COMPOSITIONS DE COLLAGE POUR PAPIER

PAPER SIZING COMPOSITIONS

Abrégé anglais

A one-shot paper sizing composition is in the
form of an aqueous dispersion containing a rosin
component, a co-reactant therefor, such as an aluminium
chlorohydrate, and an amine or an amine salt of a rosin
acid.

Revendications

-18-
The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as
follows:
1. A paper-sizing composition in the form of a
preformed stable aqueous dispersion for subsequent use
in a paper-sizing process, the composition having the
ability to size paper stock, sheet or web to an
effective extent when brought into contact with the
stock, sheet or web during the sizing process, the
composition comprising:
a rosin size component,
an amine salt of a rosin acid which is a
salt of a C1 to C4 mono-, di- or tri-alkanol amine and
a rosin acid, and
at least one aluminium compound.
2. A composition according to claim 1, wherein
the amine salt of a rosin acid is the product of
neutralization with the amine of a component selected
from rosin, fortified rosin, disproportionated rosin
and mixtures thereof.
3. A composition according to claim 1 or 2,
wherein the amine salt is present in an amount
representing from 1% to 20% of neutralization of the
acid groups in the rosin component.
4. A composition according to claim 1, 2, 3 or
4, wherein the amine salt is the salt of triethanol
amine and rosin acid.
5. A composition according to claim 1, 2 or 3
wherein said amine of said amine salt is of formula:

-14-
<IMG>
wherein R1, R2 and R3, which may be the same or
different, are selected from hydroxyalkyl of 1 to 4
carbon atoms or hydrogen, provided that at least one
of R1, R2 and R3 is a said hydroxyalkyl of 1 to 4
carbon atoms.
6. A composition of claim 1, 2 or 3, wherein
said amine of said amine salt is of formula:
<IMG>
wherein R1, R2 and R3, which may be the same or
different, are selected from alkyl or alkenyl of 1 to
4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms or
hydrogen, provided that at least one of R1, R2 and R3
is a said hydroxyalkyl of 1 to 4 carbon atoms.
7. A composition according to claim 1, 2, 3, 4,
5 or 6, wherein the aluminium compound is selected
from aluminium sulphate, papermaker's alum,
polyaluminium chloride and aluminium chlorohydrates.
8. A composition according to claim 1, 2, 3, 4,
5 or 6, wherein the aluminium compound is selected
from polyaluminium chloride and aluminium
chlorohydrate.

-20-
9. A composition according to claim 1, 2, 3, 4,
5, or 6, wherein the aluminium compound is a
polyaluminium chloride having the general formula:
Al(OH)x(SO4)y Cl z
wherein x has a value in the range from 1.35 to 1.65,
y has a value of from 0.08 to 0.15 and z has a value
of 3-(x+y), or having the general formula:
Al n(OH)m Cl3n-m
wherein n has a value of from 1 to 20, m is less than
3n and (3n-m)/m is at least 2, or an aluminium
chlorohydrate having the general formula:
Al x(OH)y Cl z
wherein x has a value of from 1 to 4, y and z, which
may be the same or different, have values of from 0.5
to 2.5 and the ratio y:z has a value in the range of
from 5:1 to 1:5.
10. A composition according to claim 1, 2, 3, 4,
or 6, wherein the aluminium compound is a
polyaluminium chloride having the general formula:
Al(OH)x(SO4)y Cl z
wherein x has a value in the range from 1.35 to 1.65,
y has a value of from 0.08 to 0.15 and z has a value
of 3-(x+y).
11. A composition according to claim 1, 2, 3, 4,
or 6, wherein the aluminium compound is a
polyaluminium chloride having the general formula:

