U.S. patent number RE46,913 [Application Number 15/477,788] was granted by the patent office on 2018-06-26 for optical brightening compositions.
This patent grant is currently assigned to ARCHROMA IP GMBH. The grantee listed for this patent is ARCHROMA IP GMBH. Invention is credited to Andrew Clive Jackson, Cedric Klein, David Puddiphatt.
United States Patent |
RE46,913 |
Jackson , et al. |
June 26, 2018 |
Optical brightening compositions
Abstract
The instant invention relates to mixed salts of optical
brighteners of formula (1), ##STR00001## wherein M represents a
mixture of Mg.sup.2+ with another cation, which provide for
superior optical brightening effects when applied to the surface of
paper.
Inventors: |
Jackson; Andrew Clive
(Muenchenstein, CH), Puddiphatt; David (Grellingen,
CH), Klein; Cedric (Brumath, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
ARCHROMA IP GMBH |
Reinach |
N/A |
CH |
|
|
Assignee: |
ARCHROMA IP GMBH (Reinach,
CH)
|
Family
ID: |
1000003024163 |
Appl.
No.: |
15/477,788 |
Filed: |
April 3, 2017 |
PCT
Filed: |
March 12, 2009 |
PCT No.: |
PCT/EP2009/052919 |
371(c)(1),(2),(4) Date: |
March 07, 2011 |
PCT
Pub. No.: |
WO2009/118247 |
PCT
Pub. Date: |
October 01, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
12934170 |
Mar 12, 2009 |
8821688 |
Sep 2, 2014 |
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Foreign Application Priority Data
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Mar 26, 2008 [EP] |
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08102906 |
Dec 10, 2008 [EP] |
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08171223 |
Dec 12, 2008 [CH] |
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08171480 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D21H
21/16 (20130101); D21H 17/66 (20130101); D21H
17/63 (20130101); D21H 21/30 (20130101); D21H
17/66 (20130101); D21H 21/30 (20130101); D21H
17/63 (20130101); D21H 21/16 (20130101) |
Current International
Class: |
D21H
21/30 (20060101); C07D 251/68 (20060101); D21H
17/66 (20060101); D21H 21/16 (20060101); D21H
17/63 (20060101) |
Field of
Search: |
;162/162 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2553556 |
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CA |
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2553556 |
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1811715 |
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DE |
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2715864 |
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DE |
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0 032 483 |
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0899373 |
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Mar 1999 |
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EP |
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1763519 |
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Mar 2007 |
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EP |
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1763519 |
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Mar 2007 |
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EP |
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760982 |
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Nov 1956 |
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773152 |
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Apr 1957 |
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GB |
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976822 |
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1140415 |
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1140415 |
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1174631 |
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1239818 |
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1239818 |
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1240020 |
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1293804 |
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Oct 1972 |
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1526004 |
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GB |
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1526004 |
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Sep 1978 |
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GB |
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5-56104970 |
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Aug 1981 |
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JP |
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S-56104970 |
|
Aug 1981 |
|
JP |
|
S58-222156 |
|
Dec 1983 |
|
JP |
|
62106965 |
|
May 1987 |
|
JP |
|
S62-106965 |
|
May 1987 |
|
JP |
|
2011515597 |
|
May 2011 |
|
JP |
|
96/00220 |
|
Jan 1996 |
|
WO |
|
9600221 |
|
Jan 1996 |
|
WO |
|
WO 96/00221 |
|
Jan 1996 |
|
WO |
|
9842685 |
|
Oct 1998 |
|
WO |
|
WO 98/42685 |
|
Oct 1998 |
|
WO |
|
03044275 |
|
May 2003 |
|
WO |
|
WO 03/044275 |
|
May 2003 |
|
WO |
|
2007/048720 |
|
May 2007 |
|
WO |
|
2009118247 |
|
Oct 2009 |
|
WO |
|
Other References
PCT International Search Report for PCT/EP2009/052919, dated Jul.
27, 2009. cited by applicant .
Clariant, Fiche de donnees de securiteconforme au Reglement (CE)
N.degree. 1907/2006, Leucophor AF liq (Safety Sheet for Leuocophor
AF liq), Jan. 8, 2009. cited by applicant .
Klaus Hunger (Editor), Industrial Dyes: Chemistry, Properties,
Applications (2003), pp. 593-596, Wiley-VCH, Germany. cited by
applicant .
Martinez, et al., "Effect of optical brighteners on the
insecticidal activity of a nucleopolyhedrovirus in three instars of
Spodoptera frugiperda," (2003) The Netherlands Entomological
Society, Entomologia Experimentalis et Applicata, vol. 109:
139-146. cited by applicant .
PCT International Search Report for PCT/EP2009/052919, mailed Jul.
24, 2009. cited by applicant .
English Abstract for JP 62106965, May 18, 1987. cited by applicant
.
"Water to Zirconium, and Zirconium, Compounds," Ullmann's
Encyclopedia of Industrial Chemistry, Sixth Edition, vol. 39, 2003.
cited by applicant.
|
Primary Examiner: Kugel; Timothy J.
