U.S. patent application number 11/913823 was filed with the patent office on 2008-08-14 for method for producing paper, paperboard and cardboard in the presence of water-swellable polymers.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Samantha Champ, Simon Champ, Roland Ettl.
Application Number | 20080190576 11/913823 |
Document ID | / |
Family ID | 37311148 |
Filed Date | 2008-08-14 |
United States Patent
Application |
20080190576 |
Kind Code |
A1 |
Champ; Simon ; et
al. |
August 14, 2008 |
Method for Producing Paper, Paperboard and Cardboard in the
Presence of Water-Swellable Polymers
Abstract
A process for the production of paper, board and cardboard in
the presence of a water-swellable polymer by adding the
water-swellable polymer to a fiber suspension, the fiber suspension
comprising water-swellable polymers being beaten.
Inventors: |
Champ; Simon; (Ludwigshafen,
DE) ; Ettl; Roland; (Ketsch, DE) ; Champ;
Samantha; (Ludwigshafen, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
37311148 |
Appl. No.: |
11/913823 |
Filed: |
May 16, 2006 |
PCT Filed: |
May 16, 2006 |
PCT NO: |
PCT/EP2006/062346 |
371 Date: |
November 7, 2007 |
Current U.S.
Class: |
162/164.1 |
Current CPC
Class: |
D21H 27/10 20130101;
D21H 27/30 20130101; D21H 21/22 20130101; D21H 23/16 20130101; D21H
27/002 20130101 |
Class at
Publication: |
162/164.1 |
International
Class: |
D21H 17/20 20060101
D21H017/20; D21H 23/04 20060101 D21H023/04 |
Foreign Application Data
Date |
Code |
Application Number |
May 18, 2005 |
DE |
10 2005 023 608.1 |
Claims
1. A process for the production of paper, board and cardboard in
the presence of water-swellable polymers by adding the
water-swellable polymer to a fiber suspension, wherein the fiber
suspension comprising water-swellable polymers is beaten.
2. The process according to claim 1, wherein the water-swellable
polymer can absorb at least 1% of its own weight of water.
3. The process according to claim 1, wherein the water-swellable
polymers are superabsorbent polymers.
4. The process according to claim 1, wherein paper process
chemicals are added after the beating of the fiber suspension
comprising water-swellable polymers.
5. The process according to claim 1, wherein the water-swellable
polymer is added as a gelatinous suspension to the fiber
suspension.
6. The process according to claim 1, wherein the water-swellable
polymer is introduced into the fiber suspension by spraying.
7. The process according to claim 1, wherein from 0.1 to 20% by
weight of a water-swellable polymer are added to the fiber
suspension.
8. (canceled)
9. A paper, board or cardboard produced by the process according to
claim 1.
10. The paper according to claim 9, characterized in that it is
tissue paper, hygiene or sanitary paper, packaging paper or
multilayer paper.
Description
[0001] The present invention describes a process for the production
of paper, board and cardboard in the presence of water-swellable
polymers. The invention furthermore relates to the use of
water-swellable polymers in the production of paper, board and
cardboard, and paper products comprising water-swellable
polymers.
[0002] Water-swellable polymers in the context of the invention are
polymers which can absorb at least 1% of their own weight of water.
They preferably absorb at least 10% of their own weight,
particularly preferably at least 25% of their own weight and
especially preferably at least 50% of their own weight of water.
Water-swellable polymers in the context of the present invention
are in particular so-called superabsorbent polymers which can
absorb at least 100% of their own weight of water. These are, for
example, polymers of (co)polymerized hydrophilic monomers, graft
(co)polymers of one or more hydrophilic monomers on a suitable
grafting base, crosslinked cellulose ethers or starch ethers,
crosslinked carboxylmethylcellulose, partly crosslinked
polyalkylene oxide or natural products, such as, for example, guar
derivatives, which are swellable in aqueous liquids. Such hydrogels
are usually used as a gelatinous suspension of absorbent product
for the production of diapers, tampons, sanitary towels and other
hygiene articles, but also as water-retaining agents in
horticulture.