-21-
Al n(OH)m Cl3n-m
wherein n has a value of from 1 to 20, m is less than
3n and (3n-m)/m is at least 2.
12. A composition according to claim 1, 2, 3, 4,
5 or 6, wherein the aluminium compound is an aluminium
chlorohydrate having the general formula:
Al x(OH)y Cl z
wherein x has a value of from 1 to 4, y and z, which
may be the same or different, have values of from 0.5
to 2.5 and the ratio y:z has a value in the range of
from 5:1 to 1:5.
13. A composition according to any one of claims
1 to 12, wherein a stabilizer selected from the group
consisting of protective colloids, starch derivatives,
cellulose derivatives, polymeric materials and
anionic, nonionic, cationic and amphoteric
surfactants, water-soluble polyaminopoly-
amide/epichlorohydrin resins, water-soluble
alkylenepolyamine/epichlorohydrin resins and poly(diallyl-
amine)/epichlorohydrin resins, is present in the
composition.
14. A composition according to any one of claims
1 to 12, wherein urea or a chemically modified urea is
present in the composition.
15. A composition according to any one of claims
1 to 12, wherein at least one alkenyl succinic
anhydride or alkyl ketene dimer synthetic size is
present in the composition.

-22-
16. A composition according to any one of claims
1 to 15, which comprises from 25 to 60% by weight of
the combined rosin component, aluminium compound and
amine salt.
17. A method of manufacturing a rosin based
paper sizing composition in the form of an aqueous
dispersion, comprising:
first forming an aqueous dispersion
comprising rosin size and an amine salt of a rosin
acid which is a salt of a C1 to C4 mono-, di- or
tri-alkanol amine and a rosin acid and then introducing at
least one aluminium compound into the dispersion.
18. A method according to claim 17, wherein the
amine salt is the triethanol amine salt of rosin acid.
19. A method according to claim 17, wherein said
amine of said amine salt is of formula:
<IMG>
wherein R1, R2 and R3, which may be the same or
different, are selected from hydroxy alkyl of 1 to 4
carbon atoms or hydrogen, provided that at least one
of R1, R2 and R3 is a said hydroxyalkyl of 1 to 4
carbon atoms.
20. A method according to claim 17, wherein said
amine of said amine salt is of formula:

-23-
<IMG>
wherein R2, R2 and R3, which may be the same or
different, are selected from alkyl or alkenyl of 1 to
4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms or
hydrogen, provided that at least one of R1, R2 and R3
is a said hydroxyalkyl of 1 to 4 carbon atoms.
21. A method according to claim 17, 18, 19 or
20, wherein the aluminium compound is a polyaluminium
chloride.
22. A method according to claim 17, 18, 19 or
20, wherein the aluminium compound is an aluminium
chlorohydrate.
23. A method according to any one of claims 17
to 22, wherein a water-in-oil emulsion comprising the
rosin component and at least one stabilizer is made
and is subjected to an inversion technique so as to
form an oil-in-water emulsion, which is then blended
with at least one aluminium compound to form said
composition.
24. A process of manufacture of a sized paper
product, wherein a paper sizing composition is added
to fibre stock which is then made into paper or is
applied as a surface size to prepared paper web or
sheet wherein the composition is a composition
according to any one of claims 1 to 16.

-24-
25. A process according to claim 24, wherein the
composition is employed in an amount in the range from
0.1% to 5.0% by weight of solids based on the weight
of fibres in the pulp used to make the paper product.

Description

13403~9
PAPER SIZING COMPOSITIONS
This invention relates to paper sizing
compositions, methods for making such compositions,
processes for sizing paper products using these
compositions and paper products which have been sized
with these compositions.
Stable dispersions of rosin or rosin-based
products are well-known and have long been used,
especially as sizing agents in the manufacture of paper.
In this specification, the term "paper" is used, for
convenience, to mean all forms of paper, paperboard and
related products whose manufacture involves the
employment of a sizing agent upon cellulosic or other
fibres. Paper sizing agents are usually employed either
by being added to the cellulosic or other fibre stock
from which a web is later made or by being applied to
the surface after the web has been formed. Rosin-based
sizing agents depend for their sizing effect upon the
formation of electrostatic bonds between the sizing
agent and the cellulosic or other fibres of the paper
stock or web. Highly efficient sizing agents have been
developed more recently which include many kinds which,
in use, form chemical bonds and these are thus known as
"reactive" sizing agents. A major development in the
paper-making size art was the discovery that reaction
products formed by rosin or unsaturated compounds
present in rosin, on the one hand, and unsaturated
carboxylic acids or their anhydrides, especially maleic
or fumaric acid or maleic anhydride, on the other hand,
have greatly enhanced sizing efficiency, as compared
with those kinds of sizing agents which are essentially
dispersions of rosin itself. These so-called
"maleated" rosin reaction products and other related
sizing agents are rather ~Ypensive to make and so they
are often used to fortify conventional rosin
B ~