Attorney, Agent or Firm: McBee Moore Woodward & Vanik
IP, LLC
Claims
The invention claimed is:
1. A compound of formula (1), ##STR00009## wherein R.sub.1 is
hydrogen or SO.sub.3.sup.-, R.sub.2 is hydrogen or SO.sub.3.sup.-,
R.sub.3 is hydrogen, C.sub.1-4 alkyl, C.sub.2-3 hydroxyalkyl,
CH.sub.2CO.sub.2.sup.-, CH.sub.2CH.sub.2CONH.sub.2 or
CH.sub.2CH.sub.2CN, R.sub.4 is C.sub.1-4 alkyl, C.sub.2-3
hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.- or
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.-, benzyl, or
R.sub.3 and R.sub.4 together with the neighboring nitrogen atom
signify a morpholine ring, .[.and.]. wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with at
least 1 further cation selected from the group consisting of
H.sup.+, alkali metal cation, alkaline earth metal cation other
than Mg.sup.2+, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof.Iadd.,
and wherein the molar ratio of the Mg.sup.2+ to the further cation
in M is between 50:50 and 99.99:0.01.Iaddend..
2. The compound of formula (1) as claimed in claim 1, wherein
R.sub.3 is hydrogen, methyl, ethyl, n-propyl, iso-propyl,
.beta.-hydroxyethyl, .beta.-hydroxypropyl, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN; R.sub.4 is
methyl, ethyl, n-propyl, isopropyl, 2-butyl, .beta.-hydroxyethyl,
.beta.-hydroxypropyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.-, or benzyl.
3. The compound as claimed in claim 1, wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with 1,
2, 3, 4, 5 or 6 further cations.
4. A compound as claimed in claim 1, wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with 1, 2
or 3 further cations.
5. A compound as claimed in claim 1, wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with 1 or
2 further cations.
6. A compound as claimed in claim 1, wherein the ratio of M to the
rest of formula (1) is between 6.25:12.5 and 50:2.
7. A compound as claimed in claim 1, wherein the ratio of M to the
rest of formula (1) is between 8:12.5 and 8:2.5.
8. The compound of formula (1) as claimed in claim 1, wherein
R.sub.1 is hydrogen or SO.sub.3.sup.-, R.sub.2 is hydrogen or
SO.sub.3.sup.-, R.sub.3 is hydrogen, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN, R.sub.4 is
C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2)CH.sub.2CO.sub.2.sup.- or
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.-, excepting that
R.sub.4 cannot be C.sub.2-3 hydroxyalkyl if R.sub.3 is hydrogen, or
R.sub.3 and R.sub.4 together with the neighboring nitrogen atom
signify a morpholine ring, and wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with at
least 1 further cation selected from the group consisting of
H.sup.+, alkali metal cation, alkaline earth metal cation other
than Mg.sup.2+, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof.
9. The compound of formula (1) as claimed in claim 1, wherein
R.sub.3 is hydrogen, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN; R.sub.4 is
.beta.-hydroxyethyl, .beta.-hydroxypropyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.-, or
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.-, excepting that
R.sub.4 cannot be C.sub.2-3 hydroxyalkyl if R.sub.3 is
hydrogen.
.[.10. The compound of formula (I) as claimed in claim 1, wherein
the molar ratio of Mg.sup.2+ to the at least one further cation in
M is between 20:80 and 99.99:0.01..].
11. The compound of formula (I) as claimed in claim 1, wherein the
at least one further cation in M is selected from the group
consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Ca.sup.2+,
N-methyl-N,N-diethanolammonium, N,N-dimethyl-N-ethanolammonium,
triethanolammonium, tri-isopropanolammonium, and mixtures
thereof.
12. The compound of formula (I) as claimed in claim 1, wherein the
at least one further cation comprises Na.sup.+.
13. A sizing composition comprising a compound as claimed in claim
1.
14. Brightened paper brightened by a sizing composition, wherein
the sizing composition comprises the compound of formula (1) as
defined in claim 1.
15. A process for optical brightening of paper comprising the steps
of a) applying a sizing composition comprising the compound of
formula (1) as defined in claim 1 to the paper to form treated
paper, b) drying the treated paper.
16. A process for the preparation of a compound of formula (1)
##STR00010## wherein R.sub.1 is hydrogen or SO.sub.3.sup.-, R.sub.2
is hydrogen or SO.sub.3.sup.-, R.sub.3 is hydrogen, C.sub.1-4
alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN, R.sub.4 is
C.sub.1-4 alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.- or
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2, CO.sub.2.sup.-, benzyl, or
R.sub.3 and R.sub.4 together with the neighboring nitrogen atom
signify a morpholine ring, and wherein M is the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with at
least 1 further cation selected from the group consisting of
H.sup.+, alkali metal cation, alkaline earth metal cation other
than Mg.sup.2+, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof,
comprising the steps of having a reaction A, followed by a reaction
B, followed by a reaction C, wherein in reaction A a compound of
formula (10) is reacted with a compound of formula (II) to form a
compound of formula (12); ##STR00011## in reaction B a compound of
formula (12) is reacted with a compound of formula (13) to form a
compound of formula (14); ##STR00012## and in reaction C the
compound of formula (14) is reacted with a compound of formula (15)
to form the compound of formula (1); ##STR00013## with R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 being as defined above; M1 is
identical or different in formula (13) and (14) and is the required
stoichiometric cationic equivalent for balancing the anionic charge
in these formulae and is at least 1 cation selected from the group
consisting of H.sup.+, alkali metal cation, alkaline earth metal
cation other than magnesium, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof, M2 is
independently from each other identical or different in formula
(10) and (12) and is the required stoichiometric cationic
equivalent for balancing the anionic charge in these formulae in
the case that either R.sub.1 or R.sub.2 or both R.sub.1 and R.sub.2
are SO.sub.3.sup.-, and has the same definition as M1, with the
proviso, that at least 1 of the reactions A, B or C is carried out
in the presence of the cation CAT, with the cation CAT being
Mg.sup.2+.