[0003] The use of water-swellable polymers can, however, also be of
interest in other areas. To date, polyurethane foams and so-called
airlaid cellulose mats have been used for increasing the water
absorptivity of tissue paper while at the same time maintaining the
wet strength. These are also used in the production of packaging
material, the packaging material being said also to retain the
strength while simultaneously absorbing liquids. This is, for
example, packaging material for frozen foods. In papermaking, an
increase in the bulk is desired without the strength of the paper
suffering. These could also be potential applications for
water-swellable polymers.
[0004] EP 0 437 816 A1 describes a highly absorbent wet-laid woven
material which is obtained by a process comprising the following
steps: mixing of the superabsorber polymer particle with a liquid
to form a slurry, mixing of the slurry thus obtained with fibers,
filtration of the superabsorber polymer/fiber mixture and
subsequent drying to obtain a highly absorbent wet-laid nonwoven
material. The materials thus obtained are used, inter alia, in
diapers, incontinence articles, packaging papers for food and
dressing materials, such as plasters.
[0005] EP 1 068 392 B1 discloses an improved wet process for the
production of an absorbent structure. According to it, a fiber
suspension which additionally comprises water-swellable,
water-insoluble superabsorber particles is processed in an
apparatus for the formation of nonwovens by a wet process. A wet
nonwoven comprising wetted superabsorber particles is formed, from
which nonwoven water is withdrawn and which nonwoven is then
transported into the dry end. It is decisive here that the contact
between superabsorber and suspension until the nonwoven runs into
the dry end is not more than 45 seconds, with the result that the
superabsorber does not have sufficient time for swelling.
[0006] U.S. Pat. No. 5,997,690 and U.S. Pat. No. 6,290,813 B1
disclose a process for the production of highly absorbent wet-laid
nonwoven material, first a slurry of water-swellable,
water-insoluble superabsorber particles with fibers being produced,
the superabsorber particles having a particle size of less than 250
micrometers before addition. A salt-containing solution is then
added to this slurry. A wet web is then formed and is washed with
water and then dried. The wet-laid nonwoven materials thus obtained
have a residual salt content of less than 40% in the dry state.
[0007] US 2002/0060013 A1 relates to a process for the production
of wet-laid nonwoven materials which comprise at least 1% by weight
of an absorbent polymer having a thermal-reversible liquid
absorption capacity.
[0008] US 2003/0014038 Al discloses superabsorbent articles which
comprise a core having swellable branched superabsorbent particles
which is in a liquid-permeable shell. Effective amounts of an
antibiotic or of an antibacterial agent can be added to the
articles disclosed in this publication, so that the end product can
be used in the medical sector.
[0009] A disadvantage of the processes of the prior art is that the
abovementioned problems are not sufficiently solved or
eliminated.
[0010] It was therefore an object of the present invention to
provide a process for the production of paper, board and cardboard
in the presence of a water-swellable polymer, which process
eliminates the abovementioned problems, namely the size of the
swollen polymer in comparison with the paper thickness and, on the
other hand, the high water content of the swollen polymer, which is
usually up to 99.9% by weight.
[0011] The object was achieved by a process for the production of
paper, board and cardboard in the presence of a water-swellable
polymer by adding the water-swellable polymer to a fiber
suspension, the fiber suspension comprising water-swellable
polymers being beaten.
[0012] A water-swellable polymer in the context of the present
invention is understood as meaning water-absorbent polymers which
can absorb at least 1% of their own weight of water. Preferably,
they absorb at least 10% of their own weight, particularly
preferably at least 25% of their own weight and particularly
preferably at least 50% of their own weight of water.
Water-swellable polymers in the context of the present invention
are in particular so-called superabsorbent polymers which can
absorb at least 100% of their own weight of water. These are, for
example, polymers of (co)polymerized hydrophilic monomers, graft
(co)polymers of one or more hydrophilic monomers on a suitable
grafting base, crosslinked cellulose ethers or starch ethers,
crosslinked carboxymethylcellulose, partly crosslinked polyalkylene
oxide or natural products, such as, for example, guar derivatives,
which are swellable in aqueous liquids. Such hydrogels are usually
used as aqueous solutions of absorbent products for the production
of diapers, tampons, sanitary towels and other hygiene
articles.
[0013] In the process according to the invention, the fiber
suspension comprising water-swellable polymers is beaten. This
beating is usually effected up to a Schopper-Riegler freeness of
10, preferably of 25, particularly preferably of 35, very
particularly preferably of 50 and particularly preferably of 70.