134033~
dispersions, rather than to replace them. This is done
by adding a quantity of a "maleated" rosin reaction
product to a conventional rosin dispersion and the
resultant compositions are commonly known as "fortified
sizing agents."
In practice, all types of paper sizing agents are
usually in the form of stable dispersions and they
cause sizing by depositing rosin-based or other
materials on to the fibre stock or the paper web, so
that sizing essentially involves breaking the stable
dispersion. This can occur on contact between the
dispersion and the stock or web, where the latter is
effective to destroy the stability of the dispersion.
Usually, however, adequate sizing does not arise from
mere contact of the paper sizing agent with the paper
stock or web. Instead, it requires the presence of a
co-reactant to break the dispersion and so cause the
desired deposition of sizing components on the fibres of
the paper stock or web. The most commonly employed
co-reactants are aluminium compounds and, especially,
aluminium sulphate, papermaker's alum and the
polyaluminium chlorides.
The majority of paper-making processes involve the
separate addition or application of the rosin-based
size and a co-reactant to the paper stock or the paper
web. There have been proposals, notably those in
published U.K. Patent Applications 2050453A and
2159183A and U.S. Patent 4522686, to prepare sizing
compositions comprising both a rosin component and a
suitable reactant, which compositions offer the
advantage of sizing using a single composition, but
these have not been entirely successful, either because
the dispersions are unstable or because their
effectiveness as a size has been reduced. For whatever
reason, the majority of paper mills utilise a sizing
process which
.~,,

13~0333
involves the use of two separate components, despite
the inherent difficulties involved.
It has been discovered that dispersions, compris-
ing a rosin component and an amine salt of a rosinacid, which are stable and which impart excellent
sizing properties to paper, can be prepared by the
incorporation of at least one aluminum compound into a
composition of a rosin size or an amine salt of a
rosin acid.
In this invention there is provided a paper-
sizing composition in the form of a preformed stable
aqueous dispersion for subsequent use in a paper-
sizing process, the composition having the ability to
size paper stock, sheet or web to an effective extent
when brought into contact with the stock, sheet or web
during the sizing process and comprising the material
obtainable by addition of at least one aluminum
compound to an aqueous dispersion comprising rosin
size and an amine salt of a rosin acid, more
especially a Cl to C4 mono-, di- or tri-alkanol amine
salt.
Thus in accordance with one aspect of the
invention there is provided a paper-sizing composition
in the form of a preformed stable aqueous dispersion
for subsequent use in a paper-sizing process, the
composition having the ability to size paper stock,
sheet or web to an effective extent when brought into
contact with the stock, sheet or web during the sizing
process, the composition comprising: a rosin size
component, an amine salt of a rosin acid which is a
salt of a Cl to C4 mono-, di- or tri-alkanol amine and
a rosin acid, and at least one aluminium compound.

13~0~33
3a
In another aspect of the invention there is
provided a method of manufacturing a rosin based
paper-sizing composition in the form of an aqueous
dispersion, comprising: first forming an aqueous
dispersion comprising rosin size and an amine salt of
a rosin acid which is a salt of a Cl to C4 mono- di-
or tri-alkanol amine and a rosin acid and then
introducing at least one aluminium compound into the
dispersion.
In still another aspect of the invention there is
provide a process of manufacture of a sized paper
product, wherein a paper sizing composition is added
to fibre stock which is then made into paper or is
applied as a surface size to prepared paper web or
sheet wherein the composition is a composition of the
invention as described hereinbefore.
Rosin is a solid resinous material which occurs
naturally in the oleoresin of pine trees. It is
obtained from one of three main sources, the oleoresin
exudate of living pine trees, the oleoresin contained
in the aged stumps of pine trees and from the tall oil
produced as a by-product in the kraft paper industry.
Rosin is a complex mixture of cyclic terpene
carboxylic acids together with a small amount of non-
acidic components. A major constituent of rosin is
the tricyclic doubly unsaturated mono-carboxylic acid,
abietic acid.
'~,
~J