17. A process for the preparation of compound of formula (1)
##STR00014## wherein R.sub.1 is hydrogen or SO.sub.3.sup.-, R.sub.2
is hydrogen or SO.sub.3.sup.-, R.sub.3 is hydrogen, C.sub.1-4,
alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN, R.sub.4 is
C.sub.1-4 alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.- or
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.-, benzyl, or R.sub.3 and
R.sub.4 together with the neighboring nitrogen atom signify a
morpholine ring, and wherein M is the required stoichiometric
cationic equivalent for balancing the anionic charge in formula (1)
and is combination of Mg.sup.2+ together with at least 1 further
cation selected from the group consisting of H.sup.+, alkali metal
cation, alkaline earth metal cation other than Mg.sup.2+, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof,
comprising the step of mixing a compound of formula (20) with a
component b), wherein component b) is a magnesium salt MS2, in
aqueous medium; ##STR00015## wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 have the definition above; and wherein T balances the
anionic charge and is the required stoichiometric equivalent of a
cation selected from the group consisting of H.sup.+, alkali metal
cation, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof.
18. The process as defined in claim 17 for the preparation of
compound of formula (1), wherein the magnesium salt MS2 is selected
from the group consisting of magnesium acetate, magnesium bromide,
magnesium chloride, magnesium formate, magnesium iodide, magnesium
nitrate, magnesium sulphate and magnesium thiosulphate.
19. The process as defined in claim 17 for the preparation of
compound of formula (1), wherein the mixing is done in aqueous
solution.
Description
The instant invention relates to mixed salts of optical brighteners
comprising Mg.sup.2+ which provide superior optical brightening
effects when applied to the surface of paper.
BACKGROUND
A high level of whiteness is an important parameter for the
end-user of paper products. The most important raw materials of the
papermaking industry are cellulose, pulp and lignin which naturally
absorb blue light and therefore are yellowish in color and impart a
dull appearance to the paper. Optical brighteners are used in the
papermaking industry to compensate for the absorption of blue light
by absorbing UV-light with a maximum wavelength of 350-360 nm and
converting it into visible blue light with a maximum wavelength of
440 nm.
In the manufacture of paper, optical brighteners may be added
either at the wet end of the paper machine, or to the surface of
paper, or at both points. In general, it is not possible to achieve
the whiteness levels required of higher-quality papers by addition
at the wet end alone.
A common method of adding optical brightener to the surface of
paper is by application of an aqueous solution of the optical
brightener at the size-press together with a sizing agent,
typically a native starch or an enzymatically or chemically
modified starch. A preformed sheet of paper is passed through a
two-roll nip, the entering nip being flooded with sizing solution.
The paper absorbs some of the solution, the remainder being removed
in the nip.
In addition to starch and optical brightener, the sizing solution
can contain other chemicals designed to provide specific
properties. These include defoamers, wax emulsions, dyes, pigments
and inorganic salts.
In order to reach higher whiteness levels, considerable effort has
been put into the development of new optical brighteners. See, for
example, Japanese Kokai 62-106965, PCT Application WO 98/42685,
U.S. Pat. No. 5,873,913 and European Patent 1,763,519.
GB 1 239 818 discloses hexasulphonated optical brighteners derived
from triazinylaminostilbenes. Examples 1 to 6 disclose their sodium
salts. Magnesium is only mentioned in a list of possible
counterions for the hexasulphonated optical brighteners, starch as
a component in a surface sizing composition is also only mentioned
in a list of possible binding agents.
The demand remains for more efficient means of achieving high
whiteness levels in paper.
DESCRIPTION OF THE INVENTION
Surprisingly, we have found that optical brighteners of formula (1)
when applied to the surface of paper, optionally in combination
with magnesium salts, in a starch sizing composition give enhanced
whitening effects.
Subject of the invention is a compound of formula (1),
##STR00002## wherein R.sub.1 is hydrogen or SO.sub.3.sup.-, R.sub.2
is hydrogen or SO.sub.3.sup.-, R.sub.3 is hydrogen, C.sub.1-4
alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN, R.sub.4 is
C.sub.1-4 alkyl, C.sub.2-3 hydroxyalkyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.- or
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.-, benzyl, or
R.sub.3 and R.sub.4 together with the neighbouring nitrogen atom
signify a morpholine ring, and wherein M represents the required
stoichiometric cationic equivalent for balancing the anionic charge
in formula (1) and is a combination of Mg.sup.2+ together with at
least 1, preferably 1, 2, 3, 4, 5 or 6, more preferably 1, 2 or 3,
even more preferably 1 or 2, further cations, the further cations
being selected from the group consisting of H.sup.+, alkali metal
cation, alkaline earth metal cation other than Mg.sup.2+, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof.
