U.S. patent application number 12/438312 was filed with the patent office on 2009-10-22 for method for treating cellulose-containing fibers or planar structures containing cellulose-containing fibers.
This patent application is currently assigned to WACKER CHEMIE AG. Invention is credited to Willibald Burger, Christian Herzig, Monika Rappl.
Application Number | 20090260769 12/438312 |
Document ID | / |
Family ID | 38668648 |
Filed Date | 2009-10-22 |
United States Patent
Application |
20090260769 |
Kind Code |
A1 |
Herzig; Christian ; et
al. |
October 22, 2009 |
METHOD FOR TREATING CELLULOSE-CONTAINING FIBERS OR PLANAR
STRUCTURES CONTAINING CELLULOSE-CONTAINING FIBERS
Abstract
Cellulosic substrates are treated with compound(s) containing at
least two primary amino groups and compounds containing at least
one .beta.-ketocarbonyl group. The substrates exhibit good strength
and hand properties.
Inventors: |
Herzig; Christian; (Waging,
DE) ; Burger; Willibald; (Burghausen, DE) ;
Rappl; Monika; (Burghausen, DE) |
Correspondence
Address: |
BROOKS KUSHMAN P.C.
1000 TOWN CENTER, TWENTY-SECOND FLOOR
SOUTHFIELD
MI
48075
US
|
Assignee: |
WACKER CHEMIE AG
Munich
DE
|
Family ID: |
38668648 |
Appl. No.: |
12/438312 |
Filed: |
August 6, 2007 |
PCT Filed: |
August 6, 2007 |
PCT NO: |
PCT/EP07/58141 |
371 Date: |
February 20, 2009 |
Current U.S.
Class: |
162/164.4 ;
162/158; 162/164.6 |
Current CPC
Class: |
D21H 27/002 20130101;
C08J 2301/00 20130101; D21H 17/59 20130101; D21H 17/55 20130101;
D21H 17/53 20130101; D21H 21/20 20130101; C08G 73/02 20130101; C08G
77/46 20130101; C08J 7/12 20130101; D21H 17/56 20130101 |
Class at
Publication: |
162/164.4 ;
162/158; 162/164.6 |
International
Class: |
D21H 17/59 20060101
D21H017/59; D21H 17/07 20060101 D21H017/07; D21H 17/56 20060101
D21H017/56 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 25, 2006 |
DE |
10 2006 039 941.2 |
Claims
1.-18. (canceled)
19. A method for treating a substrate of cellulose-containing
fibers or planar structures containing cellulose-containing fibers,
comprising treating with a combination of (1) compounds having at
least two primary amino groups and (2) compounds having at least
one .beta.-ketocarbonyl group.
20. The method of claim 19, wherein the compounds (2) contain
.beta.-ketocarbonyl groups of the formula
--Y'--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4 or their tautomeric
enol form of the formula
--Y'--C(O)--CR.sup.4.dbd.C(CH.sub.2R.sup.4)--OH in which Y' is
--O--, --NR.sup.2-- or ##STR00006## R.sup.2 is a hydrogen atom or a
monovalent hydrocarbon radical having 1 to 30 C atoms, and R.sup.4
is a hydrogen atom or a monovalent hydrocarbon radical having 1 to
18 C atoms.
21. The method of claim 19, wherein Y' is --O--.
22. The method of claim 19, wherein one or both of R.sup.2 and
R.sup.3 are hydrogen.
23. The method of claim 19, wherein polyamine(s) are used as at
least one compound (1).
24. The method of claim 19, wherein .beta.-ketocarbonyl-functional
monomeric compounds (2a) of the formula
L(--Y--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4).sub.e (I) or their
tautomeric enol forms in which e is an integer from 1 to 20, L is a
monomeric organic radical having the valency or functionality
corresponding to the index e in formula (I), and Y is --O-- or
--NR.sup.2--, R.sup.2 is a hydrogen atom or a monovalent
hydrocarbon radical having 1 to 30 C atoms, and R.sup.4 is a
hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 C
atoms, are used as compounds (2).
25. The method of claim 24, wherein e is 2 to 8.
26. The method of claim 19, wherein .beta.-ketocarbonyl-functional
oligomeric or polymeric compounds (2b) of the formula
K(--Y--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4).sub.f (III) or their
tautomeric enol forms, in which f is an integer from 1 to 10,000, K
is an oligomeric or polymeric, organic or organosilicon radical
having the valency or functionality corresponding to the index f in
formula (III), and Y is --O-- or --NR.sup.2--, and R.sup.4 is a
hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 C
atoms, are used as compounds (2).
27. The method of claim 26, wherein an organopolysiloxane radical
or an organopolysiloxane-containing copolymer radical is a radical
K in the .beta.-ketocarbonyl-functional oligomeric or polymeric
compounds (2b).
28. The method of claim 19, wherein .beta.-ketocarbonyl-functional
organosilicon compounds (2c) which contain at least one Si-bonded
radical of the general formula ##STR00007## in which --(Si.ident.)
is the bond to the silicon atom, R.sup.1 is a divalent organic
radical having 1 to 6 carbon atoms which optionally contain
non-adjacent nitrogen atoms, R.sup.3 is a divalent organic radical
having 1 to 6 carbon atoms, Y is --O-- or --NR.sup.2--, R.sup.2 is
a hydrogen atom or a monovalent hydrocarbon radical having 1 to 30
C atoms, and R.sup.4 is a hydrogen atom or a monovalent hydrocarbon
radical having 1 to 18 C atoms, Z is a divalent to hexavalent
organic radical having a monomeric, oligomeric or polymeric
structure, which has a weight-based heteroatom content of at least
10%, which is bonded via C atoms, E.sup.1 is a monofunctional
terminal group or an Si--C-bonded radical of the formula
##STR00008## a is an integer from 1 to 5, and x is 0 or an integer
from 1 to 5, are used as compounds (2).
