Note: Descriptions are shown in the official language in which they were submitted.
~2383Z~
- 1 -
1-14067/~
A process for sizing paper with anionic hydrophobic sizing
agents and cationic retention aids
It is the object of the present invention to provide
the paper manufacturer with readily accessible and simply
obtainable sizing agents which, combined with conventional
cationic retention aids into a novel combination, are capable
of giving efficient sizing in the manufacture of paper from
dispersions of the fibres.
This object is achieved in a novel manner by using,
1~ in the manufacture of paper in the presence of polymeric
cationic retention aids, sizing agents which are compounds
which have at least two~ preferably at least four, long-chain
hydrophobic substituents and at least one anionic or acidic
group which can be in salt form.
The present invention thus provides a process for
sizing paper or cardboard, wich comprises adding in any order
or simultaneously, to aqueous dispersions of the fibres which
can, if desired, also contain filler, at least
(A) an an;onic hydrophobic sizing agent which can be obtained
from
ta) ketene dimers and (b) diamines or oligoamines, and
(B) a polymeric cationic retention aid.
The invention also relates to
- the aqueous compositions for carrying out the paper-sizing
process, which, ;f the siz;ng agent (A) and the retention
aid (B) are added separately in any order to the dispersion
of the fibres, contain, in addition to optional customary
additives, the s;zing agent (A) - which can be at least
partly in the form of salts - alone, or, if the sizing agent
~F~
~2383;~4
-- 2 --
tA) and the retention aid (B) are added simultaneously to the
dispersion of the fibres, not only the sizing agent tA) but
also the retention aid (B) in addition to optional customary
additives,
- the paper or cardboard sized by the process according to the
invention and
- the use of the sizing agent (A) of the specified type for
sizing paper or board.
The specified sizing agent (A) are novel compounds.
These sizing agents per se and the process for their pre-
paration are therefore also part of the subject-matter of the
present invention.
The sizing agents (A) which are used in accordance
with the ;nvention and which can be obtained from the compon-
ents (a) and (b), have as an essentiaL feature 1 to 6, pre~er-
ably 2 to 6, potentially anion;c groups which are generally
;n the form of ac;d;c CH groups. The ab;lity of the poten-
tially anionic substituents to form anions in an aqueous
medium is a further essential characteristic of the sizing
agent. The formation of anions takes place at the pH the
dispersion of the fibres usually has in the manufacture of
paper. Under said conditions the cationic retention aids (B)
are also capable of ionising to form cations. The ability
of the sizing agents and retention aids to form anions and
cat;ons respect;vely under the cond;t;ons of paper manu-
facture can also be referred to as an;on-active and cation-
act;ve respect;vely. The an;onic sizing agents and the
cationic retent;on aids can therefore also be referred to as
an;on-active sizing agents and cation-active retention aids.
The sizing agents (A), which can be obtained from the
components (a) and tb), have as a further characteris;ng
feature 2 to 12, preferably 4 to 12, hydrophobic substituents
which solely cons;st of carbon and hydrogen and have at least
5, preferably 8 to 22, carbon atoms, for example C5-C12-cyclo-
alkyl or C6-C1~-aryl, -alkaryl or -aralkyl rad;cals.
Preferred hydrophob;c substituents, however, are alkyl or
alkenyl radicals wh;ch generally der;ve from fatty ac;ds
123~33~4
having at least 6, preferably 8 to 2Z, carbon atoms. The way
these hydrophobic substituents are linked to each other forms
another characteristic of the (A) sizing agents,for the link-
ing members with which at least two of the hydrophobic groups
S are bonded to each other preferably have 2 to 18 carbon atoms
and at least 2 hetero atoms each, preferably at least 2 nitro-
gen atoms, in the main chain. Linking members which each have
2 to 12 carbon and two nitrogen atoms are preferred. Depending
on the number of hydrophobic substituents, the sizing agents
contain 1 to 5 linking members of the specified type.
Preferably used (A) sizing agents of the specified
type have molecular weights of about 1,0nO to about 4,000.
The component ta), from which the sizing agent (A)
can be obtained, is, for example, a dimer of the ketenes of
the formulae
(1) R1-CH=C=0 and
(2) R1'-CH=~=0
in which R1 and R1' are identical or different and each
is a hydrophobic substituent having at least 5 carbon atoms,
provided that at least one of the radicals R1 and R1' has
at least 8 carbon atoms.
Preferred d;mers are of ketenes of the formulae
(3) Rz-CH=C=O and
(4) R2'-CH=C=0
;n which Rz and R2' are identical or different and each
is alkyl or alkenyl having 5 to 22 carbon atoms, cycloalkyl
having 5 to 12 carbon atoms or aryl, alkaryl or aralkyl
having 6 to 10 carbon atoms, prov;ded that at least one of
the radicals R2 and R2' has at least 8 carbon atoms.
Dimers to the fore of interest are of ketenes of the
formulae
(5) R3-CH=C=0 and
(6) R3'-CH=C=0
where both of the ketenes derive from an unsaturated or
saturated fatty acid having at least 6, preferably 8 to 22,
carbon atoms and R3 and R3' are identical or different,
provided that at least one of the radicals R3 and R3' derives
~2~ 12~
from a fatty acid which has at least 8 carbon atoms.
In the definitions of R2 and R2' in the formulae (3)
and (4), representatives of C5-C1z-cycloalkyl are, for
example, cyclopentyl, cyclododecyl and especially cyclohexyl,
and representatives of C6-c1o-aryl~ alkaryl or aralkyl are
for example naphthyl, tolyl, xylyl, phenylethyl and especially
~naphthyl, benzyl and phenyl.
The unsaturated or saturated C6-C2z, preferably
C8-C22, fatty acids from which the ketenes of the formulae
t5) and (6~ derive is for example caproic, preferably
caprylic, capric and arachidic acid, in particular lauric,
myristic, palmitic, stearic and behenic acid or myristoleic,
palmitoleic, elaeostearic, or clupanodonic acid, in particular
oleic, elaid;c, erucic, linoleic and linolenic acid. Of
these, Lauric acid, paLmitic acid, stearic acid, oLeic acid
and behenic acid are of particular importance. Stearic acid
is to the fore of interest and is used especially combined
with the other fatty acids mentioned last. Ketenes which
derive from technical mixtures of said saturated and/or un-
saturated fatty acids are particularly preferred.