The molar ratio of the Mg.sup.2+ to the further cation in M is
preferably of from between 0.01 to 99.99 and 99.99 to 0.01, more
preferably of from 20 to 80 and 99.99 to 0.01, even more preferably
of from 50 to 50 and 99.99 to 0.01.
An alkali metal cation is preferably Li.sup.+, Na.sup.+ or
K.sup.+.
An alkaline earth metal cation other than Mg.sup.2+ is preferably
Ca.sup.2+.
Preferably, the further cation in M is selected from the group
consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Ca.sup.2+,
N-methyl-N,N-diethanolammonium, N,N-dimethyl-N-ethanolammonium,
tri-ethanolammonium, tri-isopropanolammonium and mixtures
thereof.
Preferred compounds of formula (1) are those wherein R.sub.3
represents hydrogen, methyl, ethyl, n-propyl, iso-propyl,
.beta.-hydroxyethyl, .beta.-hydroxypropyl, CH.sub.2CO.sub.2.sup.-,
CH.sub.2CH.sub.2CONH.sub.2 or CH.sub.2CH.sub.2CN and R.sub.4
represents methyl, ethyl, n-propyl, isopropyl, 2-butyl,
.beta.-hydroxyethyl, .beta.-hydroxypropyl, CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CO.sub.2.sup.-,
CH(CO.sub.2.sup.-)CH.sub.2CH.sub.2CO.sub.2.sup.- or benzyl.
Compounds of formula (2) and (3) with M having the definition as
described above, also in all its preferred embodiments, are
specific examples for the compounds of formula (1); compounds of
formula (2) and (3) with M being a mixture of Mg.sup.2+ with
Na.sup.+ and/or K.sup.+ are further specific examples, but the
invention is not limited to these specific examples.
##STR00003##
Further subject of the invention is a process for the preparation
of a compound of formula (1), characterized by a reaction A, which
is followed by a reaction B, which is followed by a reaction C,
wherein
in reaction A a compound of formula (10) is reacted with a compound
of formula (11) to a compound of formula (12);
##STR00004## in reaction B a compound of formula (12) is reacted
with a compound of formula (13) to a compound of formula (14);
##STR00005## and in reaction C a compound of formula (14) is
reacted with a compound of formula (15) to the compound of formula
(1);
##STR00006## with R.sub.1, R.sub.2, R.sub.3 and R.sub.4 having the
definition as described above, also in all their preferred
embodiments, M1 is identical or different in formula (13) and (14)
and represents the required stoichiometric cationic equivalent for
balancing the anionic charge in these formulae and is at least 1
cation selected from the group consisting of H.sup.+, alkali metal
cation, alkaline earth metal cation other than magnesium, ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1Ca.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof, M2 is
independently from each other identical or different in formula
(10) and (12) and represents the required stoichiometric cationic
equivalent for balancing the anionic charge in these formulae in
the case, that either R.sub.1 or R.sub.2 or both R.sub.1 and
R.sub.2 are SO.sub.3.sup.-, and has the same definition as M1, with
the proviso, that at least 1 of the reactions A, B or C is carried
out in the presence of the cation CAT, with the cation CAT being
Mg.sup.2+.
The cation CAT may be introduced into the reaction A, B and/or C
via M1 in formula (13) comprising Mg.sup.2+ and/or M2 in formula
(10) comprising Mg.sup.2+, or by the addition of a magnesium salt
MS1 as further component to the reaction A, B and/or C. The
magnesium salt MS1 is preferably selected from the group consisting
of magnesium acetate, magnesium bromide, magnesium chloride,
magnesium formate, magnesium iodide, magnesium nitrate, magnesium
sulphates, magnesium thiosulphate, magnesium hydroxide, magnesium
carbonate, magnesium hydrogencarbonate and mixtures thereof; more
preferably the magnesium salt MS1 is magnesium hydroxide, magnesium
chloride, magnesium sulphate or magnesium thiosulphate. Even more
preferably, the magnesium salt MS1 is magnesium hydroxide,
magnesium chloride or magnesium thiosulfate.
1, 2 or all 3 reactions A, B and C can be carried out in the
presence of a magnesium salt MS1.
Preferably, M1 and M2 independently from each other are selected
from the group consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+,
Ca.sup.2+, Mg.sup.2+, N-methyl-N,N-diethanolammonium,
N,N-dimethyl-N-ethanolammonium, tri-ethanolammonium,
tri-isopropanolammonium and mixtures thereof; more preferably M1
and M2 independently from each other are selected from the group
consisting of H.sup.+, Na.sup.+, K.sup.+ and Mg.sup.2+; even more
preferably, M1 and M2 independently from each other are selected
from the group consisting of Na.sup.+, K.sup.+ and Mg.sup.2+.
Each reaction A, B and C is preferably carried out in water or in a
mixture of water and non-aqueous organic solvent. Preferably, the
compound of formula (11) is suspended in water, or the compound of
formula (11) is dissolved in a solvent.
