
(generally dimethyl) ammonium chloride and homopolymers and copolymers of dialkylaminoalkyl
acrylates and methacrylates (preferably dimethylaminoethyl acrylates and methacrylates)
present as acid addition salts or quaternary ammonium salts, generally quaternised
with methyl chloride or dimethyl sulphate. Copolymers of such monomers may be formed
with acrylamide or methacrylamide and will typically contain at least 10%, and usually
at least 30%, by weight of the cationic monomer. Other cationic acrylamides and methacrylamides
can be used. Other cationic polymers that can be used are polyamines and polyimines
such as polyamine-epi-halohydrin polymers and dicyandiamide condensates and polyethylene
imines.
[0027] Suitable non-ionic polymers include polyacrylamide.
[0028] Suitable anionic polymers include polymers formed from monomers including carboxylic
or sulphonic acid groups. These groups may be present as free acid or, more usually,
as a water soluble ammonium or alkali metal (generally sodium) salt. Suitable acids
are acrylic acid, methacrylic acid and 2-acrylamido-2-methyl-propane sulphonic acid.
The anionic polymers may be homopolymers of such acids, or mixtures thereof, or copolymers
with, for instance, acrylamide. A suitable polymer is polyacrylamide containing up
to 25% or more acrylic acid groups.
[0029] The concentrate composition is best made by adding the reactive size to a substantially
anhydrous dispersion of a polyelectrolyte in the hydrophobic liquid and thereby forming
a solution of the size in the hydrophobic liquid. The dispersion of the polyelectrolyte
in the hydrophobic liquid may be made by dispersing powdered polyelectrolyte mechanically
into the liquid or by forming a dispersion in the hydrophobic liquid of aqueous polymer
and then dehydrating this dispersion, generally by azeotroping. This dispersion may
be made by dispersing aqueous polymer solution into the hydrophobic liquid or by,
for instance, reversed phase emulsion or suspension polymerisation. Thus an aqueous
solution of the monomer or monomers from which the polyelectrolyte is to be formed
may be dispersed in an oil phase and then polymerised by emulsion or suspension polymerisation
mechanism to form aqueous polymer droplets dispersed in the oil phase, and the composition
is then dried. Any aqueous dispersion is preferably formed initially in the presence
of a polymeric dispersion stabiliser (for instance as described in British Patent
Specification No. 1,482,515) and possibly also a water-in-oil emulsifying surfactant
and the oil that will facilitate subsequent drying of the product by azeotroping.
[0030] A user composition is made from the concentrate composition, generally by the user,
by adding the concentrate composition to water and thereby forming an oil-in-water
emulsion of the size solution dispersed in water in which the polyelectrolyte is dissolved.
Formation of the oil-in-water emulsion is promoted by application of mechanical high
shear and/or by the presence of an oil-in-water emulsifying agent, such as an ethoxylated
nonyl phenyl. The oil-in-water emulsifying agent may be included in the concentrate
or in the water in which the emulsion is formed.
[0031] The water in which the emulsion is formed may be the water of the cellulosic pulp
suspension that is to be treated but preferably the concentrate is first converted
into an aqueous emulsion to give a reactive size concentration of from 0.01 to 5%,
preferably 0.05 to 1%, based on the weight of the aqueous solution.
[0032] This emulsion may then be added to the aqueous cellulosic pulp, and paper may be
made from it, in the usual way. The amount of reactive size in the aqueous pulp is
generally from about 0.01 to about 1% by weight based on the dry weight of the pulp.
Upon addition to the pulp slurry, the active size/oil droplets are retained by the
polymer on the fibres and the size reacts with the fibres. The size released from
an emulsion in this way produces results at least as good as those obtained with the
conventional ketene dimer emulsions.
[0033] Thus by the invention we obtain sizing results at least as good as those obtained
using known compositions and yet for the first time we have the ability of supplying
storage stable concentrated compositions that the user can easily convert into aqueous
solutions.
[0034] The following are examples of the invention.
Polyelectrolyte Dispersions:
[0035] A substantially anhydrous dispersion of a copolymer of methyl chloride quaternised
dimethylaminoethyl methacrylate (DMAEMA) and acrylamide was prepared by a reverse
phase dispersion polymerisation process. The acrylamide was supplied as a 57% aqueous
solution and the quaternised monomer was a 65% aqueous solution. These solutions were
dispersed in a blend of Solvent Pale Oil 150 and perchloroethylene in the presence
of a polymeric stabiliser and a very small amount of emulsifier. Polymerisation was
initiated and allowed to complete in conventional manner and the resultant product
was distilled under reduced pressure to remove the water and the perchloroethylene.