Dimers of ketenes of the formulae(7) R4-CH=C=0 and
(8) R4'-CH=C=û
where the two ketenes derive from lauric, palmitic, stearic,
ole;c or behenic ac;d or mixtures thereof and R4 and R4' are
identical or different, are thus to the fore of interest.
Ketene dimers of the specified type are known per se
and have been described, for example, in U.S~ Patent 4,317,756.
Their preparation, for example from the corresponding acid
halides, in particular fatty acid chlorides, and strong
tertiary bases, in particular trialkylamines, has been dis-
closed in, for example, U.S. Patent 2,383,863.
Said U.SO Patent 4,317,756 gives the ketene dimers
in which R1 and R1' in the formulae (1) and (2) are iden-
tical by means of the formula
~1.1) ~R1-cH=c=o]2
Z~
.
-- 5
;n which R1 ;s as defined above~ However, the ketene
dimers can also be cyclic and have the formula
1~ -CH=C--CH-R '
(1.2~
O--C=O
in which R1 and R1' are identical or different and are as
defined above.
The component (b~, from which the sizing agent (A~
can be obtained, can be an aliphatic, cycloaliphatic,
aromatic, araliphatic or heterocyclic diamine or oligoamine
having 2 to 6 nitrogen atoms and 2 to 36 carbon atoms. The
oligoamines are in particular aliphatic amines, in particular
polyalkylenepolyamines having at most 6 nitrogen atoms and
2 or 3 carbon atoms in each alkylene bridge member. The di-
amines, however~ can have between the two nitrogen atoms not
only aromatic or araliphatic bridge members, preferably
having 6 to 16 carbon atoms, or heterocyclic bridge members,
preferably of the piperazine ser;es, but also aliphatic
br;dge members hav;ng preferably 2 to 8 carbon atoms or
cycloaliphatic bridge members having preferably 5 to 12
carbon atoms.
Preferred diamines or oligoamines accordingly have
the formula
(9) D1-NH-A1-NH2
in which A1 is alkylene, hydroxyalkylene, alkenylene or
cycloalkylene having at most 12 carbon atoms, an alkaryl or
aryl radical of one of the formulae
(9.1) ~(CH2)n~ (CH2)n2_
.=.
or
(9 2) ~CH2)n3~ ; . r-.~(CH2)n
~2~3,24
-- 6 --
or naphthylene, a heterocyclic radical of ~he formula
(9 3) -E~ -El'-
or, in the case of oligoamines, an aliphatic radical of the
formula
(9 4) (E1 NH)m E1
D1 is hydrogen or an alkyl or alkenyl radical which derives
from fatty acids having 8 to 22 carbon atoms, E1 and E1' each
are ethylene or n-propylene, n1, n2, n3 and n4 each are
1, 2 or 3, and m is an integer from 1 to 4~
If A1 is alkylene, hydroxyalkylene or alkenylene,
the bridge members can be branched as weil as straight-chain.
Alkenylene rad;cals generally have 3 to 8 carbon atoms and 3
or 2 double bonds or preferably only one double bond.
Alkylene ;s preferred to alkenylene and generally has 2 to 9,
in part;cular 2 to 6, carbon atoms. Alkylene rad;cals can be
unsubstituted or be preferably subst;tuted by at most 2
hydroxyl groups, in particular only one hydroxyl group. Such
hydroxyalkylene rad;cals are generally straight-cha;n. Rep-
resentatives of cycloalkylene radicals are cyclodecylene,
cyclododecylene and, espec;ally, cyclopentylene and, ;n par~i-
cular, cyclohexylene. If D1 ;5 an alkyl or alkenyl rad;cal,
it preferably der;ves from the abovement;oned C6-C22, prefer-
ably C8-C22, fatty ac;ds. D1 ;5 preferably an alkyl or
alkenyl rad;cal only ;f A1 ;s alkylene. Ethylene is the
preferred definition of E1 and E1'. Preferably n1 and n2
each are 1 or 2 and n3 and n4 each are 1~ Preferred
representatives of the formula (~.1) are toluylene and
especially xylylene and phenylene, and the formula t9~2) pre-
ferably represents diphenylene ether.
D;amines or oligoam;nes wh;ch are to the fore of
interest thus have the formula
t10) D2-NH-A2-NH2
;n which A2 ;s unsubstituted straight-chain or branched
~2;3~3;~
alkylene or hydroxyl-substituted straight-chain alkylene
having 2 to 9 carbon atoms, cyclopentylene, cyclohexylene,
phenylene, toluylene, xylylene, diphenylene ether or
(10.1) (cH2-c~2-NH~m-cH2-cH2-o
D2 is hydrogen or~ if A2 is alkylene~ an alkyl or alkenyl
radical which derives from a fatty acid having 8 to 22 carbon
atoms, and m is an integer from 1 to 4, and in particular the
formula
(11) D3-NH-A3-N~2
in which A3 is unsubstituted or straight-chain alkylene
which is substituted by at most one methyl or hydroxyl radical
and has a total of 2 to 6 carbon atoms, cyclohexylene,
phenylene, diphenylene ether, xylylene or the radical of the
formula (1û.1), D3 is hydrogen or, ;f A3 is alkylene, an
alkyl or alkenyl radical wh;ch derives from lauric, palm;tic,
stearic, oleic or behenic acid or mixtures thereof.
The novel sizing agent (A) according to the inven-
tion can be obtained from the ketene dimers defined above and
used as component (a) and the diamines or oligoamines defined
above and used as component (b). Provided that the component
(a) used is dimers of the ketenes of the formulae (1) and (2)
or ketene dimers of the formula (1.1) or (1.2) and the com-
ponent (b) used is diamines or oligoamines of the formula (9),
the (A) sizing agents, or salts thereof, have one of the
probable formulae
Dl-N------Ao~~~NH D -N------(El------~) ---El'---NH
CO CO ro CO CO
(12) 1 1 or (13)
CH-Rl' Cil-Rl' CH-R ' CH-R ' CH-R
CO CO CO CO CO
C~2-Rl CH2-R, 2 1 CH2 1 CH -B
of which formula (12) applies if diamines are used as start-
ing components (a) and formula (13) applies if oligoamines
are used as starting component (a), and, in the formulae (12)
~2:~,3~4
-- 8 --
and (13), Ao is alkylene, hydroxyalkylene, alkenylene or
cycloalkylene having at most 12 carbon atoms, an alkaryl or
aryl radical of the formulae (9.1) or (9.2) or naphthylene,
or a heterocyclic radical of the formula (9.3), E1 and E1,
S each are ethylene or n-propylene, D1 is hydrogen or an alkyl
or alkenyl radical which derives from fatty acids having 8
to 12 carbon atoms, and R1 and R1' are identical or different
and each denotes a hydrophobic subs-tituent having at least
5 carbon atoms, provided that at least one of the radicals
R1 and R1' has at least 8 carbon atoms. If the siz;ng
agents of the formula ~12) or (13) are in the form of salts,
R1 l
the hydrogen atom in the -C0-CH-C0- groupings are at least
partly replaced by the cation of the corresponding salt.