29. The method of claim 28, wherein Z is a polyether or polyester
radical.
30. The method of claim 19, wherein the treatment of the substrate
is effected first with (1) compounds having at least two primary
amino groups and subsequently with (2) compounds having at least
one .beta.-ketocarbonyl group.
31. The method of claim 19, wherein the treatment of the substrate
is effected with a mixture of (1) compounds having at least two
primary amino groups and (2) compounds having at least one
.beta.-ketocarbonyl group, the mixture of (1) and (2) being
prepared before the treatment.
32. The method of claim 19, wherein the compounds (1) are used in
amounts of 1.1 to 500 mol of amino group per mole of
.beta.-ketocarbonyl group in compounds (2).
33. The method of claim 19, wherein as the compounds (1) and (2)
are used in the form of aqueous solutions or aqueous
dispersions.
34. The method of claim 19, wherein aqueous cellulose-containing
fiber slurries are used as cellulose-containing fibers.
35. The method of claim 34, wherein the compounds (1) and (2) are
added to the aqueous cellulose-containing fiber slurries, the
compounds (1) and (2) being added (i) either individually in
successive steps or (ii) together as a premix of (1) and (2).
36. The method of claim 19, wherein paper products, such as paper
towels, are used as planar structures containing
cellulose-containing fibers.
37. The method of claim 36, wherein paper towels are the planar
structures.
38. The method of claim 36, wherein the compounds (1) and (2) are
sprayed onto the paper products, the compounds (1) and (2) being
sprayed on (i) either individually in successive spraying steps or
(ii) together as a premix of (1) and (2).
39. A paper product containing planar structures containing
cellulose-containing fibers, the planar structures furthermore
containing a combination of (1) compounds having at least two
primary amino groups and (2) compounds having at least one
.beta.-ketocarbonyl group.
40. The paper product of claim 38, wherein the compounds (1) and
(2) are added to aqueous cellulose-containing fiber slurries which
are used for producing the planar structures.
Description
[0001] The invention relates to a method for treating
cellulose-containing fibers or planar structures containing
cellulose-containing fibers.
[0002] US 2004/0118540 A1 describes a papermaking process in which
first a high molecular weight amine component having an NH.sub.2
concentration of at least 1.5 meq/g is introduced into the aqueous
cellulose fiber mixture. Separately therefrom, a second component
which can react with amino groups and which is either a polyanionic
compound or an aldehyde-functional polymer is then added.
[0003] A paper product having increased strength is claimed in U.S.
Pat. No. 6,824,650 B2. The product contains a combination of a
polyvinylamine and a complexing agent selected from an
aldehyde-functional polymer and a polyelectrolyte. The paper
product is strengthened by reaction of polyvinylamine with the
complexing agent.
[0004] Articles which contain cellulose of which at least part was
chemically modified and where a further chemical has formed
chemical bonds are claimed in U.S. Pat. No. 6,916,402 B2. The
chemical modification of the cellulose can be carried out with
compounds which contain aldehyde, epoxy or anhydride groups, while
the further chemical then contains amino, thiol, amido, sulfonamide
or sulfinic acid groups--or vice versa.
[0005] It was the object to provide a method by means of which the
wet strength of cellulose-containing products, in particular the
wet strength of paper towels, is to be increased, it being intended
that the products also have a soft handle. The object is achieved
by the invention.
[0006] The invention relates to a method for treating
cellulose-containing fibers or planar structures containing
cellulose-containing fibers with a combination of
(1) compounds having at least two primary amino groups and (2)
compounds having at least one .beta.-ketocarbonyl group.
[0007] The compounds (1) used in the method according to the
invention may have a monomeric, oligomeric or polymeric character.
The compounds (1) preferably contain at least five primary amino
groups (--NH.sub.2), preferably at least 20 primary amino groups
(--NH.sub.2) and particularly preferably at least 100 primary amino
groups (--NH.sub.2). The density of amino groups in compounds (1)
is preferably at least 1.0 meq/g, preferably at least 3.0 meq/g
(meq/g=milliequivalent per g of substance=equivalent per kg of
substance).
[0008] Polyamines are preferably used as compounds (1). Examples of
compounds (1) are polymers of ethyleneimine in linear or branched
form and polyvinylamine. The latter obtained by polymerization of
N-vinylformamide and subsequent partial or complete hydrolysis are
generally commercially available in the form of aqueous
dilutions.
[0009] The compounds (2) used in the method according to the
invention may have a monomeric, oligomeric or polymeric character,
preferably a polymeric character. The compounds (2) preferably
contain at least two .beta.-keto-carbonyl groups and preferably at
least three .beta.-keto-carbonyl groups.
[0010] The .beta.-ketocarbonyl groups in compound (2) preferably
have the structure of the formula
--Y'--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4
or its tautomeric enol form of the formula
--Y'--C(O)--CR.sup.4.dbd.C(CH.sub.2R.sup.4)--OH
in which [0011] Y' is --O--, --NR.sup.2-- or
##STR00001##
[0011] preferably --O--, [0012] R.sup.2 is a hydrogen atom or a
monovalent hydrocarbon radical having 1 to 30 C atoms, preferably a
hydrogen atom, and [0013] R.sup.4 is a hydrogen atom or a
monovalent hydrocarbon radical having 1 to 18 C atoms, preferably a
hydrogen atom.