A preferable solvent is acetone.
Preferably, compound of formula (11) is used as a suspension in
water.
Each compound of formula (10), (13) and (15) may be used with or
without dilution, in case of dilution the compounds of formula
(10), (13) or (15) are preferably used in the form of an aqueous
solution or suspension.
Preferably, the compound of formula (10) is reacted in 0 to 10
mol-% excess with respect to compound of formula (11). One mol
equivalent of compound of formula (13) is reacted with two mol
equivalents of compound of formula (12) preferably in 0 to 10 mol-%
excess with respect to compound of formula (12). Two equivalents of
compound of formula (15) are reacted with one mol equivalent of
compound of formula (14), preferably compound of formula (15) is
reacted in 0 to 30 mol-% excess with respect to compound of formula
(14).
Preferably, any reaction A, B and C is done between atmospheric
pressure and 10 bar, more preferably under atmospheric
pressure.
In reaction A, the reaction temperature is preferably of from -10
to 20.degree. C.
In reaction B, the reaction temperature is preferably of from 20 to
60.degree. C.
In reaction C, the reaction temperature is preferably of from 60 to
102.degree. C.
Reaction A is preferably carried out under acidic to neutral pH
conditions, more preferably the pH is of from of 2 to 7.
Reaction B is preferably carried out under weakly acidic to weakly
alkaline conditions, more preferably the pH is of from 4 to 8.
Reaction C is preferably carried out under weakly acidic to
alkaline conditions, more preferably the pH is of from 5 to 11.
The pH of each reaction A, B and C is generally controlled by
addition of a suitable base, the choice of base being dictated by
the desired product composition. Preferred bases are selected from
the group consisting of aliphatic tertiary amines and of
hydroxides, carbonates and bicarbonates of alkali and/or alkaline
earth metals and of mixtures thereof. Preferred alkali and alkaline
earth metals are selected from the group consisting of lithium,
sodium, potassium, calcium, magnesium. Preferred aliphatic tertiary
amines are N-methyl-N,N-di-ethanolamine,
N,N-dimethyl-N-ethanolamine, tri-ethanolamine and
tri-isopropanolamine. Where a combination of two or more different
bases is used, the bases may be added in any order, or at the same
time. More preferably, for adjusting the pH, a basic magnesium salt
is used.
Preferably, the basic magnesium salt is selected from the group
consisting of magnesium hydroxide, magnesium carbonate, magnesium
hydrogencarbonate and mixtures thereof; more preferably the basic
magnesium salt is magnesium hydroxide.
Preferably, when a basic magnesium salt has been used to adjust the
pH in one of the reactions A and/or B, then in the consecutive
reactions B and C or in the consecutive reaction C respectively,
the base to control the pH is also a basic magnesium salt, more
preferably it is the same basic magnesium salt as used firstly in
the reaction A and/or B.
Where it is necessary to adjust the reaction pH using acid,
preferable acids are selected from the group consisting of
hydrochloric acid, sulphuric acid, formic acid and acetic acid.
Solutions containing one or more compounds of general formula (1)
may optionally be desalinated by membrane filtration.
The membrane filtration process is preferably that of
ultrafiltration. Preferably, thin-film membranes are used.
Preferably, the membrane is made of polysulphone,
polyvinylidenefluoride or cellulose acetate.
Further subject of the invention is a process for the preparation
of compound of formula (1), characterized by mixing a compound of
formula (20) with a component b), which is a magnesium salt MS2, in
aqueous medium;
##STR00007## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 have the
definition as described above, also in all their preferred
embodiments; and wherein T balances the anionic charge and
represents the required stoichiometric equivalent of a cation
selected from the group consisting of H.sup.+, alkali metal cation,
ammonium,
mono-C.sub.1-C.sub.4-alkyl-di-C.sub.2-C.sub.3-hydroxyalkyl
ammonium,
di-C.sub.1-C.sub.4-alkyl-mono-C.sub.2-C.sub.3-hydroxyalkyl
ammonium, ammonium which is mono-, di- or trisubstituted by a
C.sub.2-C.sub.3 hydroxyalkyl radical and mixtures thereof.
Preferably, the mixing is done in aqueous solution.
Preferably, T balances the anionic charge and is a cation selected
from the group consisting of H.sup.+, Na.sup.+, K.sup.+, ammonium,
N-methyl-N,N-di-ethanolammonium, N,N-dimethyl-N-ethanolammonium,
tri-ethanolammonium, tri-isopropanolammonium and mixtures
thereof.
Compounds of formula (21) and (22) are specific examples for the
compounds of formula (20), but the invention is not limited to
these specific examples.
##STR00008##
The magnesium salt MS2 is selected from the group consisting of
magnesium acetate, magnesium bromide, magnesium chloride, magnesium
formate, magnesium iodide, magnesium nitrate, magnesium sulphate
and magnesium thiosulphate. Preferably, the magnesium salt is
magnesium chloride, magnesium sulphate or magnesium thiosulphate.
Even more preferably, the magnesium salt is magnesium chloride or
magnesium thiosulphate.
Preferably, mixing temperature is of from 0 to 100.degree. C.
Preferably, the mixing is done at atmospheric pressure.