Reaction products of the formuLa (12) or (13) ar~
prepared by reacting with one another
ta) a dimer of a ketene of the formulae (1) or (2) with
(b) a diamine of the formula
(14) D1-NH-Ao~NH2
or an oligoamine of the formula
(15) D1-NH-(E1-NH)m-E1l-NH2
which Ao~ D1, E1, E1' and m are as defined above.
In this method of preparation, 1 to 1.1 equivalents,
in particular 1.0 equivalent, per amino group of component
~b) are preferably used per mol of component (a), and the
reaction is generally carried out in the melt or preferably
in at least one organic solvent, i.e. in a single solvent or
in a solvent mixture, at preferred temperatures of about 10
to about 140C.
The solvents used must be inert not only to each of
the starting components (a) and (b) but also to the end
product, i.e. the reaction products of (a) and (b). Examples
of possible solvents are halogenated or unhalogenated hydro-
carbons which have a boiling point of at most 14ûC, prefer-
ably between about 8û and about 140C, such as benzene,
especially toluene, chlorobenzene, o-, m- and p-xylene, a
technical xylene mixture or even mixtures of said hydrocarbons~
24
9 _
However, lower-boiling solvents are preferred, for example
preferably halogenated hydrocarbons which boil at about 40
to about 80C, for example dichloroethane, carbon tetra-
chloride or, especially, chloroform. It is especially advan-
tageous to carry out the reaction at the reflux temperatureof whichever solvent of the specif;ed type is used.
Before they are used as component (A) in the paper-
siz;ng process according to the invention, the sizing agents
need generally not be purified and recrystallised after they
have been prepared, but can, as a rule, be used directly.
Especially if the sizing agent (A) and the retention
aid (B) are added separately (in any order) to the disper-
sion of the fibres ;n the process according to the ;nvention
for sizing paper or board it ;s advantageous to use some of
the sizing agent in sa~t form. If desired, such salts can
be obtained by adding, when the reaction between the compon-
ents (a) and (b) has ended, to the reaction products obtained
inter alia an alkylamine or alkanolamine having a total of
at most 6 carbon atoms, for example trimethylamine, triethyl-
amine, monoethanolamine or d;ethanolamine, especially byadding ammonia or an alkali metal hydroxide, for example
potassium hydroxide or especially sodium hydroxide, and con-
verting the reaction products obtained, if desired at least
partly, into the corresponding salts, as a rule ;n an aqueous
medium at room temperature (about 15 to about 25C). It is
advantageous to use an alkali metal hydrox;de, for example
potass;um hydroxide or, especiaLly, sodium hydroxide, or in
particular ammonia, generally in the form of their dilute,
approximately 1 to 10 per cent by weight, aqueous solution.
It is generally advantageous to use at most 2 mol, especi-
ally at most 1 mol, preferably 0.1 to 0.9, in part;cular 0.1
to 0.7, mol of ammon;a or alkal; metal hydrox;de per grouping
of the formula -~H- present in the reaction products of the
formula (11) or (12). The reaction products thus present
in salt form have the formula (11) or (12) ;n which at
least some of the acidic groupings are converted ;nto the
corresponding -~- anions whose negative charge~3 is
~X38329~
- 10 -
neutralised by the corresponding amine, ammonium or alkali
metal cations.
The paper-sizing process according to the invention
is always carried out with, in addition to the anionic or
acidic sizing agent (A) which is described above and which
is novel per se, a polymeric cationic retention aid (B) which
generally has a molecular weight of at least 1,000, especi-
ally at least about 2,500, preferab~y about 2,000 to about
2,000,000, in particular about 5,000 to about 2,000,000.
~etention aids having molecular weights within the range
from 10,~00 to 100,000 are particularly preferred. In prin-
ciple, any commercially available retention aid can be used
in the process according to the invention.
Examples of conventional retention ai~s (B) which are
particuLarLy suitable for use, together with the sizing
agent (A), in the paper-sizing process according to the
invention are polyalkyleneimines, epihalogenohydrin adducts
of reaction products of polyalkylenepolyamines and of ali-
phatic dicarboxylic acids or of reaction products of poly-
alkylenepolyamines, of dicyanodiamide and free or alkanol-
esterified organic dicarboxylic acids, reaction products of
dicyanGdiamide, of formaldehyde, of ammonium salts of strong
inorganic acids and of alkylenediamines or polyalkylenepoly-
amines, cationically modif;ed starches or carbohydrates of
carob bean or guar bean flour, copolymers based on poly-
amide-amines and reaction products of epihalogenohydr;ns and
of polymerised diallylamines.
Preferred epichlorohydrin adducts of reaction pro-
ducts of polyalkylenepolyamines and aliphatic dicarboxylic
acids are described, for example, in British Patent 865,727,
epichlorohydrin adducts of reaction products of dicyanodi-
amide and diethylenetriamine or triethylenetetramine, for
example, in German Offenlegungsschrift 2,710,061 and in
British Patent 1,125,486, epichlorohydrin adducts of reaction
products of diethylenetriamine, dicyanodiamide and free or
preferably lower-alkanol-esterified dicarboxylic acids, in
particular dimethyl adipate, for example, in British Patent
~324
1,125,486, and reaction products of dicyanodiamide, formalde-
hyde, ammonium salts of strong organic acids and of ethylene-
diamine or triethylenetetramine, for example, in U.S. Patent
3,491,064. Preferred cationically modified starches and
carbohydrates from carob bean and guar bean flour are alkyl-
ene oxide adducts of these starches or carbohydrates, the
alkylene oxide used having 2 or 3 carbon atoms in the alkyl-
ene radical and quaternary ammonium groups~ Copolymers based
on polyamide-amines have molecular weights of 103 to 105,
preferably 103 to 104, and can be obtained from, for
example, aliphatic saturated dicarboxylic acids having 2 to
10, preferably 3 to 6, carbon atoms, in particular adipic
acid, and polyalkylenepolyamines, for example polypropylene
polyamine and polyethylenepolyamine, in particular dimethyl-
aminohydroxypropyldiethyLenetriamine. They are described,for example, in the CTFA Cosmetic Ingredient Dictionary, 3rd
edition 1902, of the Cosmetic Toiletry and Fragrance Asso-
ciation. Reaction products of epihalogenohydrins and poly-
merised diallylamines preferably have molecular weights of
1,000 to 2,000 and are described, for example, in U~S. Patents
3,700,623 and 4,279,794.