[0014] In the method according to the invention,
.beta.-keto-carbonyl-functional monomeric compounds (2a) of the
general formula
L(--Y--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4).sub.e (I)
or their tautomeric enol forms in which [0015] e is an integer from
1 to 20, preferably 2 to 20, preferably 2 to 8, [0016] L is a
monomeric organic radical having the valency or functionality
corresponding to the index e in formula (I), i.e. a monofunctional
to 20-functional monomeric organic radical, preferably a
monofunctional to 8-functional monomeric radical, [0017] Y is --O--
or --NR.sup.2--, preferably --O--, [0018] R.sup.2 is a hydrogen
atom or a monovalent hydrocarbon radical having 1 to 30 C atoms,
preferably a hydrogen atom, and [0019] R.sup.4 is a hydrogen atom
or a monovalent hydrocarbon radical having 1 to 18 C atoms,
preferably a hydrogen atom, can be used as compounds (2).
[0020] .beta.-Ketocarbonyl-functional monomeric compounds (2a) can
be prepared by known methods, preferably by reacting compounds of
the general formula
L(--YH).sub.e (II)
in which L, Y and e have the meaning stated above therefor, with
diketenes, diketene-acetone adducts and thermally labile
acetoacetates.
[0021] The radical L is preferably a hydrocarbon radical which has
1 to 18 carbon atoms and may contain one or more oxygen or nitrogen
atoms separate from one another.
[0022] Examples of the compounds L(--YH).sub.e of the formula (II)
on which the .beta.-ketocarbonyl-functional monomeric compounds
(2a) are based are
CH.sub.3OH
C.sub.2H.sub.5OH
C.sub.4H OH
C.sub.3H.sub.5OH
(C.sub.2H.sub.5).sub.2NH
C.sub.4H.sub.9NH.sub.2
C.sub.6H.sub.5NHCH.sub.3
HOC.sub.2H.sub.4NH.sub.2
HOC.sub.2H.sub.4NHCH.sub.3
HOC.sub.2H.sub.4OH
HOC.sub.3H.sub.6OH
CH.sub.3C(CH.sub.2OH).sub.3
C(CH.sub.2OH).sub.4
HN(C.sub.2H.sub.4OH).sub.2
N(C.sub.2H.sub.4OH).sub.3
N(C.sub.3H.sub.6OH).sub.3
H.sub.2NC.sub.2H.sub.4NH.sub.2
H.sub.2N(C.sub.2H.sub.4NH).sub.3H
(HOCH.sub.2).sub.3CCH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3
[0023] Compounds (2) in polymeric form are selected from the group
consisting of the [0024] organosiloxane polymers [0025] polyesters
[0026] polyethers [0027] polyacetals [0028] polyetheracetals [0029]
polyesterpolyols [0030] polyamides
[0031] Compounds (2) may correspond either to only one of these
species or may correspond to a combination of two or more species
from this group. These in turn may be present in separate compounds
and/or may be combined in one polymer type, as is the case with
silicone polyethers.
[0032] In the method according to the invention,
.beta.-keto-carbonyl-functional oligomeric or polymeric compounds
(2b) of the general formula
K(--Y--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4).sub.f (III)
or their tautomeric enol forms in which [0033] f is an integer from
1 to 10 000, preferably 2 to 2000, preferably 2 to 200, [0034] K is
an oligomeric or polymeric, organic or organo-silicon radical
having the valency or functionality corresponding to the index f in
formula (III), i.e. a monofunctional to 10 000-functional
oligomeric or polymeric, organic or organosilicon radical, and
[0035] Y and R.sup.4 have the meaning stated above therefor, can
therefore be used as compounds (2).
[0036] Examples of the radical K are therefore polymer radicals
selected from the groups consisting of the
organopolysiloxanes, polyesters, polyethers, polyacetals,
polyetheracetals, polyesterpolyols, polyamides and mixtures and
copolymers thereof.
[0037] .beta.-Ketocarbonyl-functional polymeric compounds (2b) can
be prepared by known methods--analogously to the preparation of the
.beta.-ketocarbonyl-functional monomeric compounds (2a)--preferably
by reacting compounds of the general formula
K(--YH).sub.f (IV)
in which K, Y and f have the meanings stated above therefor, with
diketenes, diketene-acetone adducts and thermally labile
acetoacetates.
[0038] Examples of compounds K(--YH).sub.f of the formula (IV) on
which the .beta.-ketocarbonyl-functional polymeric compounds (2b)
are based are
MeO(C.sub.2H.sub.4O).sub.pH where p=2-20 000
HO(C.sub.2H.sub.4O).sub.pH
[0039] HO(C.sub.3H.sub.6O).sub.qH where q=2-200
HO(C.sub.4H.sub.8O).sub.qH
[0040] HO-functional polyesters obtained from dicarboxylic acid and
diols HO-functional polyesters obtained from dicarboxylic esters
and diols HO-functional polyesters obtained from diols and
caprolactone
Polyesterpolyols
[0041] Partial or complete hydrolysis products of polyvinyl acetate
Partial or complete hydrolysis products of polyvinyl-formamide
Silicone polyethers obtained from
.alpha.,.omega.-dihydroorgano-polysiloxanes and allylpolyethers
Silicone polyethers obtained from siloxanes having MeHSiO units and
allylpolyethers Polyaminoamides obtained from dicarboxylic acids
and diethylenetriamine Polyaminoamides obtained from methyl
dicarboxylates and triethylenetetramine Aminosilicones containing
H.sub.2NC.sub.3H.sub.6(Me)SiO groups Aminosilicones containing
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6(Me)SiO groups Condensates of
polydimethylsiloxanediols and secondary .alpha.-aminosilanes, such
as cyclohexylaminomethylmethyl-diethoxysilane, Me being a methyl
radical.