Preferably, the mixing time is of from 5 second to 24 hours.
Preferably, in addition to water further organic solvents may be
present, more preferably, the organic solvents are selected from
the group consisting of C.sub.1-C.sub.4 alcohols and acetone.
Preferably, compound of formula (20) is used in a concentration of
from 0.01 g/l to 20 g/l for the mixing.
Preferably, 0.1 to 50, more preferably 0.1 to 45, even more
preferably 0.1 to 40, especially 0.1 to 15, more especially 0.15 to
10 parts of component (b) are present in the aqueous medium per
part of component of formula (20).
Further subject of the invention is the use of a compound of
formula (20) for the preparation of a compound of formula (1).
Further subject of the invention is the use of the compound of
formula (1) in sizing compositions for brightening paper,
preferably in the size-press.
Preferably, the sizing composition is an aqueous composition.
For the treatment of paper in the size-press, sizing compositions
containing 0.2 to 30, preferably 1 to 15 grams per liter of the
compound of formula (1), may be used.
The sizing composition also contains one or more binding agents,
preferably 1, 2, 3, 4 or 5 binding agents, more preferably 1, 2 or
3, even more preferably 1 or 2 binding agents.
The sizing composition contains the binding agent preferably in a
concentration of preferably 2 to 15% by weight, based on the total
weight of the sizing composition. The pH is typically in the range
5-9, preferably 6-8.
The binding agent is preferably selected from the group consisting
of starch, gelatin, alkali metal alginates, casein, hide glue,
protein, cellulose derivatives, for example hydroxyethylcellulose
or carboxymethylcellulose, polyvinylalcohol,
polyvinylidenechloride, polyvinylpyrrolidone, polyethylene oxide,
polyacrylates, saponified copolymer of vinylacetate and maleic
anhydride and mixtures thereof.
More preferably, the binding agent is starch, polyvinylalcohol,
carbomethylcellulose or mixtures thereof.
The binding agent or size is even more preferably starch. More
preferably, the starch is selected from the group consisting of
native starch, enzymatically modified starch and chemically
modified starch. Modified starches are preferably oxidized starch,
hydroxyethylated starch or acetylated starch. The native starch is
preferably an anionic starch, an cationic starch, or an amphoteric
starch. While the starch source may be any, preferably the starch
sources are corn, wheat, potato, rice, maize, tapioca or sago.
Polyvinyl alcohol and/or carboxymethylcellulose are preferably used
as secondary binding agent.
In addition to the compound of formula (1), the binding agent and
usually water, the sizing composition may comprise by-products
formed during the preparation of the compound of formula (1) as
well as other conventional paper additives. Examples of such paper
additives are antifreezes, biocides, defoamers, wax emulsions,
dyes, inorganic salts, solubilizing aids, preservatives, complexing
agents, thickeners, surface sizing agents, cross-linkers, pigments,
special resins etc. and mixtures thereof.
Further subject of the invention is a process for the optical
brightening of paper comprising the steps of a) applying a sizing
composition comprising the compound of formula (1) to the paper, b)
drying the treated paper.
Preferably, a defoamer, a wax emulsion, a dye and/or a pigment is
added to the sizing composition.
EXAMPLES
The cation content was determined by capillary electrophoresis.
The following examples shall explain the instant invention in more
details without limiting the claimed scope. If not indicated
otherwise, "%" and "parts" are meant by weight.
Example 1
Sizing compositions are prepared by adding an optical brightener of
formula (21) in such an amount, that a range of final
concentrations of from 2.5 to 12.5 g/l of optical brightener is
achieved, to a stirred, aqueous solution of magnesium chloride
(final concentration is 8 g/l) and an anionic oxidized potato
starch (Perfectamyl A4692 from AVEBE B.A.) (final concentration is
50 g/l) at 60.degree. C.
The sizing solution is allowed to cool, then poured between the
moving rollers of a laboratory size-press and applied to a
commercial 75 g/m.sup.2 AKD (alkyl ketene dimer) sized, bleached
paper base sheet. The treated paper is dried for 5 minutes at
70.degree. C. in a flat bed drier. The dried paper is allowed to
condition, then measured for CIE whiteness on a calibrated Elrepho
spectrophotometer.
The Example is repeated both in the absence of magnesium chloride,
i.e. only the sodium salt of the optical brightener is present, and
with the magnesium chloride replaced by an equivalent amount of
calcium chloride.
The results are summarized in Table 1, and clearly demonstrate the
advantage of using magnesium chloride over the use of calcium
chloride and over the use only of the sodium salt of the optical
brightener in order to reach higher whiteness levels. The
surprising nature of the invention is further illustrated by the
observation that chloride salts of other divalent Group II metal
ions, such as calcium chloride, even have a negative impact on the
whitening effect of the optical brightener.