The beating can be effected, for example, in a conventional
pulper.
[0014] The fiber suspension comprising water-swellable polymers is
then subjected to the customary papermaking process. After the
beating, paper process chemicals are preferably added. However, it
is of course possible to add paper process chemicals to the fiber
suspension even before the addition of the water-swellable
polymer.
[0015] The mixture comprising water-swellable polymers can pass
through one or more shearing stages both before the addition of the
paper process chemicals and thereafter. The mixture is then drained
with sheet formation on a wire and drying of the sheets.
[0016] The paper process chemicals added are the additives usually
used in papermaking, in the conventional amounts, for example
fixing agents, retention aids, including microparticle systems, dry
and wet strength agents, engine sizes, biocides and/or dyes.
[0017] In the process according to the invention, from 0.1 to 20%
by weight of a water-swellable polymer are added to the fiber
suspension. The amount of water-swellable polymers in the fiber
suspension is preferably from 0.5 to 10% by weight, particularly
preferably from 0.8 to 5% by weight and very particularly
preferably from 1 to 2.5% by weight, based in each case on the
solids content of the suspension.
[0018] The fiber suspension to which the water-swellable polymer is
added comprises, as a rule, from 0.5 to 4% by weight of fibers,
preferably from 0.5 to 2.5% by weight of fibers and very
particularly preferably from 0.8 to 1.5% by weight of fibers, based
in each case on the solids content of the suspension. Particularly
preferably, the suspension has a proportion of about 1% by weight
of fibers, based on the solids content of the suspension.
[0019] Before swelling in aqueous solution, the water-swellable
polymers may have any particle size; the particle size is
preferably in the range from 10 nm to 10 mm, particularly
preferably in the range from 50 nm to 5 mm and particularly
preferably in the range from 100 nm to 1 mm. After swelling, the
water-swellable polymers usually have particle sizes in the range
from 100 nm to 100 mm, preferably in the range from 0.5 mm to 25 mm
and particularly preferably in the range from 0.1 mm to 10 mm.
[0020] The form in which the water-swellable polymer is added to
the fiber suspension is unimportant. Thus, for example, a solid
mixture of the fibers with a solid mixture of the water-swellable
polymers can be mixed with one another in the abovementioned
quantity ranges of the individual components. Sufficient water is
then added to the mixture so that a fiber suspension comprising
water-swellable polymers forms. In this way, the water-swellable
polymer is given the opportunity to swell in the presence of the
fibers.
[0021] It is also possible to prepare a gelatinous suspension of a
water-swellable polymer in water, in which the water-swellable
polymer swells, this gelatinous suspension then being added to the
fiber suspension. In this embodiment of the process according to
the invention, it is possible, if the gelatinous suspension
comprising swollen water-swellable polymer is subjected to a
shearing stage. The duration and shearing rate depend on the
water-swellable polymer used. The optimum duration and shearing
rate are determined by the person skilled in the art as part of his
customary experiments.
[0022] In another embodiment of the process according to the
invention, the water-swellable polymer is introduced into the fiber
suspension by spraying.
[0023] It is of course also possible to use a plurality of
water-swellable polymers in the process according to the invention.
These may be added to the fiber suspension both simultaneously as a
mixture and separately from one another. Preferably, however, one
water-swellable polymer is used.
[0024] Preparation processes for superabsorbent polymers are
described in "Modern Superabsorbent Polymer Technology", F. L.
Buchholz and A. T. Graham, Wiley-VCH, 1998, pages 69 to 118. There,
a monomer solution is polymerized to give a base polymer, for
example in a kneader or a belt reactor.
[0025] The superabsorbent polymer particles which can be used in
the process according to the invention can be prepared by
polymerization of a monomer solution comprising [0026] i) at least
one ethylenically unsaturated monomer carrying acid groups, [0027]
ii) at least one crosslinking agent, [0028] iii) if appropriate,
one or more ethylenically and/or allylically unsaturated monomers
copolymerizable with i) and [0029] iv) if appropriate, one or more
water-swellable polymers onto which the monomers i), ii) and, if
appropriate, iii) can be at least partly grafted, the base polymer
obtained being dried, classified, [0030] v) if appropriate,
aftertreated with at least one postcrosslinking agent, dried and
thermally postcrosslinked.