Examples of retention aids (B) which are to the fore
of interest for use together with siz,ing agents (A) in the
paper-sizing process according to the invention are a corn
or potato starch which has been modified with a propylene
oxide conta;n;ng quaternary ammonium groups and whose 25%
suspension in dist;lled water at 20C has a pH of 4.2 -
4.6, a polyethyleneimine which has a molecular weight of
10,000 to 100,000, an epichlorohydrin adduct of a reaction
product of triethylenetetramine and dicyanodiamide, an epi-
chlorohydrin adduct of a reaction product of diethylenetri-
amine, dicyanodiamide and d;methyl adipate, a reaction pro-
duct of d;cyanodiamide, formaldehyde, ammonium chloride and
ethylenediamine, an epichlorohydrin adduct of a poly-N-
methyldiallylamine and a copolymer of adipic acid anddimethylaminohydroxypropyldiethylenetriamine.
In the process generally 0.02 to 3, preferably 0.1
~23~3~4
- 12 -
to 3, in particular O.Z to 0.~, per cent by weight of the
sizing agent (A) and 0.02 to 5, preferably 0.1 to 3, in par-
ticular 0.2 to 0O4~ per cent by weight of the retention aid
(B~, each based on dry substance in ~A) and (~) and on the
solids content of the dispersion of the fibres, are used.
0.02 to less than 0~1 per cent by weight of the sizing agent
(A) and of the retention aid (B) are only sufficient for size
press control, which cannot be detected in conventional
sizing tests (cf., for example, the article "ControL and
understanding of si~e press pickup" by D.R. Dill in the jour-
nal TAPPI (Proceedings of the Technical Association of the
Pulp and Paper Industry), Volume 57, No. 1, of January 1974,
pages 97 to 100).
The dispersion of the fibres, to which sizing a~ents (A)
and the retention aids (B) are added, generally has a
solids content of 0.1 to 5, preferably 0.3 to 3, in particular
û.3 to 1, per cent by weight and a Schopper-Riegler freeness
of 20 to 60, preferably 20 to 45, in particular 25 to 35.
It generally contains pulp, in particular pulp from conifers,
that is softwood, for example pinewood, or from hardwood, i.e. deciduous
wood, for example beechwood, which is prepared by conventional
methods, for example the sulfite or, especially, the sulfate
methods. The dispersion of the fibres can, if desired, also
contain mechanical wood pulp. Even alum-containing waste
paper can be present in the dispersion of the fibres. It is
even possible to use dispersions of cellulose fibres which
are prepared by the CMP or CTMP processes (Chemimechanical
and chemithermomechanical pulping processes, cf., for example,
the article "Developments in refiner mechanical pulping" by
S.A. Collicutt et al. in TAPPI, Volume 64, No. 6 of June
1981, pages 57 to 61).
The dispersion of the fibres can also contain organic
or mineral fillers. Possible organic fillers are, inter
alia, synthetic pigments, for example polycondensation pro-
ducts of urea or melamine and formaldehyde, which have large
.specific surface areas, which are present in highly dispersedform and have been described, inter alia, in Pritish Patents
~23~33%~
- 13 -
1,043,937 and 1,318,244, and possible mineral fillers are,
inter alia, montmorillonite, titanium dioxide, calcium sul-
fate and, especially, talc, kaolin and/or chalk Scalcium car-
bonate). The dispersion of the fibres generally CGntains 0 to
40, preferably 5 to 25, in particular 15 to 20~ per cent by
weight, based on the solids content of the dispersion of the
fibres, of dry substance of the fillers of the specified type.
The pH of the dispersion of the fibres can be within
a wide range, for example between 3.5 and about 10.
Adding calcium carbonate, for example, gives alkaline
dispersions of the fibres, which have a pH of about 7 to
about 9, preferably 7.5 to 8.5. Acid dispersions of the
fibres, ~hich have a pH of 3.5 to 7, preferably 5 to 7, in
particular 5 to 6, can be obtained in the absence of caLcium
carbonate by adding acids, for example sulfuric or formic
acid or especially, for example, latent acidic sulfates, such
as aluminium sulfate (alum).
D;spersions of the fibres wh;ch are free of filler
can be within a wide pH range, for example from 3.5 to 10.
Preferred dispersions of the fibres have a pH of about 7
to about 9, if appropriate as the result of adding chalk,
and they are advantageous in that they prevent possible
corrosion of the sensitive paper machines.
The dispersion of the fibres can also contain addi-
tives, for example starch or its degradation products, whichincrease the fibre-fibre or fibre-filler bond.
Even high molecular weight polymers of the acrylic
acid series, for example polyacrylamides having molecular
weights of above 1,000,000, can be added to the dispersions
of the fibres as an aid for retaining very fine cellulose
particles, very low levels of about 0.005 to 0.02 per cent
by weight, based on dry substance of the high molecular weight
polymer and the solids content of the dispersion of the
fibres, being sufficient.
The dispersion of the fibres is processed in the pro-
cess according to the invention into paper or board in a
manner known per se, namely on sheet formers or, preferably,
- 14 -
continuously on paper machines of convent;onal design.
Drying at about 100 to 140C for about 0.5 to 10 minutes
gives papers having a variable weight per unit area, for
example from 50 to 200 g/m2.
As mentioned above, the aqueous composition for
carrying out the paper-sizing process according to the inven-
tion contains, in addition to optional customary additives,
the sizing agent (A) if the sizing agent (A) and the reten-
tion aid (B) are added separately to the dispersion of the
fibres. In this case, the formulation preferably contains
some of the s;zing agent in the form of its salts (obtained
by using, for example, ammonia, an alkylamine, an alkanol-
amine or an alkali metal hydroxide of the specified type in
the abovementioned ratios). These compositions generally
contain 5 to 30, preferably 5 to 20, per cent by weight of
dry substance of the sizing agent which is partly in salt
form, based on the weight of the aqueous composition.