1~03~9
Abietic acid undergoes Diels-Alder addition with
dienophiles. Rosin may therefore be reacted with
dienophilic carboxylic acids such as maleic acid,
maleic anhydride or fumaric acid to form a tetracyclic
polycarboxylic acid. This reaction with these
dienophiles is commonly termed fortification. The
product of such reaction between rosin and a
dienophile is commonly termed a fortified rosin.
Fortified rosin dispersions are used as sizing
compositions in the paper sizing industry and the
novel dispersions of this invention may comprise
either rosin or fortified rosin or a mixture of the
two. The rosin may have been treated with
formaldehyde in order to enhance their stability.
Esterified or disproportionated rosins may also be
used in the compositions of this invention.
Esterified rosins are rosins which have been reacted
with an alcohol which is preferably a polyol such as
glycerol. Disproportionated rosins are rosins which
have been treated by a catalytic process in order to
improve their stability to oxidation. Mixtures of any
of these types of rosin may be used in the
compositions of this invention.
The preferred rosin for use in the composition of
this invention are fortified rosins. The preferred
fortified rosins are those wherein the rosin has been
reacted with from 5 to 50% of its own weight and
generally about 10% by weight of a dienophile. Such
rosins comprise a mixture of fortified and unfortified
rosin. The two are normally used in combination in
view of the fortification which would render the use
of a product comprising fortified rosin only
prohibitively expensive. The most preferred type of
rosin is fortified tall oil rosin.

13~0 ~3g
4a
The amine salt of the rosin acid may be produced
by the neutralization of any of the rosin or rosin
derivatives described above. It may be prepared
separately and added to the rosin dispersion, but more
usually it will be produced in situ by the addition of
sufficient amine to bring about the partial
neutralization of the acid content of the rosin. Thus
in a preferred embodiment the amine salt is the salt
of the rosin acid or acids present in the rosin
component of the dispersions of this invention.
The salt of the rosin acid may be produced by
neutralization the acid either prior to or after its
conversion to a rosin derivative. The neutralization
may be carried out using an amine having the formula:
N
/ \
R2 R3

13~0~39
wherein substituents Rl, R2 and R3, which may be the
same or different, represent alkyl or alkenyl groups
comprising from 1 to 4 carbon atoms or a hydrogen
atom, with the proviso that at least one of the
substituent is not a hydrogen atom, and at least one
of Rl, R2 and R3 is a Cl to C4 alkyl substituted by
hydroxyl. Preferably at least two of the substituents
groups Rl, R2 and R3 represent alkyl groups and, most
preferably, all three of these substituents represent
alkyl groups. Those of Rl, R2 and R3 which represent
alkyl groups may represent branched or straight chain
saturated alkyl groups such as methyl, ethyl, or n- or
iso- propyl, n-, sec- or tert- butyl groups or they
may represent alkyl groups which contain one or more
substituent groups such as hydroxyl, alkoxy, carboxy
or amino groups, for example, two hydroxyethane groups
or hydroxypropane groups. Particular amines which are
useful in the composition of this invention include
monoethanolamine, diethanolamine and triethanolamine.
The most preferred amine is triethanolamine. The
amount of amine which is added to the rosin will be
that which is required in order to produce the desired
amount of amine salt. Where the product is to be used
directly to provide both
D