TABLE-US-00001 TABLE 1 Compound of formula Magnesium Calcium (21)
(g/l) Chloride (g/l) Chloride (g/l) CIE Whiteness 0 0 0 104.6 0 8 0
104.7 0 0 8 104.8 2.5 0 0 122.3 2.5 8 0 126.7 2.5 0 8 123.4 5.0 0 0
128.3 5.0 8 0 133.1 5.0 0 8 128.0 7.5 0 0 129.8 7.5 8 0 133.7 7.5 0
8 128.6 10.0 0 0 131.1 10.0 8 0 134.5 10.0 0 8 128.2 12.5 0 0 130.6
12.5 8 0 134.2 12.5 0 8 127.3
Example 2
Sizing solutions are prepared by adding an optical brightener of
formula (22) in such an amount, that a range of final
concentrations of from 2.0 to 10.0 g/l of optical brightener is
achieved, to a stirred, aqueous solution of magnesium chloride
(final concentration is 8 g/l) and an anionic oxidized potato
starch (Perfectamyl A4692 from AVEBE B.A.) (final concentration 50
g/l) at 60.degree. C.
The sizing solution is allowed to cool, then poured between the
moving rollers of a laboratory size-press and applied to a
commercial 75 g/m.sup.2 AKD (alkyl ketene dimer) sized, bleached
paper base sheet. The treated paper is dried for 5 minutes at
70.degree. C. in a flat bed drier. The dried paper is allowed to
condition, then measured for CIE whiteness on a calibrated Elrepho
spectrophotometer.
The Example is repeated both in the absence of magnesium chloride,
and with the magnesium chloride replaced by an equivalent amount of
calcium chloride.
The results are summarized in Table 2, and clearly demonstrate the
advantage of using magnesium chloride to reach higher whiteness
levels in comparison to where the optical brightener is present
only as the sodium salt.
TABLE-US-00002 TABLE 2 Compound of formula Magnesium Calcium (22)
(g/l) Chloride (g/l) Chloride (g/l) CIE Whiteness 0 0 0 104.6 0 8 0
104.7 0 0 8 104.8 2.0 0 0 119.2 2.0 8 0 122.5 2.0 0 8 121.5 4.0 0 0
127.2 4.0 8 0 131.1 4.0 0 8 127.9 6.0 0 0 131.1 6.0 8 0 135.4 6.0 0
8 131.6 8.0 0 0 133.7 8.0 8 0 138.1 8.0 0 8 133.5 10.0 0 0 136.0
10.0 8 0 139.7 10.0 0 8 134.7
Example 3
Sizing compositions are prepared by adding an optical brightener of
formula (22) in such an amount, that a range of final
concentrations of from 0 to 12.5 g/l of optical brightener is
achieved, to a stirred, aqueous solutions of magnesium chloride
(final concentrations are 6.25 and 12.5 g/l) and an anionic
oxidized corn starch (final concentration 50 g/l) (Penford Starch
260) at 60.degree. C. Each sizing solution is allowed to cool, then
poured between the moving rollers of a laboratory size-press and
applied to a commercial 75 g/m.sup.2 AKD (alkyl ketene dimer)
sized, bleached paper base sheet. The treated paper is dried for 5
minutes at 70.degree. C. in a flat bed drier.
The dried paper is allowed to condition, and then measured for CIE
whiteness on a calibrated Auto Elrepho spectrophotometer. The
results are shown in Table 3.
Example 4
Sizing compositions are prepared by adding an optical brightener of
formula (22) in such an amount, that a range of final
concentrations of from 0 to 12.5 g/l of optical brightener is
achieved, to a stirred, aqueous solutions of magnesium thiosulphate
hexahydrate (final concentrations are 10 and 20 g/l) and an anionic
oxidized corn starch (final concentration 50 g/l) (Penford Starch
260) at 60.degree. C. The sizing solution is allowed to cool, then
poured between the moving rollers of a laboratory size-press and
applied to a commercial 75 g/m.sup.2 AKD (alkyl ketene dimer)
sized, bleached paper base sheet. The treated paper is dried for 5
minutes at 70.degree. C. in a flat bed drier.
The dried paper is allowed to condition, and then measured for CIE
whiteness on a calibrated Auto Elrepho spectrophotometer. The
results are shown in Table 3.
TABLE-US-00003 TABLE 3 CIE Whiteness Magnesium salt added Magnesium
Magnesium thiosulphate Compound no Mg salt, chloride (g/l)
hexahydrate (g/l) of formula i.e. Na salt (example 3) (example 4)
(22) (g/l) only 6.25 12.5 10.0 20.0 0 102.8 102.9 103.5 102.2 102.7
2.5 119.6 122.4 125.5 125.1 123.6 5.0 128.9 131.1 132.5 132.9 132.7
7.5 135.1 136.3 137.9 137.7 137.9 10.0 139.2 140.9 141.4 141.1
141.0 12.5 141.1 142.3 142.8 142.4 142.4
The results clearly demonstrate the advantage of using magnesium
chloride or magnesium thiosulphate to reach higher whiteness levels
in comparison to where optical brightener is present only as the
sodium salt.
Example 5
115.6 parts of aniline-2,5-disulphonic acid monosodium salt are
added to 74.5 parts of cyanuric chloride in 400 parts of ice and
300 parts of water. The pH of the reaction is maintained at approx.