If, however, the sizing agent (A) and the retention
aid (B) are added simultaneously to the dispersion of the
fibres, the aqueous composition, in addition to the optional
customary additives, contains
(A) 2 to 40, preferably 5 to 30, in particular 5 to 10, per
cent by weight of sizing agent (calculated as dry substance),
based on the weight of the aqueous composition, and
Z5 (B) 0.1 to 20, preferably 0.5 to 10, in particular 3 to 8,
per cent by weight of retention aid (calculated as dry sub-
stance), based on the aqueous composition.
The aqueous compositions of the specified type can,
if desired, also conta;n, as customary additives, surface-
active compounds, for example dispersants or also emulsifiersand/or water-soluble organic solvents. Possible dispersants
and emulsifiers are, for example, conventional ligninsulfon-
ates, ethylene oxide adducts of alkylphenols, fatty amines,
fatty alcohols or fatty acids, fatty acid esters of polyhydric
alcohoLs, substituted benzimidazoles or condensation pro-
ducts of aromatic sulfonic acids and formaldehyde. Other
surface-act;ve compounds are preferably anionic surfactants,
~23~i3Z4
- 15 -
in particular sulfate surfactants, for example diethanolamine
lauryl sulfate or ethoxylated lauryl sulfates. Possible
water-soluble organic solvents are aliphatic ethers having 1
to 10 carbon atoms, for example dioxane, methylene glycol n-
S butyl ether or diethylene glyccl monobutyl ether, or alcoholshaving 1 to 4 carbon atoms, for example isopropanol, ethanol
or methanol.
The compositions are prepared in a conventional
manner, namely by stirring the sizing agent (A) together with
the retention aid (B) or the sizing agent (A), for example
partly in the form of its salt, by itself, either in a molten
state or preferably in a solid state, in particular in pul-
verulent form, generally in the presence of glass beads and,
if necessary, emulsifiers (in the case of sizing agents in
the molten state) or dispersants (in the case of sizing agents
in pulverulent form) at at most 90C, preferably at about
5D to 85C in the case of emulsions, in particular at about
15 to 25C in the case of d;spers;ons, to obta;n stable
homogeneous emulsions or preferably dispersions. Since the
sizing agents together w;th the retention aids or the sizing
agents partly in salt form are generally self-dispersing or
self-emulsifying, the use of dispersants or emulsifiers is
generally not necessary. This also applies to the optional
addition of solvents and/or surfactants, which are only used
if the dispersions or emulsions have an insufficiently long
shelflife.
It may be mentioned as an advantage of the process
according to the invention that var;ous dispersions of the
f;bres can be processed with relatively small amounts of
sizing agent and retention aid in a simple manner into paper
which has good sizing properties (ink flotation period and
especially Cobb water absorption). The paper sized by the
process of the invention has good mechanical properties, i.e.
good strength, in particular good tear strength. Good re-
produc;b;lity of the process is ensured. In particular,d;spersions of the f;bres which contain mechanical wood pulp
or waste paper can be processed. Also, the compatibility of
24
- 16 -
the sizing agent used in the process according to the inven-
tion with a very wide variety of fillers and also their addi-
tives, for example kaolin or alums in the acid range of dis-
persions of the fibres, is advanta~eous~ The sizing agents
S also have excellent compatibility with fluorescent brighteners.
Furthermore, the whiteness of the sized paper is not signi-
ficantly affected by the sizing and can, in certain circum-
stances, even be improved. An especially great advantage is
the surprisingly long shelflife of the sizing agent disper-
sions of the specified type. This advantageous stabilityapplies not only to dispersions of sizing agents (A) by them-
selves but also to dispersions of mixtures of sizing agents
(A) and retention aids (s). It is, in particular, sig-
nificantly better for dispersions of reaction products of the
components (a) and (b) as ~A) sizing agents or m;xtures
thereof with (B) retention aids than for dispersions of com-
ponent (a) by itself or mixtures thereof w;th (B) retent;on
a;ds.
The parts and percentages g;ven in the follo~ing
preparation methods and illustrative embodiments are by
weight.
Preparat;on Examples
Example 1: 75 parts (0.15 mol) of the dimer of the ketenes
of the formulae
(16) CH3 (CH2)13 CH C 0 and
(17) CH3 (CH2)15 CH=C=0
are dissolved in 300 parts of chloroform. 5.2 parts ~0.05
mol) of diethylenetriamine are added to the ketene dimer solu-
tion in the course of 5 m;nutes, the reflux temperature of
the react;on m;xture of about 62C comes about by ;tself.
The react;on m;xture ;s then held at th;s temperature for
2.5 hours. Remov;ng the chloroform under rèduced pressure
g;ves, ;n the form of a d;st;llat;on residue, 80.2 parts
(100~ of theory) of the crude react;on product of the formula
~;~3832~
- 17 -
(18) NH - CH2 - C~2 - N - CH2 - CH2 - NH
CO CO CO
I ( 2)q 3 1 ( 2)q 3 1 ( 2)q 3
CO CO CO
(CH2) ~-CH3 (CH2)q'-cH3 (CH2) ,-CH3
q = 13 and q' = 16 or q = 14 and q' = 15
For analytical purposes the crude reaction product is
recrystallised from ethanol. The recrystallised product is
S in the form of a crystalline colourless powder. Infrared
spectroscopy and liquid chromatography show it to be free of
unconverted ketene dimer.
Melting po;nt: 70-75C.
Elemental analysis:
10 calculated C 78.70X H 12.77% N 2.60X 0 5.93X
found C 78.5% H 12.6% N 2.7% 0 6.2%~
Example 2: Example 1 is repeated, except that 51 parts ~0.1
mol) of the dimer of the ketenes of the formulae (16) and (17)
and 3.6 parts (0.025 mol) of triethylenetetramine are used,
afford;ng 54.6 parts t100X of theory) of the crude reaction
product of the formula
(19) 1 2 2 =N - CH - CH - - NH
CO CO CO
~ ( 2)q 3 I ( 2)q 3 I ( 2)q 3
CO CO CO
(CH2)ql~CH3 (CH2)ql~CH3 2(CH2) ' CH3
q and q' as defined ;n formula (18).
The recrystallised product is likewise in the form of
a crystalline colourless powder which is free of unconverted
ketene dimer.
Melting point: 56 - 61C
3Z~
- 18
Elemental analysis:
calculated C 78.75% H 12.75% N 2.59% 0 5.91%
found C 79.0% H 12.5% N 2u7% 0 5.8%.