[0031] Suitable monomers i) are, for example, ethylenically
unsaturated carboxylic acids, such as acrylic acid, methacrylic
acid, maleic acid, fumaric acid and itaconic acid, or derivatives
thereof, such as acrylamide, methacrylamide, acrylates and
methacrylates. Particularly preferred monomers are acrylic acid and
methacrylic acid. Acrylic acid is very particularly preferred.
[0032] The monomers i), in particular acrylic acid, preferably
comprise up to 0.025% by weight of a hydroquinone monoether.
Preferred hydroquinone monoethers are hydroquinone monomethyl ether
(MEHQ) and/or tocopherols.
[0033] Tocopherol is understood as meaning compounds of the formula
below
##STR00001##
where R.sup.1 is hydrogen or methyl, R.sup.2 is hydrogen or methyl,
R.sup.3 is hydrogen or methyl and R.sup.4 is hydrogen or an acid
radical having 1 to 20 carbon atoms.
[0034] Preferred radicals R.sup.4 are acetyl, ascorbyl, succinyl,
nicotinyl and other physiologically tolerated carboxylic acids. The
carboxylic acids may be mono- di- or tricarboxylic acids.
[0035] alpha-Tocopherol where R.sup.1=R.sup.2=R.sup.3=methyl is
preferred, in particular racemic alpha-tocopherol. R.sup.4 is
particularly preferably hydrogen or acetyl. RRR-alpha-tocopherol is
particularly preferred.
[0036] The monomer solution preferably comprises not more than 130
ppm by weight, particularly preferably not more than 70 ppm by
weight, preferably at least 10 ppm by weight, particularly
preferably at least 30 ppm by weight, especially preferably about
50 ppm by weight, of hydroquinone monoether, based in each case on
acrylic acid, acrylic acid salts being taken into account in the
calculation as acrylic acid. For example, an acrylic acid having a
corresponding content of hydroquinone monoether can be used for the
preparation of the monomer solution.
[0037] The superabsorbent polymers are crosslinked, i.e. the
polymerization is carried out in the presence of compounds having
at least two polymerizable groups which can be incorporated in the
form of polymerized units into the polymer network by free radical
polymerization. Suitable crosslinking agents ii) are, for example,
ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl
methacrylate, trimethylolpropane triacrylate, triallylamine,
tetraallyloxyethane, as described in EP-A-0 530 438, di- and
triacrylates, as described in EP-A 547 847, EP-A 559 476, EP-A 632
068, WO 93121237, WO 03/104299, WO 03/104300 and WO 03/104301 and
in the German Patent Application with the application number DE 103
31 450.4, mixed acrylates which comprise further ethylenically
unsaturated groups in addition to acrylate groups, as described in
the German Patent Applications with the application numbers DE 103
31 456.3 and DE 103 55 401.7, or mixtures of crosslinking agents,
as described, for example, in DE-A-195 43 368, DE-A-196 46 484,
WO-A-90/15830 and WO-A-02/32962.
[0038] Suitable crosslinking agents ii) are in particular
N,N'-methylenebisacrylamide and N,N'-methylenebismethacrylamide,
esters of unsaturated mono- or polycarboxylic acids with polyols,
such as diacrylate or triacrylate, for example butanediol or
ethylene glycol diacrylate or dimethacrylate and trimethylolpropane
triacrylate, and ally compounds, such as allyl (meth)acrylate,
triallyl cyanurate, diallyl maleate, polyallyl esters,
tetraallyloxyethane, triallylamine, tetraallylethylenediamine,
allyl esters of phosphoric acid and vinylphosphonic acid
derivatives, as described, for example, in EP-A-0 343 427. Further
suitable crosslinking agents ii) are pentaerythrityl di-,
pentaerythrityl tri- and pentaerythrityl tetraallyl ethers,
polyethylene glycol diallyl ether, ethylene glycol diallyl ethers,
glyceryl diallyl ethers and glyceryl triallyl ethers, polyallyl
ethers based on sorbitol and ethoxylated variants thereof.
Di(meth)acrylates of polyethylene glycols can be used in the
process according to the invention, the polyethylene glycol used
having a molecular weight of from 300 to 1000.