[0042] .beta.-Ketocarbonyl-functional polymeric compounds (2b) are
preferably, entirely or at least in proportions,
organopolysiloxanes or copolymers containing organo-polysiloxanes,
such as silicone polyethers. The organo-polysiloxanes or their
copolymers preferably have a linear or branched structure. These
polymeric compounds (2b) are prepared by reacting
organopolysiloxanes or their copolymers which contain at least two
carbinol functions (.ident.C--OH) and/or primary or secondary
SiC-bonded amino groups with the same substances, such as compounds
of the general formula (II), i.e. with diketenes, diketene-acetone
adducts and thermally labile acetoacetates.
[0043] Since the increase in the wet strength of
cellulose-containing products is preferably effected in the wet-end
region as a result of production, it is advantageous if the
organosiloxane polymers used in the method according to the
invention are soluble or at least dispersible in water.
Organosiloxane polymers having components of relatively high
polarity are necessary for this purpose.
[0044] In the method according to the invention,
.beta.-keto-carbonyl-functional organosilicon compounds (2c) which
contain at least one Si-bonded radical of the general formula
##STR00002##
or its tautomeric enol forms, where [0045] --(Si.ident.) is the
bond to the silicon atom, [0046] R.sup.1 is a divalent organic
radical having 1 to 6 carbon atoms which may optionally contain
nitrogen atoms separate from one another, preferably a divalent
hydrocarbon radical having 1 to 6 C atoms which may optionally
contain one or more nitrogen atoms separate from one another,
[0047] R.sup.3 is a divalent organic radical having 1 to 6 carbon
atoms, preferably having 2 to 6 carbon atoms, preferably a divalent
hydrocarbon radical having 2 to 6 carbon atoms, [0048] Y, R.sup.2
and R.sup.4 have the meanings stated above therefor, [0049] Z is a
divalent to hexavalent organic radical having a monomeric,
oligomeric or polymeric structure, which has a weight-based
heteroatom content of at least 10%, which is bonded via C atoms,
[0050] E.sup.1 is a monofunctional terminal group or an Si--C--
bonded radical of the general formula
[0050] ##STR00003## [0051] a is an integer from 1 to 5, preferably
1 or 2, and [0052] x is 0 or an integer from 1 to 5, preferably 0
or 1, preferably 1, can as compounds (2) for this purpose.
[0053] The .beta.-ketocarbonyl-functional organosilicon compounds
(2c) are prepared by a procedure in which,
in a first stage, aminosilicon compounds (i) which contain at least
one Si--C-bonded amino group A of the general formula
HNR.sup.2--(R.sup.3--NH--).sub.aR.sup.1--(Si.ident.) (VI)
are reacted with compounds (ii) which contain at least one
.beta.-ketocarbonyl-functional radical of the general formula
(E.sup.2).sub.xZ-Y--C(O)--CR.sup.4.dbd.C(CH.sub.2R.sup.4)--OH
(VIIa) or
(E.sup.2).sub.xZ-Y--C(O)--CHR.sup.4--C(O)--CH.sub.2R.sup.4
(VIIb)
in which organosilicon compounds (2c') of the general formula
(E.sup.2).sub.xZ-Y--C(O)--CR.sup.4.dbd.C(CH.sub.2R.sup.4)--NR.sup.2--(R.-
sup.3--NH--).sub.aR.sup.1--(Si.ident.) (V')
are obtained, in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y, Z, a
and x have the meanings stated above therefor, and E.sup.2 is a
monofunctional terminal group or a radical of the general formula
--Y--C(O)--CR.sup.4.dbd.C(CH.sub.2R.sup.4)--OH or
--Y--C(O)--CHR.sup.4-- C(O)--CH.sub.2R.sup.4, and, in a second
stage, the organosilicon compounds (2c') obtained in the first
stage are reacted with diketenes (iii) of the general formula
##STR00004##
in which R.sup.4 has the meaning stated above therefor.
[0054] In the method according to the invention, the aminosilicon
compounds (i) are reacted in a first stage with acetoacetyl
compounds (ii) of the tautomeric forms (VIIa) or (VIIb) and are
reacted in a subsequent second stage with diketenes (iii). This
reaction sequence can be advantageously carried out in a one-pot
process. A particularly preferred procedure is the upstream
preparation of compound (ii) from the parent compounds (iv) by
reacting these with diketenes (iii), after which aminosilicon
compounds (i) are metered in at the end of the reaction and the
organosilicon compounds (2c) according to the invention are then
obtained in a particularly economical method by further metering in
of diketenes (iii) after the reaction thereof.
[0055] Preferred examples of Si--C-bonded amino groups A of the
formula (VI) are [0056] H.sub.2N--C.sub.2H.sub.4--NH--CH.sub.2--
[0057] H.sub.2N--C.sub.3H.sub.6--NH--CH.sub.2-- [0058]
H.sub.2N--C.sub.3H.sub.6--NH--C.sub.3H.sub.6--NH--CH.sub.2-- [0059]
H.sub.2N--C.sub.2H.sub.4--NH--C.sub.3H.sub.6-- [0060]
H.sub.2N--C.sub.3H.sub.6--NH--C.sub.3H.sub.6-- [0061]
H.sub.2N--C.sub.2H.sub.4--NH--C.sub.2H.sub.4--NH--C.sub.3H.sub.6--
[0062]
H.sub.2N--C.sub.3H.sub.6--NH--C.sub.3H.sub.6--NH--C.sub.3H.sub.6--
[0063] H.sub.2N--C.sub.2H.sub.4--NH--C.sub.4H.sub.8-- R.sup.2 is
preferably a hydrogen atom. R.sup.3 is particularly preferably an
alkylene radical having 2 to 6 carbon atoms. R.sup.4 is preferably
a hydrogen atom.
[0064] Z preferably has a weight-based heteroatom content of at
least 20% and particularly preferably at least 25%.
[0065] Preferred aminosilicon compounds (i) are
organopoly-siloxanes having at least one Si--C-bonded radical A of
the formula (VI).