Example 3: Example 1 is repeated, except that 35.4 parts
(0.07 mol) of the dimer of the ketenes of the formulae (16~
and (17) and 2.7 parts (0.014 mol) of tetraethylenepentamine
are used, affording 38.1 parts (100% of theory) of the crude
reaction product of the formula
(20) NH CH2 CH2 1 2 2 - NH
CO CO CO
I ( 2)q 3 I ( 2)q 3 I ( 2)q 3
CO CO ~0
2 q 3 _ 2 q 3 _ (CH2)q'-cH3
q and q' as defined in formula (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It is like~ise free of uncon-
verted ketene dimer.
15 Melting po;nt: 49 - 55C
Elemental analysis:
calculated C 78.78% H 12.74% N 2.58% 0 5.90%
found C 78.~% H 12.6% N 2.9% 0 6.2%.
Example 4: Example 1 is repeated, except that 35.4 parts
(0.07 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 2.8 parts (0.012 mol) of pentaethylenehexamine
are used, affording 38.2 parts (100% of theory) of the crude
reaction product of the formula
~23l3324
- 19 -
( 2 1 ) NH - CH2 - CH2 - = N - CH - CH - - N~
CO CO CO
Cl (CH2)q CH3 CIH (CH2~q CH3 I (CH2)q CH3
CO CO CO
2 q 3 _ 2 q' 3 _ (CH2)ql~CH3
q and q' as def;ned ;n formula (18).
The crude product is recrystallised from acetone for
analyt;cal purposes. The recrystallised product is in the
form of a colourless powder. It is likewise free of uncon-
verted ketene d;mer.
Melting point: 49 - 51C
Elemental analysis:
calculated C 78.8û% H 1Z.73% N 2.58% 0 5.89%
10 found C 78.7Y. H 12.8% N 2.9% 0 5.6%.
Example 5: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 1.5 parts (0.025 mol) of 1,2-diaminoethane are
used, affording 26.8 parts (100~ of theory) of the crude
reaction product of the formula
( 2 2 ~ NH - CH - CH - NH
CO CO
2)q 3 1 ( 2)q 3
CO CO
( CH2 ) q ~ -CH3 ( CH2 ) , -CH3
q and ~' as defined in formula (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
20 form of a colourless powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 110 - 113C
~23~3~
- 20 -
Elemental analysis:
calculated C 78.59% H 12.81% N 2.62~ 0 5.98%
found C 78.6% H 13.7~ N 2.8% 0 5.9%
Example 6: Example 1 is repeated, except that 25.3 parts
tO.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 1.8 parts (0.025 mol) of 1,3-diaminopropane are
used, affording 27.1 parts (100% of theory) of the crude
reaction product of the formula
~23) NH - CH2 - CH2 - CH2 - NH
CO Co
I ( 2 q 3 1 ( 2 q 3
CO CO
2 q 3 (CH2)q,~CH3
q and q' as defined in formula (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It ;s likewise free of uncon-
verted ketene dimer.
15 Melting point: 89 - 91C
Elemental analysis:
calculated C 78.68% H 12.84% N 2.58% 0 5.90%
found C 78.2% H 12.6% N 2.8% 0 6.4%.
Example 7: Example 1 is repeated, except that 35.4 parts
(0.07 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 4.1 parts (û.035 mol) of 1,6-diaminohexane are
used, affording 39.5 parts (100% of theory) of the crude
reaction product of the formula
~2~83Z~
- 21 -
(24)
z CTI;~ CH2 - CH2 - CH - CH - NH
CO CO
2 ) q 3 ~ 2 q 3
CO CQ
(CH2\ql-cH3 (C~2) q, -CH3
q and q' as defined in formula (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
S form of a colourless powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 96 - 98C
Elemental analysis:
calculated C 78.94% H 12.89% N 2.49% 0 5.68%
10 found C 79.0% H 13.1% N 2.9% 0 5.0%.
Example 8: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 2.2 parts (0.017 mol) of bis(3-aminopropyl)-
amine are used, affording 27.5 parts ~100% of theory) of the
crude reaction product of the formula
I H2 CH2 CH2 - NH - C~2 - CH2 - CH2 - NH
CO CO ~0
( 2) q 3 CH ( 2)q 3 CH (CH2)q 3
CO CO
CO
(CH2)q~~C~3 (C;~)ql~CH3 2 q 3
ci and q' as def;ned in formuLa (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 68 - 70C
- 22 -
Elemental analysis:
calculated C 78.S0% H 12.99% N 2.59% 0 5.92%
found C 78.7% H 13.1% N 2.9% 0 5.3%.
Example 9: Example 1 is repeated, except that 25.3 parts
(0~05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 2.2 parts (0.013 mol) of 1,2-bis(3-aminopropyl-
amino)-ethane are used, affording 27.5 parts (100% of theory)
of the crude reaction product of the formula
(26) ~NH - CH2 - CH2 ~ CH~ - NH CH2
CO CO
CH (C 2)q C 3 C ( 2)q 3
CO CO
2 q 3 2 S' 3 _ 2
q and q' as defined in formula (18)~
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 52 - 55C
Elemental analysis:
calculated C 78~84% H 12~78% N 2.55% 0 5.83%
found C 78~8% H 12r4% N 3.0% 0 5~8%~
Example 10: Example 1 is repeated, except that 25~3 parts
(0~05 mol) of the dimer of the ketenes of the formula (16)
and (17) and 8.2 parts (about 0.025 mol~ of a technical mix-
ture of N-(3-aminopropyl)hexadecylamine, N-(3-aminopropyl)-
heptadecylamine and N-(3-aminopropyl)octadecylamine, afford-
ing 33A5 parts (100% of theory) of the crude reaction product
mixture of the formula
~23~32~
- 23 -
(27) Ql - N - CH~- CH2 - CH2 - NH
CO Co
2 q 3 1 ( 2 q 3
CO CO
(CH2)ql-cH3 2 q 3
q and q' as defined in formula (18).
r~1 = a mixture of C16-, C~7- and C18- alkyl.
The crude product mixture is recrystallised from
S acetone. The recrystallised product m;xture is in the form
of a yelLow;sh powder. It is l;kewise free of unconverted
ketene d;mer.
Melt;ng po;nt: 69 - 72C.