-- 13~0~
the rosin component and the amine salt component of the
dispersion, the amount of amine which is added will
normally be sufficient to neutralise from 1 to 20%,
preferably from 3 to 6% of the acid groups present in
the rosin. Where the rosin component and amine salt
component are prepared separately, and subsequently
mixed, the amount of amine salt will normally be such
that the mixture comprises the same proportions of
neutralised and non-neutralised rosin acids.
The co-reactant component of the dispersions of
this invention may be of any of the aluminium salts
known to be useful in the sizing of paper such as
aluminium sulphate, paper maker's alum A12(SO4)3.18H2O,
polyaluminium chlorides such as those having the formula
Al(OH)x(sO4)yclz
wherein x has a value in the range 1.35 to 1.65, y has a
value of from 0.08 to 0.15 and z has a value of 3-(x+y),
or those having the formula:
Aln(OH)m~Cl3n-m
wherein n has a value of from 1 to 20, m is less than 3n
and 3n-m is at least 2 and preferably at least 5.
m
A particular type of polyaluminium chloride which
is useful in the dispersions of this invention are those
described in published European Patent Application
145686 and those produced by the processes described in
published European Patent Application 181847. Another
type of useful polyaluminium chloride are the aluminium
chlorohydrates having the formula:
Alx(OH)yClz
wherein x has a value of from 1 to 4, preferably a value
of 1, y and z, which may be the same or different, have
values of from 0.5 to 2.5 and the ratio y:z has a value
in the range 5:1 to 1:5.
The preferred co-reactant for use in the
compositions of the present invention are the aluminium
chlorohydrates.
,, ~'

1340~3~
The dispersions of the present invention may be
prepared by simple admixture of the components thereof
or by using any of the conventional tPchn;ques of the
art. In particular the dispersions may be prepared
using the inversion tPchnique. In another aspect of the
present invention, there is provided a method of
manufacture of the paper-sizing composition which
comprises first forming an aqueous dispersion comprising
the rosin size and amine salt of a rosin acid and then
introducing the aluminum compound into the dispersion.
The rosin, preferably a fortified rosin, optionally
treated with para formaldehyde in the presence of a para
toluene sulphonic acid to inhibit crystallisation, and
optionally one which has been at least partially
neutralised with an amine, may be melted and a
stabilising agent or mixture of stabilising agents may
then be added as a concentrated (e.g. 50% by weight
solids) aqueous solution. Sufficient water is stirred
in to form a creamy water-in-oil emulsion (e.g. 20 to
40% based on the weight of rosin). On dilution with
water the emulsion inverts to provide a stable oil-in-
water emulsion, typically having solids content of from
20% by weight up to the maximum achievable oil-in-water
concentration (often about 80% by weight solids) and
preferably from 30% to 40% by weight solids. The rosin
content of the emulsion or dispersion usually contains
at least 90% of unsaponified rosin acids. The
emulsions may then be blended with an aqueous solution
of one or more co-reactants.
The emulsions may be used for sizing paper,
including alumed paper. In a further aspect, the
present invention provides a process of manufacture of a
sized paper product wherein a paper-sizing composition
in accordance with the one aspect of the invention is
addéd to fiber stock which is then made into paper or is
L~
. . ..

13~0~33
applied as a surface size to a prepared paper melt or
sheet.
The rosin dispersions may be formulated so as to
comprise other ingredients known in the art. In parti-
cular the dispersions may comprise one or more stabil-
isers. A variety of surface active agents or
emulsifiers may be used to stabilise the dispersions
either in admixture with one another or with other
known emulsifying agents or in conjunction with other
known auxiliary stabilising agents. A preferred class
of auxiliary stabilising agents are the protective
colloids such as casein and compositions comprising
rosin, an amine salt of a rosin acid, a co-reactant and
a protective colloid form a preferred aspect of this
invention. Other compounds which may be used to sta-
bilise the dispersions include starch derivatives,
cellulose derivatives such as hydroxyethyl cellulose, or
polymeric materials such as polyvinyl pyrolidone.
Anionic, non-ionic, amphoteric, or cationic
surfactants may be utilised as stabilisers in the
dispersions of this invention. In general we prefer to
utilise anionic or non-ionic surfactants.
Examples of surface active agents which find use in
the compositions of this invention include
(i) salt of sulphonic acids having the general
formula:-
(R')m ~ ~ ~(C2H4~)n -CH2 CH CH2 SO3M
where R' represents a hydrocarbon residue having from
4-18 carbon atoms, m is an integer having a value of 1
or 2, n is an integer having a value of 4 to 25, X
represents a hydrogen atom or a hydroxyl group and M
represents a monovalent cation and
f
L B