[0066] Preferred aminosilicon compounds (i) are
organopoly-siloxanes of the general formula
A.sub.gR.sub.3-gSiO(SiR.sub.2O).sub.l(SiRAO).sub.kSiR.sub.3-gA.sub.g
(IXa),
(R'O )R.sub.2SiO(SiR.sub.2O).sub.l(SiRAO).sub.kSiR.sub.2(OR')
(IXb)
in which A has the meaning stated above therefor, R is a monovalent
hydrocarbon radical having 1 to 18 C atoms, R' is a hydrogen atom
or a monovalent hydrocarbon radical having 1 to 18 C atoms,
preferably a hydrogen atom, g is 0 or 1, k is 0 or an integer from
1 to 30 and l is 0 or an integer from 1 to 1000, with the proviso
that at least one radical A is present per molecule.
[0067] Aminosilicon compounds (i) preferably contain amino group
concentrations in the range of 0.01 to about 10 meq/g, in
particular from about 0.05 to 5 meq/g. Preferred viscosities are in
the range from about 100 to 50 000 mPas at 25.degree. C., the range
500 to 10 000 mPas at 25.degree. C. being particularly
preferred.
[0068] The aminosilicon compounds (i) are preferably used without
prior conversion of the amino groups by means of protective group
reagents, such as aldehydes or ketones.
[0069] The aminosilicon compounds (i) are preferably prepared from
"diamino" monomers, such as aminoethylamino-propyl- or
aminoethylaminoisobutylsilanes, the Si--C-- bonded amino group A
containing both a primary and a secondary amino radical, bonded to
the same Si atom. In the radicals A, preferably the primary amino
radicals react with the compounds (ii), the secondary amino
radicals being retained as basic centers.
[0070] The compounds (ii) can be used as reactants for the
aminosilicon compound (i) in two tautomeric forms of the formulae
(VIIa) and (VIIb).
[0071] The compounds (ii) are preferably obtained by reacting the
parent compounds (iv) of the formula (E.sup.2).sub.xZ-Y (X), which
are saturated with hydrogen at the free valencies,
[0072] in which E.sup.2, Z, Y and x have the meanings stated above
therefor, with diketenes, acetylketenes, alkyl-diketenes,
diketene-acetone adducts or acetoacetates, preferably with
diketenes or their acetone adducts, by methods known in the
literature.
[0073] The radical "Z" is defined as an organic radical which,
owing to its bifunctionality to hexafunctionality, is linked to 2
to 6 further groups E or Y: the sum of "E" plus "Y" corresponds in
its numerical value to this bifunctionality to hexafunctionality.
In the simplest case, which is also preferred, "Z" is bifunctional,
i.e. divalent. In this case, "Z" is bonded either to two Y groups
or to one Y group and one monofunctional terminal group.
Monofunctional terminal groups may be saturated or unsaturated
hydrocarbon radicals having 1 to 18 C atoms or acyl radicals, such
as the acetate, butyrate, palmitate or stearate radical, as well as
the acrylate, methacrylate or benzoate radical.
[0074] The radical "Z" has a heteroatom content of at least 10% by
weight. Heteroatoms are selected from the group consisting of the
O, N, B, P and S atoms; preferably O and N atoms, particularly
preferably O atoms. The radical "Z" has the function of introducing
higher polarity and hence a higher degree of hydrophilicity into
the organosilicon compounds (1) according to the invention, and it
is for this reason that a relatively high content of heteroatoms is
preferred. The radical "Z" is particularly preferably a polyether
or polyester. Examples of polyethers are polyethylene oxide,
polypropylene oxide or polybutylene oxide (also poly-THF) and also
copolymers of the general formula
(C.sub.aH.sub.2aO).sub.nC.sub.aH.sub.2a where a=2, 3 or 4 and n is
an integer from 1 to 500, preferably from 1 to 100 and particularly
preferably from 5 to 60.
[0075] Trifunctional to hexafunctional radicals "Z" are usually
started from alcohols of the same functionality as well as from
amines. Thus, trimethylolpropane or ammonia gives, with ethylene
oxide, parent compounds (iv) with "Z" of the general formula
C.sub.2H.sub.5C[CH.sub.2(OC.sub.2H.sub.4).sub.m/3].sub.3 or N
[C.sub.2H.sub.4 (OC.sub.2H.sub.4).sub.(m-1)/3].sub.3, in which m is
the total number of moles of ethylene oxide, preferably 5 to 100,
the free valencies of which are linked to oxygen atoms (Y) which in
turn are saturated with hydrogen. For the preparation of parent
compounds (iv) having a higher functionality, the correspondingly
more highly functionalized carbinol or amino compounds are usually
used: tetrafunctionality from pentaerythritol or ethylenediamine,
hexa-functionality from sorbitol or tris(aminoethyl)amine.
[0076] Corresponding polyesters can be prepared from identical or
similar starter compounds by ring-opening polymerization of cyclic
esters (lactones) by generally known methods. Preferred parent
compounds (iv) are polyethylene glycol, polypropylene glycol and
the copolymers thereof, and the monoalkyl ethers thereof. The
latter are a special case where "Y" is oxygen and "E" is an alkyl
group (methyl, alkyl, butyl). With regard to the conversion into
compounds (ii), these parent compounds (iv) are monofunctional.
Compared with the aminosilicon compounds (i), the compounds (ii)
prepared therefrom are likewise monofunctional and accordingly
serve for saturating amino groups with polar polymers.
[0077] In contrast, bifunctional reactants (ii) which have a
chain-extending effect with respect to likewise bifunctional
aminosilicon compounds (i), i.e. which contain two amino groups A
per molecule, are obtained from polyalkylene glycols. In this way,
it is also possible to obtain branched products (2c) provided that
the aminosilicon compounds (i) contain at least three amino groups
A per molecule. An alternating siloxane-polyether structure
forms.