Example 11: Example 1 is repeated, except that 25.3 parts
(0.05 mol~ of the dimer of the ketenes of the formula (16)
and (17) and 10.9 parts (about O.OZ5 mol) of a technical mix-
ture o~ N-(3-aminopropyl)eicosylamine and N-(3-aminopropyl)-
docosylamine, affording 36.2 parts (100% of theory) of the
crude reaction product mixture of the formula
15 (2~) Q2 N CH2 CH2 - CH2 - NH
CO CO
I ( 2 q 3 CIH (CH2)q 3
CO CO
(CH2)4~-CH3 2 q 3
q and q~ as defined in formula ~18).
Q2 = a mixture of C20- and C22-alkYl'
The crude product mixture is recrystallised from
acetone. The recrystallised product mixture is in the form
of a yellowish powder. It is likewise free of unconverted
ketene dimer.
MeLting point: 48 - 52C.
- 24 -
Example 12: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 2.7 parts (0.025 mol) of 1,3-diaminobenzene are
used, affording 28.0 parts (100% of theory) of the crude
reaction product of the formula
(29) ~ H
CO \- CO
1 2 q 3 ICH (CH2)q CH3
CO CO
2 q 3 2 q 3
q and q' as defined in formula (18).
The crude product is recrystallised from acetone for
analytical purposes. The recrystallised product is in the
form of a colourLess powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 52 - 55C.
Elemental analysis:
calculated C 79.51% H 12.26% N 2.51% 0 5.72%
15 found C 78.8% H 12.4% N 2.3% 0 6.5%.
ExampLe 13: Example 1 is repeated, except that 35.4 parts
tO.07 mol~ of the dimer of the ketenes of the formulae ~16)
and ~17) and 4.8 parts (0.035 mol~ of a~a~-diamino-m-xylene
are used, affording 40.2 parts (100% of theory) of the crude
reaction product of the formula
NH - CH - ~ - CH - Na
CO CO
I ( 2)q 3 Cla (CH2)q ~H3
CO Co
(CH2) q -CH3 2 q 3
q and q' as defined ;n formula (18).
3æ~
The crude product is recrystallised from dioxane for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It is likewise free of uncon-
verted ketene dimer.
Melting point: 105 - 108C
Elemental analysis:
calculated C 79.67% H 12.31% N 2.44% 0 5.58%
found C 80.0% H 12O3% N 2.4% 0 5.3%.
Examele 14: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 5.0 parts (0.025 mol) of 4,4'-diaminod;phenyl
ether are used, affording 30.3 parts (100% of theory) of the
crude reaction product of the formuLa
( 31 ) NH ~
CO CO
C~H (CH2)q 3 1 ( 2 q 3
CO CO
(CH2)q' ~H3 (CH2)ql-cH3
q and q' as defined in formula (18).
The crude product is recrystallised from acetone for
analyt;cal purposes. The recrystallised product is slightly
yellowish. It is likewise free of unconverted ketene dimer.
Melting point: 105 - 108C
2û Elemental analysis:
calculated C 79.41% H 11.66% N 2.32% 0 6.61%
found C 79.4% H 11.5% N 2.2% 0 6.9%.
Example 15: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketene of the formulae ~16)
and (17) and 2.3 parts (0.025 mol) of 1,3-diamino-2-propanol
are used, affording 27.6 parts (100% of theory) of the crude
reaction product of the formula
~23~B329t
- 26 -
OH
(32) NH - CH2 - CH - CH2 - NH
CO CO
2 ) q 3 1 ( 2 ) q 3
CO CO
2 q 3 ( CH2 ) q, -CH3
q and q' as defined in formula (18)~
The crude product is recrystallised from dioxane for
analytical purposes. The recrystallised product is in the
form of a colourless powder. It is likewise free of uncon-
verted ke~ene dimer.
Melting point: 98 - 100C.
Elemental analysis:
calculated C 77.53% H 12.65% N 2~55% 0 7.27%
10 found C 77.7~ H 12.6% N 2.1% 0 7.6%.
Example 16: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae tl6)
and (17) and 1.8 parts (0.025 mol) of 1,2-diaminopropane are
used, affording 27.1 parts (100% of theory) of the crude
reaction product of the formula
1 3
2 2
(33)
Co CO
CH- (CHZ) q~CH3 1 ( 2 q 3
CO CO
(CH ) q, -CH3 (CH2) q, -CH3
q and q' as defined in formula (18)~
The crude product is recrystallised from ethyl ace-
tate for analyt;cal purposes. The recrystallised product is
in the form of a colourless powder. It is l;kewise free of
unconverted ketene dimer.
~Z3~32~
Melting point: 98 - 100.
Elemental analysis:
calculated C 78.68% H 12.83~ N 2.59% 0 5.90%
found C 78.8~ H 12.6% N 2.6% 0 6.0%.
xample 17: Example 1 is repeated, except that 25.3 parts
(0.05 mol) of the dimer of the ketenes of the formulae (16)
and (17) and 2.9 parts (0.025 mol) of 1,~-diaminocyclohexane
are used, affording 28.2 parts (100% of theory) of the crude
reaction product of the formula
10 (34) ~lH C~ ~2 ~-\CH - NH
i CH - CH
CO co
CH ( 2)q 3 IH (CH2)q 3
CO CO
2 q 3 (CH2)q'-c~3
q and q' as defined in formula (18).
The crude product is recrystallised from ethyl ace-
tate for analytical purposes~ The recrystallised product is
in the form of a colourless powder. It is likewise free of
15 unconverted ketene dimer.
Melting point: 120 - 125C.
Elemental analysis:
calculated C 79.08% H 12.74% N 2.49% 0 5.69%
found C 78.2% H 12.5% N 2.7% 0 6.6%.
ZO Application Examples
Examples 18 and 19: A dispersion of bleached birch sulfate
pulp and pine sulfate pulp fibres in a weight rat;o of 1:1
in 1û hard tGerman degrees of hardness) water and having
a Schopper-Riegler freeness of 35 and a solids content of
0.5% is admixed with 20% of chalk as a filler, followed by
0.01% of PERCOL 292~ (a cationic h;gh molecular weight
(> 1x107) polyacrylamide) as an aid for retaining very fine
pulp fibre particles, the dispersion of the fibres attaining
the pH given in Table I below. The percentages are based
~23~24
- 28 -
on dry substance cf aid and filler, based on the solids con-
tent of the dispersion of the fibres~
Formulations of the sizing agent are prepared by
stirring 7~ each of the specified reaction products as crude
S produc~ in powder form~ as sizing agent, with, in each case,
3.5% of POLYMIN P~ (a polyethyleneimine which has a mole-
cular weight of 10,000 to 100,000), as a retention aid, in
the presence of deionised water and glass beads having a dia-
meter of 2 mm. The resulting dispersions are homogeneous,
pourable and stable. The percentages are based on dry sub-
stance of sizing agent and retention aid, based on the total
weight of the formulation.