[0039] Particularly advantageous crosslinking agents ii) are,
however, di- and triacrylates of glycerol having a degree of
ethoxylation of from 3 to 20, of trimethylolpropane having a degree
of ethoxylation of from 3 to 20, and of trimethylolethane having a
degree of ethoxylation of from 3 to 20, in particular di- and
triacrylates of glycerol or of trimethylolpropane having a degree
of ethoxylation of from 2 to 6, of tripropoxylated glycerol or
trimethylolpropane, and of glycerol trialkoxylated with a mixture
of ethylene oxide and propylene oxide, of glycerol or
trimethylolpropane having a degree of ethoxylation of 15, and of
glycerol, trimethylolethane or trimethylolpropane having a degree
of ethoxylation of at least 40.
[0040] Very particularly preferred crosslinking agents ii) are the
polyethoxylated and/or propoxylated glycerols esterified with
acrylic acid or methacrylic acid to give di- or triacrylates, as
described, for example, in the prior German Application with the
application number DE 103 19 462.2. Di- and/or triacrylates of
glycerol having a degree of ethoxylation of from 3 to 10 are
particularly preferred. Di- or triacrylates of ethoxylated and/or
propoxylated glycerol having a degree of alkoxylation of from 1 to
5 are very particularly preferred. Most preferred are the
triacrylates of ethoxylated and/or propoxylated glycerol having a
degree of alkoxylation of from 3 to 5. These are distinguished by
particularly low residual contents (typically less than 10 ppm by
weight) in the superabsorbent polymer, and the aqueous extracts of
the superabsorbent polymers prepared therewith have a virtually
unchanged surface tension (typically at least 0.068 N/m) in
comparison with water at the same temperature.
[0041] Ethylenically unsaturated monomers iii) copolymerizable with
the monomers i) are, for example, acrylamide, methacrylamide,
crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl
acrylate, dimethylaminopropyl acrylate, diethylaminopropyl
acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl
methacrylate, diethylaminoethyl methacrylate,
dimethylaminoneopentyl acrylate and dimethylaminoneopentyl
methacrylate.
[0042] Polyvinyl alcohol, polyvinylpyrrolidone, starch, starch
derivatives, polyglycols or polyacrylic acids, preferably polyvinyl
alcohol and starch, can be used as water-soluble polymers iv).
[0043] The preparation of a suitable base polymer and further
suitable hydrophilic ethylenically unsaturated monomers i) are
described in DE-A 199 41 423, EP-A 686 650, WO 01/45758 and WO
03/104300.
[0044] The reaction is preferably carried out in a kneader, as
described, for example in WO 01/38402, or on a belt reactor, as
described, for example, in EP-A 955 086.
[0045] After leaving the polymerization reactor, the hydrogel is
advantageously stored at a relatively high temperature, preferably
at least 50.degree. C., particularly preferably at least 70.degree.
C., very particularly preferably at least 80.degree. C., and
preferably less than 100.degree. C., for example in insulated
containers. As a result of the storage, usually from 2 to 12 hours,
the monomer conversion is further increased.
[0046] Some, preferably from 25 to 95 mol %, preferably from 27 to
80 mol %, particularly preferably from 27 to 30 mol % or from 40 to
75 mol %, of the acid groups of the hydrogels obtained are usually
neutralized, it being possible to use the conventional neutralizing
agents, preferably alkali metal hydroxides, alkali metal oxides,
alkali metal carbonates or alkali metal bicarbonates, and mixtures
thereof. Instead of alkali metal salts, it is also possible to use
ammonium salts. Sodium and potassium are particularly preferred as
alkali metals, but sodium hydroxide, sodium carbonate and sodium
bicarbonate and mixtures thereof are very particularly preferred.
Usually, the neutralization is achieved by mixing in the
neutralizing agent as aqueous solution, as melt or preferably as
solid. For example, sodium hydroxide may be present with a water
content substantially lower than 50% by weight as a waxy material
having a melting point above 23.degree. C. In this case, metering
in the form of fragments or as a melt at elevated temperature is
possible.