13~0~3~
(ii) salts of sulphuric acid half esters having the
general formula:-
R2 _ ~ -A 2 ~ ~ ~ o(C2H40)pS03Q
wherein R2 represents a hydrogen atom or an alkyl group
having from 1 to 4 carbon atoms, A represents a straight
chain or branch chain alkylene group having 2 or 3
c~rhon atoms, p is an integer having a value of from 4
to 25 and Q is a monovalent cation including all those
comp~nA~ described in United States Patent 4309338.
Alkyl benzene sulphonates wherein the alkyl
substituent comprises from 8 to 24 carbon atoms
including all those compounds described in United States
Patent 4157982.
Sulphosuccinate half esters of fortified rosin
having the formula:-
H(3_m). R- t(CH2CH20)n -OC.C2H3S03Na. COONa]m;
wherein R is a fortified rosin acid tricarboxylate
group, m has an average value of from 1.5 to 3, and n
has an average value from 4.5 to 25; including all those
described in published European Patent Application
159794.
Compounds having one of the formula:-
~ 0(cH2cH2o)n S03 M~
or
R~ _ 0(cH2cH2o)n S03 M+
wherein R represents an alkyl group comprising from 4 to18 carbon atoms and R' represents an alkyl or alkenyl
group comprising from 4 to 18 carbon atoms and n is an
g' -?,

134Q~
integer having a value of from 4 to 25 including all
those described in United States Patent 4,199,369.
Sulphnc~ccinate salts of ethylene oxide ron~nC~tes
having the general formula:-
0 0
~ 0(CH2CH20)n C - C~ CH2 C0~ M+
wherein R represents an alkyl group comprising from 4 to
18 c~rho~ atoms and n i5 an integer having a value of
from 4 to 25; including all those compounds described in
United States Patent 4,203,776.
- organic phosphate esters having the general
formulae:-
R 0 (CH2 CH2 ~)n ~ ~ ~
O X / ~ o X
R 0 (CH2 CH2 ~)n ~ ~
p
/ \O X
R 0 (CH2 CH2~)n
and mixtures thereof
wherein R represents an alkyl an alkyl phenol, alkenyl
or alkaryl group comprising from 5 to 20 carbon atoms, n
has a value of from 5 to 20 and X represents a
monovalent cation or hydrogen.

1340~39
~ o
Cationic resin dispersant systems may also be used to stabilise
the rosin dispersion of this invention. Examples of suitable
materials include water soluable polyaminopolyamide epichlorohydrin
resins, water soluble alkylene polyamine epichlorohydrin resins or
poly(diallyl-amine) epichlorohydrin resins.
A further type of compound which can usefully be incorporated
into the dispersions of this invention is that comprising ammonia or
an ammonium salt or a precursor thereof such as urea, a chemically
modified urea or a precursor thereof. Examples of compounds which
are useful in the compositions of this invention include urea~
thiourea, biuret. melamine, water-soluble urea-formaldehyde and
melamine formaldehyde resins and derivatives of urea, especially
those reaction products obtained by reacting urea with an acid
selected from the group comprising sulphamic acid, phosphoric acid,
trichloroacetic acid, nitric acid, sulphuric acid, hydrochloric
acid, stearic acid and acetic acid as described in United States
Patent 4022634 and 4093779, the reaction products of urea with a
Lewis acid such a p-toluene sulphonic acid as described in United
States Patent 4141750, the reaction products of urea and sulphamic
acid such as are described in United States Patent 4025354 and the
products obtained by the reaction of urea and formic acid as
described in United States Patent 4437894.
The preferred sources of ammonia or ammonium salt for use in
the compositions of the present invention are the products obtained
by the reaction of urea with sulphamic acid including all those
products which are described in United States Patent 4025354. These
modified ureas may be produced by combining urea with sulphamic acid
and water. Ideally, the parts by weight of water equal the parts by
weight of urea plus sulphamic acid, although the urea may be treated
with the sulfamic acid with more water or with little or no water.
The urea-sulphamic acid solution may be heated to a temperature
which causes a change in the pH for example to rise in the pH to at
least about 7.5.