4 to 5 by dropwise addition of an approx. 30% aqueous NaOH solution
while keeping the temperature below 10.degree. C. by using an
external ice/water bath. After completion of the reaction, the
temperature is gradually increased to 30.degree. C. using an
external heating system and 74.1 parts of
4,4'-diaminostilbene-2,2'-disulphonic acid are added. The resulting
mixture is heated to 50 to 60.degree. C. while maintaining the pH
at approx. 5 to 7 by dropwise addition of an approx. 30% NaOH
aqueous solution until completion of the reaction. 63.8 parts of
aspartic acid are then added followed by 89.8 parts of magnesium
hydroxide and the resulting slurry is heated to 90 to 95.degree. C.
until completion of the reaction. The temperature is gradually
decreased to room temperature and insoluble materials are filtered
off. The final concentration was adjusted to 0.125 mol of compound
of formula (3) per kg of solution, for this purpose water was
either added or removed by distillation. M in this case is composed
of a mixture of sodium and magnesium cations.
Example 6
115.6 parts of aniline-2,5-disulphonic acid monosodium salt are
added to 74.5 parts of cyanuric chloride in 400 parts of ice and
300 parts of water. 26.8 parts of magnesium hydroxide are added
while keeping the temperature below 10.degree. C. by using an
external ice/water bath. After completion of the reaction, the
temperature is gradually increased to 30.degree. C. using an
external heating system. 25.7 parts of magnesium hydroxide are
added, followed by 74.1 parts of
4,4'-diaminostilbene-2,2'-disulphonic acid. The resulting mixture
is heated to 50 to 60.degree. C. until completion of the reaction.
63.8 parts of aspartic acid and 100 parts of water are then added
followed by 89.8 parts of magnesium hydroxide and the resulting
slurry is heated to 90 to 95.degree. C. until completion of the
reaction. The temperature is gradually decreased to room
temperature and insoluble materials are filtered off. The final
concentration was adjusted to 0.125 mol of compound of formula (3)
per kg of solution using UV spectroscopy, for this purpose water
was either added or removed by distillation. M in this case is
composed of a mixture of sodium and magnesium cations.
Comparative Example 7
Comparative optical brightening solution 7 is prepared by
dissolving compound of formula (22) in water with a final
concentration of 0.125 mol/kg.
Example 8
Sizing compositions are prepared by adding an aqueous solution of
an optical brightener, prepared according to example 5, in such an
amount, that final concentrations of from 0 to 80 g/l of the
aqueous solution of the optical brightener, prepared according to
example 5, are achieved, to a stirred, aqueous solution of an
anionic oxidized potato starch (Perfectamyl A4692 from AVEBE B.A.)
(final concentration 50 g/l) at 60.degree. C. Each sizing solution
is allowed to cool, then poured between the moving rollers of a
laboratory size-press and applied to a commercial 75 g/m.sup.2 AKD
(alkyl ketene dimer) sized, bleached paper base sheet. The treated
paper is dried for 5 minutes at 70.degree. C. in a flat bed
drier.
The dried paper is allowed to condition, and then measured for CIE
whiteness on a calibrated Auto Elrepho spectrophotometer. The
results are shown in Table 4.
Example 9
Sizing compositions are prepared by adding an aqueous solution of
an optical brightener prepared according to example 6, in such an
amount, that final concentrations of from 0 to 80 g/l of the
aqueous solution of the optical brightener, prepared according to
example 6, are achieved, to a stirred, aqueous solution of an
anionic oxidized potato starch (Perfectamyl A4692 from AVEBE B.A.)
(final concentration 50 g/l) at 60.degree. C. Each sizing solution
is allowed to cool, then poured between the moving rollers of a
laboratory size-press and applied to a commercial 75 g/m.sup.2 AKD
(alkyl ketene dimer) sized, bleached paper base sheet. The treated
paper is dried for 5 minutes at 70.degree. C. in a flat bed
drier.
The dried paper is allowed to condition, and then measured for CIE
whiteness on a calibrated Auto Elrepho spectrophotometer. The
results are shown in Table 4.
Comparative Example 10
Sizing compositions are prepared by adding an aqueous solution of
an optical brightener prepared according to example 7, in such an
amount, that final concentrations of from 0 to 80 g/l of the
aqueous solution of the optical brightener, prepared according to
example 6, are achieved, to a stirred, aqueous solution of an
anionic oxidized potato starch (Perfectamyl A4692 from AVEBE B.A.)
(final concentration 50 g/l) at 60.degree. C. Each sizing solution
is allowed to cool, then poured between the moving rollers of a
laboratory size-press and applied to a commercial 75 g/m.sup.2 AKD
(alkyl ketene dimer) sized, bleached paper base sheet. The treated
paper is dried for 5 minutes at 70.degree. C. in a flat bed
drier.
The dried paper is allowed to condition, and then measured for CIE
whiteness on a calibrated Auto Elrepho spectrophotometer. The
results are shown in Table 4.
TABLE-US-00004 TABLE 4 CIE Whiteness Concentration of Comparative
the optical application brightening example solution (g/l) example
8 example 9 10 0 101.5 101.5 101.5 10 119.5 119.6 119.2 20 127.4
128.4 126.7 40 133.6 135.0 132.6 60 137.1 138.6 135.8 80 138.2
140.2 136.8
The results clearly demonstrate the advantage of using a mixed salt
of an optical brightener comprising magnesium cation.
* * * * *