[0047] The neutralization can be carried out after the
polymerization at the stage of the hydrogel. However, it is also
possible to neutralize up to 40 mol %, preferably from 10 to 30 mol
%, particularly preferably from 15 to 25 mol %, of the acid groups
before the polymerization by adding a part of the neutralizing
agent to the monomer solution beforehand and establishing the
desired final degree of neutralization only after the
polymerization at the stage of the hydrogel. The monomer solution
can be neutralized by mixing in the neutralizing agent. The
hydrogel can be mechanically comminuted, for example by means of a
chopping machine, it being possible for the neutralizing agent to
be sprayed on, sprinkled over or poured on and then carefully mixed
in. For this purpose, the gel material obtained can be treated
several times in the chopping machine for homogenization. The
neutralization of the monomer solution directly to the final degree
of neutralization is preferred.
[0048] The neutralized hydrogel is then dried using a belt or drum
drier until the residual moisture content is preferably below 15%
by weight, in particular below 10% by weight, the water content
being determined by test method No. 430-2-02 "Moisture content"
recommended by EDANA (European Disposables and Nonwovens
Association). Alternatively, however, a fluidized-bed drier or a
heated plowshare mixer can also be used for the drying.
[0049] The dried hydrogel is then milled and classified, it usually
being possible to use one-speed or multispeed roll mills,
preferably two- or three-speed roll mills, pinned-disk mills,
hammer mills or vibratory mills for the milling.
[0050] In order to improve the performance characteristics, such
as, for example, liquid conductivity (SFC) in the diaper and
absorption under load (AUL), superabsorbent polymer particles are
generally postcrosslinked. This postcrosslinking can be carried out
in the aqueous gel phase. Preferably, however, milled and sieved
polymer particles (base polymer) are coated on the surface with a
postcrosslinking agent, dried and thermally postcrosslinked.
Crosslinking agents suitable for this purpose are compounds which
comprise at least two groups which can form covalent bonds with the
carboxylate groups of the hydrophilic polymer or which can
crosslink at least two carboxyl groups or other functional groups
of at least two different polymer chains of the base polymer with
one another.
[0051] Postcrosslinking agents v) suitable for this purpose are
compounds which comprise at least two groups which can form
covalent bonds with the carboxylate groups of the polymers.
Suitable compounds are, for example, alkoxysilyl compounds,
polyaziridines, polyamines, polyamidoamines, di- or polyglycidyl
compounds, as described in EP-A 083 022, EP-A 543 303 and EP-A 937
736, polyhydric alcohols, as described in DE-C 33 14 019, DE-C 35
23 617 and EP-A 450 922, or .beta.-hydroxyalkylamides, as described
in DE-A 102 04 938 and US 6,239,230. Furthermore suitable are
compounds having a mixed functionality, such as glycidol,
3-ethyl-3-oxetanemethanol (trimethylolpropanoxetane), as described
in EP-A 1 199 327, aminoethanol, diethanolamine, triethanolamine or
compounds which form a further functionality after the first
reaction, such as ethylene oxide, propylene oxide, isobutylene
oxide, aziridine, azetidine or oxetane.
[0052] Furthermore, DE-A 40 20 780 describes cyclic carbonates,
DE-A 198 07 502 describes 2-oxazolidone and derivatives thereof,
such as N-(2-hydroxyethyl)-2-oxazolidone, DE-A 198 07 992 describes
bis- and poly-2-oxazolidinones, DE-A 198 54 573 describes
2-oxotetrahydro-1,3-oxazine and derivatives thereof, DE-A 198 54
574 describes N-acyl-2-oxazolidones, DE-A 102 04 937 describes
cyclic ureas, the German Patent Application with the application
number DE 103 34 584.1 describes bicyclic amidoacetals, EP-AL 199
327 describes oxetanes and cyclic ureas and WO 03/031482 describes
morpholine-2,3-dione and derivatives thereof as suitable
postcrosslinking agents v).
[0053] The postcrosslinking is usually carried out in a manner such
that a solution of the postcrosslinking agent is sprayed onto the
hydrogel or the dried base polymer particles. After the spraying
on, thermal drying is effected, it being possible for the
postcrosslinking reaction to take place both before and during the
drying.
[0054] Spraying on of a solution of the crosslinking agent is
preferably carried out in mixers having moving mixing tools, such
as screw mixers, paddle mixers, disk mixers, plowshare mixers and
blade mixers. Vertical mixers are particularly preferred and
plowshare mixers and blade mixers are very particularly preferred.