13~0 ~39
When little or no water is used the temperature affecting the
pH may be higher. In the preferred embodiment, however, where a 50
water-50X urea sulphamic acid solution is used, a temperature of
about 212~ to 235~F, preferably about 215~ to 230~F will
increase the pH up to at least about 7.9. Generally, the solution
boils at the temperature which changes the pH and heating should be
continued until after boiling has stopped to effect an irreversible
pH change. Althoush the pH range is an important measurement of
reaction completion, a more important consideration is the acidity
of the first stage product measured as parts of water (ppm). When
the sulphamic acid is heated with the urea, undetenmined reactions
occur which not only raise the pH to a basic value, but also affect
the acidity of the solution. The desired minimum acidity is at
least 1,000 ppm, with a preferred minimum 4,300. The actual amount
of sulphamic acid is probably at least about 0 1~ by weight of urea,
with preferred amounts ranging from about 0.2~ to about 8.0X. The
maximum amount of sulphamic acid need~d would be 15 or at most 20X
by weight of urea to achieve the desired results. It has been found
that 5X sulphamic acid produces an acidity of about 86,000 ppm with
a pH of between 7.9 and 8.3 when processed in a 50X water, 50X urea
plus sulphamic acid solution. Accordingly, sulphamic acid at 0 25X
by weight of urea produces a first stage product with an acidity of
4,300 ppm. As indicated, the amount of sulphamic acid added to the
solution is not as important as its resulting acidity in defining
the first stage product of the novel size composition of this
embodiment.
In a preferred embodiment the proportion of ammonia or ammonia
salt (or in the preferred embodiment the precursor thereof) to rosin
or fortified rosin in the dispersions of this invention may be in
the range 5 to 60X and preferably 10 to 35~ by weight.
A further class of ingredients which may usefully be
incorporated into the compositions of this invention are the
synthetic sizes such as alkenyl succinic anhydrides and especially
the alkyl ketene dimers. These reagents may be used as well as or
as a partial replacement for the rosin sizes. ~n general the ratio
, . _

13~0339
of the weight of the rosin components to the synthetic
size components will be in the range 2:1 to 5:1.
The novel dispersions will normally be formulated
as relatively concentrated compositions which are
diluted prior to their use in the sizing process. In
general, the dispersions will comprise from 25 to 60%
and more usually from 30 to 45% by weight of the
combined weight of the rosin, amine salt and co-
reactant.
The compositions of the invention my be employed as
an internal size or as a surface size. Their use as an
internal size forms a preferred aspect of the present
invention. Internal sizing processes comprise the
dilution of the concentrated composition with water and
the addition of the diluted composition to a pulp
suspension. The amount of size composition employed is
generally in the range 0.1 to 5.0% by weight of solids
based on the weight of fibres in the pulp slurry.
The emulsions may be used for sizing paper,
including alumed paper.
The emulsions may contain biocides such as
bactericides, slimicides and/or fungicides or diluents
such as wax.
The invention is illustrated by the following
Examples:
Example 1
Preparation of a Fortified Rosin and a Dispersion of
that Rosin
509 kg of modified tall oil rosin were prepared by
reacting a 100 parts of tall oil rosin (ring and ball
softening point = 60~C) with 0.1 parts of paratoluene
sulphonic acid at a temperature of 165-175~C. After a
15 minute period 2~ parts of paraformaldehyde (82%) was
added over a period of about one hour, maintaining a
temperature of 165-175~C. To this was added 6 parts of
maleic anhydride, this was again allowed to
~,