The aqueous formulation of the sizing agent and the
retention aid is then added to the dispersion of the fibres
in such an amount that the amount of s;zing agent present in
the dispersion is 0.5~ on the dry substance of the sizing
agent, based on the solids content of the dispersion of the
fibres. The dispersion of the fibres is then processed in
a laboratory sheet former to give sheets of paper which,
following a first drying at 130C for 3 minutes, have a
weight per unit area of 80 g/m2. The sheet of paper thus
obtained is subjected to an additional thermal treatment at
140C for 3 minutes.
The two surfaces of the sheets of paper obtained~
i.e. the surface obtained on the sieve side of the sheet
former and the opposite surface are tested for their sizing
properties. For this purpose, the Cobb water absorption on
30 seconds' exposure (WA Cobb30) is measured in accordance
with DIN 53,132. The results of the WA Cobb30 measurements
in g/m on the sieve s;de (SS) and the opposite side (OS)
are given in Table I, before and after the thermal treatment
at 140C and before and after storage at 20C for one day.
The lower the water absorption, the better is the sizing of
the paper. WA Cobb30 ualues above 100 correspond to com-
pletely unsatisfactory sizing of the paper.
~23~332~
- 29 -
L t
=.~ .
1~1 Q ~ Q ~
C~) C Q ~ Q
O ~ O ~
' V 11~ V UJ
~1 o ~ 1_
''1 U ~
~3~3Z9~
- 30 -
Examples 20 and 21: The method of Examples 18 and 19 is
repeated, except that each of the formulations is prepared
with one of the reaction products given in Table II, below,
as a sizing agent.
The sizing results are summarised in Table II, bel.ow~
~2383Z~
r
:L
~1 ~ . ;~ ;
W24
- 32 -
Examples 22 to 24: The method of Examples 18 and 19 is
repeated, except that each of the formulations is prepared
with one of the reaction products given in Table III, below,
as a sizing agent.
S The s;zing results are summarised in Table III, below.
~.23fl324
- 33 -
_ ~ ; ~ ~ ~
E ':) _
~ ~V) O`
,~ ~V~ ~_ N1~1
E ~
G~
~,
O ~ ___ ..~ __
D (l~>~
O E ~
I~ . <~) U~ ~J~)
3 L ~O ~ ~ ~
V
_ ~V~ 00 00O
E ~v~ ~1 r~l u~
t_ ..
a
C O ~ r~
L O
O ~ ~ (~I O1~)
Q Il~ ~ r~l ~ ~
~ - - - ~
~ ~ l~ o~
I ~ 00 CO CO
CL ~ .
~ ~ ~ ~ O
L O O`L
n~ Q ~IJQ ~IJ ~1 ~
~) C QC Q C Q
C O E O E O E
., ~- ~U ~_ ~ _ ns
N ~ X ~ X ~ X
., ~ LU ~ ~11
a~ ~ ~ ~ a
~ ~ O Q~ O ~ O ,
_ ~Ll
_ E O I~J ~ ~
n ~ z N ~1 N
l_ X
, ~
3Z4
- 34 -
ExampLes 25 and Z6: The method of Examples 18 and 19 ;s
repeated, except that each of the formulations is prepared
with one of the reaction products given in Table IV, below,
as a sizing agent.
The sizing results are summarised in Table IV, below~
~23832~
~
J
O Q 00 00
I ~
_ _
Il) L O ~-
(~l Q ~ Q
~) _
., O E O E
N ~ X ~ X
'V~ LL Q~
'I , o ~r o
_ E O Il~ ~o
I_ Z , `J 1~1
~;~3~3~24
- 36 -
Example 27: The method of Examples 18 and 19 is repeated,
except that each of the formulations is prepared w;th one of
the reaction products given in Table V, below, as a sizing
agent.
The sizing results are summarised in Table V, below.
~8324
-- 37 --
3 ~ ~ O 1~
; ~ ~
, n ~o ~ N
O
aJ
O n ~
_ __ .__
~ V
O
t~ Q
C O E
N ~ X
.~ LL
_ ~Y O .
_ ¦ E O I~
~1 ~x
, ~ LL
~3~324
- 38 -
Examples 28 and 29: The method of Examples 18 and 19 is
repeated, except that each of the formulations is prepared
with one of the reaction products given in Table VI, below,
as a sizing agentO
The sizing results are summarised in Table VI below.
Table VI
Example Siz~ng agent pH of the WA Cobb30 ~g/m )
No. dispersion _ _ _
before thermal treatment
~_ _ after 1 day
.. ~ . _._
28 Reaction product
_ of ExampLe 5 8.4 17
29 Reaction product
of Example 6 8.3 17 17
Example 30: The method of Examples 18 and 19 is repeated,
except that the following formulation is used of the sizing
agent which is emulsified at 80C in the molten state in the
presence of water:
7 % of the reaction product of Example 11, as sizing agent
3.5% of POLYMIN P~, as a retention aid
0.7% of sorbitan monostearate as an oil-in-water emulsifier
0.7% of an adduct of ethylene oxide and sorbitan monostearate
as a water-in-oil emulsifier.
This formulation is homogeneous and stable.
The sizing results are summarised in Table VII~ below.
~L23~;~24
- 39 -
Table VII
Example pH of the WA Cobb30 (g/m )
No. dispers~on __
before thermal treatment after thermal
treatment
_ .. ... __ _ __
at once after 1 day at once
,
OS SS OS SS I OS
8.4 16 33 12 34 ¦ 13
Examples 31 and 34: The method of Examples 18 and 19 is
repeated, except that each of the formulations is prepared
with one of the reaction products given in Table VIII, below,
as a sizing agent.
The sizing results are summarised in Table VIII,
below.
Table VIII
Example Sizing agent pH of the WA Cobb30
No. dispersion
before thermal treatment
at once
_ _. ~ SS OS
31 Reaction product
. of Example 14 8.8 39 14
32 Reaction product
of Example 15 9.0 42 17
33 Reaction product
of Example 16 8.8 46 15
34 Reaction product
of Example 17 9.1 55 15