The Intrinsic Viscosity of this polymer (and of the polymers in each of Dispersions
A to E below) was in the range 4 to 6.
[0036] In one process the ratio DMAEMA:acrylamide was 80:20 by weight and the resultant
polymer dispersion, labelled Dispersion A, contained 47.5% by weight of active polymer.
A 1% solution of the polymer in water had a RVT Brookfield Viscosity of 6,400 cps
at room temperature using spindle No. 3 rotating at 10 rpm.
[0037] In another experiment the monomer proportions were the same and the molecular weight
of the resultant polymer was above 10
6. The resultant dispersion was labelled Dispersion B.
[0038] In another process, a dispersion, labelled Dispersion C, was obtained broadly as
described for Dispersion A and was a 50% active polymer dispersion in mineral oil.
[0039] In another process the ratio DMAEMA:acrylamide was 30:70 by weight and the resultant
dispersion, labelled Dispersion D, contained 50% by weight active polymer. The polymer
in the dispersion was of low molecular weight, having an intrinsic viscosity of 3.16.
[0040] In another process a substantially anhydrous dispersion of a polyamine-epichlorhydrin
condensate was prepared by emulsifying the polymer produced in an aqueous phase polymerisation
process into a mixture of solvent pale oil 60 and SBP 11 with a very small amount
of emulsifiers prior to distilling off the water under reduced pressure. The resultant
polymer dispersion, labelled Dispersion E, contained 37.6% by weight of active polymer.
EXAMPLES 1 to 5
[0041] A series of concentrate compositions according to the invention were made by dissolving
a reactive size in each of Dispersions A to E.
[0042] In Example 1 the size was hexadecenyl dimer and the concentrate contained 1.05g Dispersion
A and 4g of hexadecenyl ketene dimer, and 1g of an oil-in-water emulsifier to give
a 64.5% active sizing composition. The water content of the concentrate was less than
1%. The product is concentrate A.
[0043] In Example 2 the concentrate was made by mixing 2 ml of Dispersion B with 2 ml octadecenyl
ketene dimer, to make concentrate B.
[0044] In Example 3 one part by weight Dispersion C was mixed with one part by weight alkenyl
succinic anhydride reactive size to form concentrate C.
[0045] In Example 4 alkenyl succinic anhydride was dissolved into a mixture of Dispersion
D and a mineral oil such that concentrate D contained 2g Dispersion D, 5g alkenyl
succinic anhydride, 2.25g mineral oil and 0.75g of an oil-in-water emulsifier to give
a 50% active sizing concentrate D, having a water content of less than 1%.
[0046] In Example 5 alkenyl succinic anhydride was dissolved into Dispersion E in the presence
of emulsifiers to form concentrate E containing 5g alkenyl succinic anhydride, 5.31g
Dispersion E and 1.28g of the oil-in-water emulsifiers to give a 43.1% active size
concentrate.
[0047] Each of concentrates A to E was used to prepare a corresponding aqueous emulsion,
having a 1% by weight active size content, by stirring the appropriate amount of dispersion
into water. Each of these 1% active emulsions was further diluted to 0.1% by weight
active size content and these 0.1% emulsions were labelled Emulsions A to E (having
been prepared from, respectively, concentrates A to E).
[0048] The effectiveness of each of the emulsions for sizing cellulosic fibres was determined
by the 1 minute Cobb Test. In each of these tests hand sheets were prepared on a standard
laboratory sheet making machine from a stock containing calcium carbonate and the
sheets were then dried and the 1 minute Cobb value determined. For Emulsions A to
D the stock was a bleached sulphate/bleached bird stock but for Emulsion E it was
a bleached sulphate (kraft).
[0049] In Test A the hand sheets were 100 g.sm and the stock contained 20% calcium carbonate
and was a 0.5% constituted stock. The emulsion was either Emulsion A or, as a comparison,
with Emulsion F which was a conventional emulsion prepared from a commercially available
6% emulsion of ketene dimer in water stabilised with cationic starch.
[0050] In Test B hand sheets were prepared from a furnish of 50% bleached sulphate, 40%
bleached birch and 10% calcium carbonate, beaten to a freeness of 52° S.R. The stock
was sized with Emulsion B or, as a comparison, with Emulsion G obtained by mixing
2 ml of the 50% dispersion of polymer in oil used in the preparation of Dispersion
B into 196 mls deionised water followed by rapid stirring with a Silverson mixer at
maximum speed and injection into the resultant solution of 2 mls octadecenyl ketene,
Silverson mixing being continued for a further 25 seconds. The resultant 1% emulsion
was diluted to 0.1% to form Emulsion G.