[0078] The surprisingly high selectivity of the compounds (ii)
having primary amino radicals in the amino groups A of the
aminosilicon compounds (i) permits virtually complete conversion of
the H.sub.2N radicals into enamines, and it is for this reason that
a stoichiometric ratio of primary NH.sub.2 radicals in amino groups
A of compounds (i) to acetoacetyl groups in compounds (ii) close to
1.0 is preferably used in the first stage of the method for the
preparation of (2c). This ratio is particularly preferably 0.8 to
1.0. However, it may also be above 1.0. In this case, not all
primary amino radicals are converted, which are then however
additionally available for reaction with diketenes (iii). This
procedure is technically possible but is not preferred.
[0079] In the method for the preparation of (2c), the acetone
adducts of diketenes (iii) can also be used as said diketenes.
Preferably used diketenes (iii) are
##STR00005##
or their acetone adducts.
[0080] In the method for the preparation of (2c), the
stoichiometric ratio of secondary --NH groups in amino groups A of
compounds (i) to diketenes (iii) is 5:1 to 0.5:1, preferably 2:1 to
0.8:1, in the subsequent reaction with diketenes (iii). A ratio of
about 1:1 is particularly preferred.
[0081] The method for the preparation (2c) can be effected in the
presence of organic solvents or the products (2c) according to the
invention can be diluted with organic solvents.
[0082] The reaction of the compounds (ii) with aminosilicon
compounds (i) in the first stage of the method for the preparation
of (2c) takes place spontaneously even without external heating but
supply of heat accelerates the synthesis of (2c).
[0083] The method for the preparation of (2c) is preferably carried
out at temperatures of 10 to 100.degree. C., preferably 40 to
80.degree. C. Furthermore, the method is preferably carried out at
the pressure of the ambient atmosphere but can also be carried out
at higher and lower pressures.
[0084] The treatment of the cellulose-containing fibers or planar
structures containing cellulose-containing fibers can be effected
in two different variants of the method.
[0085] In one variant of the method, the treatment of the
cellulose-containing fibers or planar structures containing
cellulose-containing fibers is effected preferably first with (1)
compounds having at least two primary amino groups and subsequently
with (2) compounds having at least one .beta.-ketocarbonyl
group.
[0086] The application of the compound (2) is effected only after
the action of the compound (1) on the cellulose-containing fibers
or planar structures containing cellulose-containing fibers.
[0087] In a second variant of the method, the treatment of the
cellulose-containing fibers or planar structures containing
cellulose-containing fibers is preferably effected with a mixture
of (1) compounds having at least two primary amino groups and (2)
compounds having at least one .beta.-ketocarbonyl group, the
mixture of (1) and (2) being prepared before the treatment. Thus, a
premix of (1) and (2) is first prepared and the premix is then
applied to the cellulose-containing fibers or planar structures
containing cellulose-containing fibers.
[0088] In the method according to the invention, compounds (1) and
(2) are used in amounts such that the compounds (1) are used in
amounts of preferably 0.1 to 1000 mol, preferably 0.5 to 500 mol,
particularly preferably 1.1 to 500 mol of amino group, based in
each case on 1 mol of .beta.-ketocarbonyl group in compounds
(2).
[0089] Examples of cellulose-containing fibers which are treated
according to the invention are all cellulose-containing fibers and
all aqueous cellulose-containing slurries from which paper products
can be produced, such as bleached fibers, recycled fibers, fibers
which are produced via chemical digestion methods, such as the
sulfate or sulfite method, fibers which are produced from vegetable
raw materials (fibrous plants) and which have a sufficient
cellulose content, and mechanical pulps which are produced
predominantly by mechanical defibration of wood. The cellulose
fiber-containing materials are materials such as wood, grass
fibers, straw, bamboo, corn fibers and hemp, in each case in any
desired forms, such as scraps, chips or sawdust.
[0090] Examples of planar structures containing
cellulose-containing fibers are all paper products produced from
cellulose-containing fibers, such as paper towels, toilet paper,
tissues, kitchen paper, paper napkins, facial tissues.
[0091] The paper to be treated according to the invention may be
low-quality paper varieties, such as absorptive papers, including
base paper, i.e. kraft paper not pretreated with chemicals and/or
polymeric natural substances having a weight of 60 to 150
g/m.sup.2, unsized papers, paper having a low freeness,
wood-containing papers, unglazed or uncalendered papers, papers
which are smooth on one side owing to the use of a calendar stack
in their production without further expensive measures and are
therefore referred to as "papers machine-finished on one side",
uncoated papers and papers produced from paper waste, i.e.
so-called waste papers. However, the paper to be treated according
to the invention can of course also be high-quality paper
varieties, such as low-absorption papers, sized papers, papers
having a high freeness, wood-free papers, calendered or glazed
papers, glassine papers, parchmentized papers or precoated papers.
The boards may also be of high or low quality.
[0092] Preferably, the compounds (1) and (2) are used in the form
of aqueous solutions or aqueous dispersions in the treatment of the
cellulose-containing fibers or planar structures containing
cellulose-containing fibers. In the aqueous solutions or aqueous
dispersions, compound (1) is preferably present in amounts of 0.1
to 20% by weight, preferably 0.2 to 10% by weight.
[0093] In the aqueous solutions or aqueous dispersions, compound
(2) is preferably present in amounts of 0.1 to 50% by weight,
preferably 0.5 to 20% by weight.