13~0;339
l3
react over a period of one hour, after an initial exothenm the
temperature was kept at 165-175~C. The rosin was tested for
r~sidual maleic anhydride, using a water wash through a toluene
solution of the rosin product.
. .
The fortified rosin was loaded into a one tonnne pot using an
agitator speed of 300 rpm, water and 10 kg of triethanolamine
was added both to cool and partially neutralise the rosin
product.
When the temperature had dropped to below 100~C a solution
comprising 10 kg of casein, 2 kg of borax and 60 kg of water at
89~C were added quickly to effect inversion.
After allowing to thicken for a period not exceeding S minutes
the emulsion was diluted.
Example 2
S09 kg of a rosin produ~t as produced in Example 1 were loaded
into a one tonne pot using an agitator speed of 300 rpm, water
and 10 kg of triethanolamine was added.
When the temperature had dropped below 100~C a solution
comprising 7 kg casein, 1~ kg borax, 5 kg of an organic
phosphate ester surfactant, as described previously, and 60 kg
of water at 80~C were added quickly to effect inversion.
Example 3
Preparation of a modified urea
358 kg of urea was placed into a 2 tonne vessel capable of both
stirring and heating the resulting solution. 600 kg of water
was added. Heating and stirring was commenced. To this was
added 18 kg of sulphamic acid. After a solution was achieved
the acidity was measured and found to be 20,000 ppm.

13~0339
14
After 1 1/4 hours of stirring and when boiling (103~C) had
ceased the acidity was measured at 0 ppm.
Example 4
Preparation of a Rosin Dispersion Comprising a Co-Reactant
800 kg of the 30X rosin emulsion produced in Example 2 was
placed into a 3 tonne production unit. To this was added 400
kg of a 30X urea solution. The stirrer was switched on at
3,000 rpm (Greaves mixer). To this was added quickly (1-5 secs)
160 kg of an aluminium chlorohydrate solution. An additional
640 kg of the aluminium chlorohydrate solution was added over a
period of one minute. The stirrer was switched off and the
product filtered through a 40 mesh filter basket.
., .
Example S -~- ~
A dispersion was produced using the ingredients and procedures
described in Example 4,~except a 30X Lewis acid reacted urea
waS substituted for the 30X urea solution.
Example 6
. . .
A dispersion was produced using the ingredients and procedures
described in Example 4, with the exception that no urea was
added.
Example 7
A dispersion was produced using the ingredients and procedures
described in Example 4, except that a polyaluminium chloride
was substituted for the aluminium chlor
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1340339
Example 8
A dispersion was produced using the ingredients and procedures
described in Example 4, except that aluminium sulphate (paper
maker's alum) was substituted for the aluminium chlorohydrate.
Example 9
A dispersion was produced using the ingredients and procedures
described in Example 4, except that 50 mole ~ of the aluminium
chlorohydrate was substituted with a polyaluminium chloride.
Example 10
Sizing tests were carried out as follows~
Bleached sulphite pulp was beaten to Schopper Reigler 40~ at
2~ consistency.
To 600 cc of this pulp was added 800 cc of water and sufficient
sizing agent to give the level listed in Table II. This was
mixed gently.
A further 1 litre of water was added and sufficient sulphuric
(O.lN) acid to control the pH to 6.5 after 30 mins standing.
Sheeets were prepared on a British standard sheet former. The
wet sheets were blotted off the wire, pressed at 50 psi for 5
minutes and dried at 95~C for 4 minutes on a phototgraphic
print drier. After overnight conditioning the sizing
efficiency was assessed using the Cobb test (1 minute).
. ~
_~
~'

16 134033~
- Table I
Internal Sizing
(a) Bleached sulphite Schopper Reigler = 40~
(b) 100 gsm
(c) No additional flocculants added
(d) Final thin stock pH = 6.5
Product of 24 Hour conditioned Cobb
Example~ Rosin/Fibre 60 seconds
4 0.4 25.7
0.6 25.4
- 0.8 22.2
7 0.4 35.6
0.6- 25.4
- 0.8 23.9
8 0.4 30.0
0.6 23.4
0.8 22.8
9 0.4 34.1
0.6 25.9
0.8 23.8
The external, (surface sizing) was simply carried out by
drawing paper through a trough of the diluted sizing agent,
w ~ ~
_

t3~0339
External Sizing- Surface - --
(a) Waste furnishing Schopper Reigler s 40~
(b) 100 Gsm
(c) No additional flocculants added
Product of 24 Hour condi tioned cobb
ExampleX Rosin/Fibre 60 seconds
4 0 . 055 50
0.075 19.4
0 . 111 18 . 5 - -
0.222 17.8
0.333 18.5