Suitable mixers are, for example, Lodige.RTM. mixers, Bepex.RTM.
mixers, Nauta.RTM. mixers, Processall.RTM. mixers and Schugi.RTM.
mixers.
[0055] The thermal drying is preferably carried out in contact
driers, particularly preferably paddle driers, very particularly
preferably disk driers. Suitable driers are, for example,
Bepex.RTM. driers and Nara.RTM. driers. In addition, fluidized-bed
driers may also be used.
[0056] The drying can be effected in the mixer itself, by heating
the jacket or blowing in warm air. A downstream drier, such as, for
example, a tray drier, a rotary kiln or a heatable screw, is also
suitable. However, it is also possible to use, for example,
azeotropic distillation as a drying method.
[0057] Preferred drying temperatures are in the range from 50 to
250.degree. C., preferably from 50 to 200.degree. C. and
particularly preferably from 50 to 150.degree. C. The preferred
residence time at this temperature in the reaction mixer or drier
is less than 30 minutes, particularly preferably less than 10
minutes.
[0058] The papers, boards and cardboards produced by the process
according to the invention have higher water absorption capacities
compared with conventional paper qualities, without losses in
strength having to be accepted. The papers can absorb water and can
retain it even under the action of heat, such as, for example, when
used in laser printers.
[0059] All paper qualities can be produced by the process according
to the invention, for example cardboard, single-layer/multilayer
folding boxboard, single-layer/multilayer liner, corrugated
material, papers for newsprint, so-called medium writing and
printing papers, natural gravure printing papers and light-weight
coating papers. In order to produce such papers, it is possible to
start from, for example, groundwood, thermomechanical pulp (TMP),
chemothermomechanical pulp (CTMP), pressure groundwood (PGW),
mechanical pulp and sulfite and sulfate pulp. The chemical pulps
may be both short-fiber and long-fiber.
[0060] Preferably, so-called tissue papers, such as lavatory paper,
paper handkerchiefs and cosmetic cloths and kitchen paper, and
furthermore hygiene and sanitary papers, packaging papers, for
example for food, or multilayer papers which can be used in hygiene
articles or packaging materials are preferably produced by the
process according to the invention. The last-mentioned multilayer
papers consist of a plurality of different paper layers, the paper
layer which was produced by the process according to the invention
being incorporated either above a conventional paper layer or
between two conventional paper layers.
[0061] The present invention furthermore relates to the use of
water-swellable polymers in the production of paper, board and
cardboard in the process according to the invention.
[0062] The present invention furthermore relates to paper, board
and cardboard which are produced by the process according to the
invention. In particular, the invention relates to so-called tissue
papers, such as lavatory paper, paper handkerchiefs and cosmetic
cloths and kitchen paper, and furthermore hygiene and sanitary
papers, packaging papers, for example for food, or multilayer
papers which can be used in hygiene articles or packaging
materials.
[0063] The invention is explained in more detail with reference to
the following, nonlimiting examples.
EXAMPLES
[0064] The stated percentages in the examples are percentages by
weight, unless otherwise evident from the context.
[0065] The dry breaking length of the dried paper sheets was
determined by the test method according to DIN EN ISO 1924-2.
[0066] Water-Swellable Polymer 1
[0067] At room temperature, Luquasorb.RTM. 1280 from BASF
Aktiengesellschaft was swelled as the water-swellable polymer in a
small excess of water for one hour.
Example 1
[0068] 1% by weight, based on the solids content of the paper stock
suspension, of the previously swelled water-swellable polymer 1 was
added to a mixture of bleached birch sulfate and bleached pine
sulfite in the ratio of 70:30 at a solids concentration of 1%. This
mixture was beaten in a laboratory pulper until free of fiber
bundles and until a Schopper-Riegler freeness of 35 was
reached.
Example 2
[0069] Example 1 was repeated, except that 2.5% by weight, based on
the solids content of the paper stock suspension, of the previously
swollen water-swellable polymer 1 were added to the mixture of
bleached birch sulfate and bleached pine sulfite.
Example 3
[0070] 1% by weight, based on the solids content of the paper stock
suspension, of the previously swelled water-swellable polymer 1 was
added to a mixture of bleached birch sulfate and bleached pine
sulfite in the ratio of 70:30 at a solids concentration of 1%. This
mixture was beaten in a laboratory pulper until free of fiber
bundles and until a Schopper-Riegler freeness of 35 was reached.