[0094] The treatment of cellulose-containing fibers or planar
structures containing cellulose-containing fibers can be effected
by the methods known in the prior art, in particular by the methods
known in the production and finishing of paper products, as
described, for example, in U.S. Pat. No. 6,824,650 B2, column 12,
line 1 to column 13, line 15.
[0095] The production of paper products as treated according to the
invention is described in U.S. Pat. No. 6,824,650 B2, column 15,
line 20 to column 19, line 11.
[0096] Some possible treatments are mentioned by way of
example:
[0097] The treatment can be effected by metering the compounds (1)
and (2)--either individually in successive steps or together as a
premix of (1) and (2)--into the aqueous cellulose-containing fiber
slurry from which the planar structures containing
cellulose-containing fibers, such as paper products, are produced
or during the concentration or drying process.
[0098] The treatment can also be effected by spraying the compounds
(1) and (2)--either individually in successive spraying steps or
together as a premix of (1) and (2)--onto the planar structures
containing cellulose-containing fibers, such as paper products. The
planar structures may be moist or dry during the process.
[0099] The treatment can also be effected by coating the surface of
the planar structures, such as paper products, with the compounds
(1) and (2)--either individually in successive steps or together as
a premix of (1) and (2).
[0100] The treatment can also be effected by impregnating the wet
or dry planar structures with the compounds (1) and (2)--either
individually in successive steps or together as a premix of (1) and
(2)--the planar structures being completely or partly penetrated
therewith.
[0101] The invention furthermore relates to paper products
containing
planar structures containing cellulose-containing fibers, the
planar structures furthermore containing a combination of [0102]
(1) compounds having at least two primary amino groups and [0103]
(2) compounds having at least one .beta.-ketocarbonyl group.
[0104] The compound (1) and (2) are preferably added to
cellulose-containing fiber slurries which are used for the
production of the planar structures.
[0105] The compounds (1) and (2) are preferably used in each case
in amounts of 0.1 to 50% by weight, preferably 0.2 to 20% by
weight, based on the total weight of the dry cellulose-containing
fibers or dry planar structures containing cellulose-containing
fibers.
[0106] In addition to the compounds (1) and (2), further substances
which are usually concomitantly used in the treatment of
cellulose-containing fibers or planar structures containing
cellulose-containing fibers can also be concomitantly used. An
example of further substances are antifoams, dry strength agents,
such as (modified) starch, carboxymethylcellulose or (modified)
polyacrylamides, softening agents, drainage aids or retention
aids.
[0107] The treatment according to the invention is preferably
carried out at temperatures of 5 to 60.degree. C., preferably 15 to
35.degree. C. The treatment according to the invention is
preferably carried out at the pressure of the ambient atmosphere,
i.e. at 1020 hPa, but can also be carried out at higher or lower
pressures.
EXAMPLES
Compound (I)
[0108] All tests relate to the combination of (1) with various
compounds (2). Exclusively Lupamin 9095 (BASF), a high molecular
weight polyvinylformamide having a degree of hydrolysis of about
95% and an amino group concentration of about 3.8 meq/g for the 20%
strength aqueous solution (commercial product) was used as compound
(1).
Preparation Examples for the Compound (2)
Example 1
[0109] 73.1 g of N,N,N,N-tetrakis(2-hydroxypropyl)ethylene-diamine
are heated to 50.degree. C. Thereafter, 92 g of diketene are
metered in with cooling so that the temperature of the reaction
mixture is kept between 50 and 70.degree. C. The reaction is
allowed to continue for a further hour and excess diketene is
removed in vacuo at 100.degree. C. A pale orange product having an
acetoacetate content of 6.3 meq/g is obtained.
Example 2
[0110] 250.5 g of a trimethylsilyl-terminated aminosiloxane which
contains dimethylsilyloxy and aminoethylamino-propylmethylsilyloxy
units and has a concentration of 2.24% by weight of basic nitrogen
are mixed with 411.4 g of a polyether acetyl acetate of the average
formula
CH.sub.3O(C.sub.2H.sub.4O).sub.19.4(C.sub.3H.sub.6O).sub.17.1C(.dbd.O)--C-
H.sub.2C(.dbd.O)--CH.sub.3 and heated to 70.degree. C. On
clarification, the viscosity of the reaction mixture increases
sharply, whereupon 70 g of isopropanol are metered in. At
70.degree. C., 16.8 g of diketene are slowly added dropwise,
followed by altogether a further 156 g of isopropanol after a
further hour. The high-viscosity product has a solids content of
75% and an acetoacetamide content of 0.22 meq/g.
Example 3
[0111] 400 g of 75% strength solution obtained in example 2 are
homogeneously mixed with 0.75 g of isophoronediamine at 25.degree.
C. and slowly heated to 40.degree. C. With a considerable increase
in viscosity, a clear, high-viscosity polymer solution having an
acetoacetamide content of 0.20 meq/g is obtained in 2 hours.
Example 4
[0112] 13.3 g of the 75% strength solution obtained in example 2
are homogeneously mixed with 10.0 g of the diacetoacetate of PEG
1000 and diluted with isopropanol to 200 g. The clear solution
contains 0.105 meq/g of .beta.-ketocarbonyl groups per g.
Example 5
[0113] 0.1 g of triethylamine and thereafter 20.6 g of diketene are
slowly metered into 200 g of a silicone polyether prepared from 2
parts of allylpolyether of the formula
CH.sub.2.dbd.CH--CH.sub.2O(C.sub.2H.sub.4O).sub.10H and 1 part of
hydrogen-siloxane of the formula
HO(HSiMeO).sub.14.3(SiMe.sub.2O).sub.60H. After an exothermic
reaction, the batch is kept at 70.degree. C. for a further hour. A
pale brownish product which has a viscosity of about 20 000
mm.sup.2/s in undiluted form is obtained. The concentration of
acetoacetate is 1.10 meq/g.