[0051] In Test C 70 gsm hand sheets were prepared from a stock of 50 parts bleached sulphate,
40 parts bleached birch and 10 parts calcium carbonate and these were sized either
with Emulsion C or with comparison Emulsion H. This was prepared as follows. A 12%
aqueous dispersion of a cationic starch was cooked at 95°C for 20 minutes with constant
stirring. The cooked starch was cooled and diluted to 9% activity. 2 parts by weight
of alkenyl succinic anhydride was added to 3 parts by weight of cationic starch with
agitation. High shear mixing using a Silverson mixer was continued to achieve a fine
particle size emulsion. This emulsion was diluted with water to 0.75% active size,
which was further diluted to 0.1%.
[0052] In Test D 70 gms hand sheets were prepared from a stock of 50 parts bleached sulphate,
40 parts bleached birch and 10 parts calcium carbonate beaten to 50° S.R. and after
manufacturer the sheets were placed on glazing plates and pressed at 3.5 kg/cm
2 for 5 minutes prior to drying on rings at 110°C for 2 hours. Emulsion D was used
for sizing each of these sheets.
[0053] In Test E 70 gms hand sheets were prepared from a bleached sulphate stock in conventional
manner and dried and pressed as in Test D, the sheets being sized using Emulsion E.
[0054] The dosage and the Cobb value are shown in the following Table. The dosage is recorded
as percent active size based on dry weight of paper. The Cobb figure is the 1 minute
Cobb value.

[0055] These results show that the methods and emulsions of the invention, A to E, are all
capable of giving satisfactory sizing. Test C shows that the results can be similar
to those obtainable with a conventional commercially available 2-pack system H while
Test B shows that the results can be surprisingly better than the results obtained
by sequential formation of a single emulsion, G. Test A shows that the results can
be better than obtainable with a conventional emulsion system. Similarly satisfactory
results are obtained when the polymer is polyacrylamide containing 10% molar acrylic
acid groups (as sodium salt) and the stock contains alum and has a pH of 5.5.
[0056] Additional to these results is the remarkable convenience of the invention to the
mill operator in that instead of having to purchase or prepare large volumes of a
dilute emulsion, which then have to be stored at the mill, it is possible for the
mill operator to purchase or prepare small volumes of a very concentrated emulsion
and merely dilute this at the point of use when required.
1. A concentrate composition suitable, upon dilution with water, for sizing cellulosic
fibres and comprising a substantially anhydrous dispersion of a polyelectrolyte in
an organic liquid comprising a solution of a reactive size in a hydrophobic solvent.
2. A composition according to claim 1 in which the concentration of reactive size
is above 20% by weight of the total composition and above 40% by weight of the combined
weight of size and solvent.
3. A composition according to claim 1 in which the concentration of the reactive size
is 30 to 85% by weight of the total composition and the weight ratio organic solvent:reactive
size is from 1:10 to 1:0.67.
4. A composition according to any preceding claim in which the weight ratio polyelectrolyte:
reactive size is from 1:1 to 1:10.
5. A composition according to any preceding claim containing, by weight, 1 part solvent,
1 to 3 parts reactive size and 0.5 to 2 parts polyelectrolyte.
6. A composition according to any preceding claim in which the reactive size is selected
from ketene dimer and anhydride reactive sizes.
7. A composition according to any preceding claim in which the polyelectrolyte is
selected from water soluble cationic, anionic and non-ionic polymers.
8. A composition according to any preceding claim in which the polyelectrolyte is
selected from polymers formed from at least one monomer selected from dialkylaminoalkyl
acrylates and methacrylates and their acid addition salts and their quaternary ammonium
salts, diallyl dialkyl ammonium chlorides acrylamide, acrylic acid, methacrylic acid
and 2-acrylamido-2-methyl propane sulphonic acid and from polyamine and polyimine
polymers.
9. A composition according to any preceding claim additionally including an oil-in-water
emulsifier.
10. A composition according to any preceding claim that has been made by adding the
reactive size to a substantially anhydrous dispersion of the polyelectrolyte in the
hydrophobic liquid.
11. A composition according to any preceding claim that has been made by forming an
aqueous dispersion of the polyelectrolyte in hydrophobic liquid by reverse phase polymerisation,
dehydrating the dispersion by azeotroping and then adding the reactive size.
12. An aqueous composition obtained by dispersing into water a concentrate according
to any preceding claim in an amount sufficient to give a reactive size concentration
in the water of from 0.01 to 5% by weight.
13. A method in which cellulosic fibres are sized by treating aqueous cellulosic pulp
or cellulosic paper made from such pulp with an aqueous composition according to claim
12.