Immediately thereafter, a cationic polyacrylamide was metered as a
retention aid (Polymin.RTM. KE 2020 from BASF Aktiengesellschaft)
into this mixture. The amount of retention aid metered was 0.03% of
polymer, based on the solids content of the paper stock
suspension.
Example 4
[0071] Example 3 was repeated, except that 2.5% by weight, based on
the solids content of the paper stock suspension, of the previously
swollen water-swellable polymer 1 were added to the mixture of
bleached birch sulfate and bleached pine sulfite.
Example 5
[0072] 1% by weight, based on the solids content of the paper stock
suspension, of the previously swelled water-swellable polymer 1 was
added to a mixture of bleached birch sulfate and bleached pine
sulfite in the ratio of 70:30 at a solids concentration of 1%. This
mixture was beaten in a laboratory pulper until free of fiber
bundles and until a Schopper-Riegler freeness of 35 was reached.
Immediately thereafter, a cationic polyacrylamide as a retention
aid (Polymin.RTM. KE 2020 from BASF Aktiengesellschaft) and a
filler (Hydrocarb.RTM. OG from Omya) were metered into this
mixture. The amount of retention and of filler metered was 0.03% of
polymer and 20% of filler, based on the solids content of the paper
stock suspension.
Example 6
[0073] Example 5 was repeated, except that 2.5% by weight, based on
the solids content of the paper stock suspension, of the previously
swollen water-swellable polymer 1 were added to the mixture of
bleached birch sulfate and bleached pine sulfite.
Comparative Example 1
[0074] A mixture of bleached birch sulfate and bleached pine
sulfite in the ratio of 70:30 was beaten in a laboratory pulper at
a solids concentration of 1% until free of fiber bundles, until a
Schopper-Riegler freeness of 35 was reached. A cationic starch
(Solvitose.RTM. BKN) was then added in an amount of 0.06% by
weight, based on the solids content of the paper stock
suspension.
Comparative Example 2
[0075] A mixture of bleached birch sulfate and bleached pine
sulfite in the ratio 70:30 was beaten in a laboratory pulper at a
solids concentration of 1% until free of fiber bundles, until a
Schopper-Riegler freeness of 35 was reached. A cationic starch
(Solvitose.RTM. BKN) was then added in an amount of 0.06% by
weight, based on the solids content of the paper stock suspension.
Immediately thereafter, a cationic polyacrylamide as a retention
aid (Polymin.RTM. KE 2020 from BASF Aktiengesellschaft) and a
filler (Hydrocarb.RTM. OG from Omya) were metered into this
mixture. The amount of retention aid and of filler metered was
0.03% of polymer and 20% of filler, based on the solids content of
the paper stock suspension.
[0076] Production of Paper Sheets
[0077] The paper sheets were produced in each case on a
Rapid-Kothen sheet former according to ISO 5269/2 with a sheet
weight of 80 g/m.sup.2 and then dried for 5 minutes at 100.degree.
C. The dry breaking length of the paper sheets was then tested. The
results are summarized in table 1.
TABLE-US-00001 TABLE 1 Example Dry breaking length [m] 1 6418 2
5563 3 5493 4 5329 5 4842 6 4727 Comparative example 1 5219
Comparative example 2 2790
[0078] Testing of the Water Absorption by the Wicking Test
[0079] The paper sheets were cut in each case to a size of 200
mm.times.15 mm. These cut paper strips were each suspended in a
beaker which was filled with water, the upper end of the paper
strip having been fastened with a clip to the edge of the beaker.
At the beginning of the test, the paper strips dipped about 10 to
20 mm into the water, the position of immersion (lower limit) being
marked. After 10 minutes, the paper strips were withdrawn from the
water. The upper limit up to which the water had run was also
marked. The distance between lower and upper limits, i.e. the
distance covered by the water, was then measured. The results are
summarized in table 2.
TABLE-US-00002 TABLE 2 Distance between the lower and upper limits
Example [mm] 1 82 2 90 3 81 4 88 5 91 6 87 Comparative example 1 72
Comparative example 2 76
* * * * *