Example 6
[0114] 50 g of the polymeric acetoacetate obtained in example 5 are
further condensed at 100.degree. C. after dropwise addition of 0.2
g of a 10% strength solution of p-toluenesulfonic acid in THF, with
the result that a gel-like high polymer which is soluble in the
same amount of isopropanol to give a clear solution is obtained.
The 50% strength solution contains aceto-acetate groups at a level
of 0.55 meq/g.
Example 7
[0115] By dilution of a commercially available aqueous solution
(Lupamin 9095, BASF) of a high molecular weight polyvinylamine
(about 19 meq of NH.sub.2 per g) with the same amount of water, a
10% strength solution is prepared. 6.0 g of a 10% strength aqueous
solution of the diacetoacetate of PEG 2000 are added to 200 g of
this dilution and homogeneously mixed. After 3 days, a clear
aqueous solution which no longer contains detectable acetoacetate
is obtained. The mixture is a ready-to-use one-component
formulation of the compounds (1) and (2). The molar ratio of amino
to acetoacetate groups is about 700:1.
Example 8
[0116] For the preparation of a 10% strength aqueous solution of
the combination of compounds (1) with an exclusively monofunctional
compound (2), 24 g of Lupamin 9095 (BASF), 67.2 g of water and 4.8
g of ethyl acetoacetate are mixed in succession. A clear colorless
mixture is obtained, to which 0.65 g of acetic acid is added after
24 hours. The mixing ratio of amino to acetoacetate groups is about
2.5:1.
Example 9
Dry and Wet Strength Tests
[0117] The dry and wet strength of paper towels is tested.
[0118] Regardless of the preparation process, all examples of the
compounds (2) are used as a 10% strength aqueous solution. This
also applies to the one-component formulation of examples 7 and
8.
[0119] In the case of two-component applications, the polyamine (1)
is in principle applied first as a 1% strength aqueous solution by
the spray process described below and is dried at 105.degree. C.
for 5 minutes. The active substance application of compound (1) is
stated in the table and is 0.5 or 0.9% by weight, based on the dry
weight of the paper towel.
[0120] The substrate, the paper towel, is preconditioned
therewith.
[0121] The specified paper towel having a very low tensile strength
is cut to a size of 1.times.w=15.times.35 cm. This is placed
without creases in a vertical clamping apparatus and sprayed
uniformly (3.times.per sheet of paper towel) from top to bottom
using a Sata 200 Dekor spray gun. The settings on the spray gun
always remain the same and are 2 bar compressed air with a spray
nozzle of 0.5 mm. Depending on amount of product and type, this
process is repeated until 4.8-5.2% by weight of active product
(=compound (2)) is present on the paper towel. In the table, the
active substance application of compound (2) is stated in % by
weight, based on the dry weight of the paper towel. This product
application is determined by weighing the uncoated and the wet
paper towel. The product application is effected on one side.
Thereafter, the coated paper towel is dried at 105.degree. C. for 5
min.
TABLE-US-00001 TABLE Test results of the testing of dry and wet
strength of paper towels Compound (2) Polyamine Soft TEA TEA (2) in
%* (1) in %* handle (wet) (dry) Example 1 4.9 0.5 - 11 42 Example 2
5.0 0.9 + 11 32 Example 3 4.8 0.5 + 9 32 Example 4 5.0 0.5 + 7
Example 5 5.0 0.5 + 6 23 Example 6 5.1 0.5 + 7 29 Comparison -- 0.5
-- 6 42 1 Comparison -- 0.9 -- 9 2 Blank -- -- 0 2 31 sample
Example 7** 0.02 0.5 - 8 46 Example 8** 0.5 0.5 - 8 50 *The active
substance application is stated in % by weight, based on the dry
weight of the paper web. **Polyamine (1) and compound (2) applied
premixed. The soft handle was assessed as softer (+) or harder (-
or --) than the blank sample.
[0122] Description of the dry breaking strength (cf. DIN EN 29 073
part 3 or ISO 9073-3):
[0123] The paper towel to be tested is cut into at least 10 strips
having a minimum length of 152 mm and a width of 25 mm in the
running direction.
[0124] Five test specimens thereof are used for measuring the dry
breaking strength and 5 for the wet strength.
[0125] The test specimens are clamped in the ZWICK 1446 tensile
tester, likewise in the running direction, and the following
parameters are set:
traction speed=0.21 mm/s (12.7 mm/min) sample length=152 mm (6
inches)
[0126] By starting the tester, the force in F-Max [N or g/force],
the elongation at F-max [%] and the resulting area (load-elongation
curve) TEA or energy up to breaking in [J] are recorded.
[0127] By inputting the weight, it is also possible to determine
the tensile force per tex in cn/tex. This process is repeated at
least 5 times and the mean value and standard deviation of each
parameter is determined.
[0128] Description of the wet breaking strength (cf. DIN ISO
3781):
[0129] In the measurement of the wet breaking strength, the paper
towel is moistened in the middle by brief immersion in
demineralized water to at least 25 mm to not more than 50 mm. The
ends remain dry for clamping. (Cf. also point 8.2 in DIN ISO 3781.)
The evaluation and settings are the same as for the dry breaking
strength method.
[0130] The energy (in Joule) absorbed by the test strips was
compared with the blank sample (TEA=2) and the strips treated only
with polyamine (1) (TEA=6 and 9), comparative experiments 1 and 2,
respectively. The improvement in the wet strength of the test
strips by the additional compound (2) is clear from the higher TEA
values, with improved soft handle throughout in the comparison with
the test strips treated only with (1). In most cases, even an
improvement in the soft handle compared with the blank sample is
achieved.
[0131] All test strips proved to be hydrophilic with drop
absorption times of less than two seconds.
* * * * *