Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2001-10-30
2003-07-22
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C252S301230, C252S008630, C008S566000, C008S190000
Reexamination Certificate
active
06596864
ABSTRACT:
The invention relates to novel brighteners, a process for their preparation and their use for brightening substrates.
DE-A-2 335 570 discloses stilbene brighteners whose terminal triazinyl radicals are substituted with short-chain polyether alcohols.
EP-A-24 380 discloses stilbene brighteners whose terminal triazinyl radicals are substituted with phenyl-saturated ethylene oxide units.
Surprisingly, there have now been found optical brighteners conforming to the formula (I)
where
Z is SO
3
M, COOR
1
, CONR
1
, SO
2
NHR
1
, NHCOR
1
, COR
2
or CN, where
R
1
is M or C
1
-C
3
-alkyl and
R
2
is C
1
-C
3
-alkyl or phenyl,
X is O or NR
3
, where
R
3
is hydrogen or C
1
-C
4
-alkyl,
Y is hydrogen or C
1
-C
4
-alkyl, especially methyl,
M is hydrogen, an alkali metal cation or an optionally substituted ammonium ion,
n is from 4 to 35, especially from 5 to 25, preferably from 7 to 25 and
m is 0, 1 or 2.
The index n is herein to be understood as a statistical variable and preferably represents the mean.
Preferred brighteners are those in which the radical of the formula
is derived from compounds of the formula (V)
Preferred compounds of the formula (V) are phenol, phenolsulfonic acid, aniline, sulfanilic acid, dimetanilic acid (2,5-disulfoaniline).
Preferred brighteners of the formula (I) are those where
Z is SO
3
M,
m is 0, 1 or 2
X is NH,
n is from 4 to 15, especially from 5 to 15, preferably from 7 to 15,
Y is hydrogen and
M is hydrogen, Na, K or a C
1
-C
4
-mono-, -di-, -tri- or -tetra-alkanolammonium.
Particularly preferred brighteners of the formula (I) are those where
Z is SO
3
M,
m is 1,
X is NH,
n is from 4 to 15, especially from 5 to 15, preferably from 7 to 15,
Y is hydrogen and
M is Na or K.
Particularly preferred brighteners of the formula (I) conform to the formula (II)
where
M is hydrogen, Na or K and
n is from 4 to 15, preferably from 5 to 15, especially from 7 to 15.
The invention further provides a process for preparing the compounds of the formula (I), which is characterized in that compounds of the formula (III)
where
A is Cl or F, especially Cl,
are reacted with polyglycols or polyglycol ethers of the general formulae (IV)
Y—O—[CH
2
CH
2
O—]—
n
H (IV)
where Z, X, Y, m and n are each as defined above.
In a particular embodiment of the process according to the invention, the reaction is effected at a temperature of 20 to 100° C., preferably in the presence of an acid-binding agent, such as for example sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
The reaction is generally carried out similarly to the procedure disclosed in DE-2 335 570.
Compounds of the formula (III) are known for example from EP-A-860 437.
Preferred compounds of the formula (IV) are for example polyethylene glycols, especially those where n=4 to 35, especially 4 to 25, preferably 5 to 25, particularly preferably 7 to 25, preferably with an average molecular weight of 200 to 1000 g/mol, especially 200, 300, 400, 600 and 1000 g/mol, and also their corresponding monomethyl ethers.
Particular preference is given to using compounds of the formula (IV) which are polyethylene glycols having average molecular weights of 200 to 600 g/mol.
The compounds of the formula (I) according to the invention are generally prepared using an excess of compounds of the formula (IV). The molar excess of IV, based on III, is preferably 5 to 20 mol. This excess of (IV) can be removed from the end product by diafiltration for example. Preferably, however, the excess stays in the end product, since it has a positive influence on the stability of the liquid formulation and also on the whiteness of the brightened material.
The invention also provides brightener preparations containing the brightener of the formula (I) according to the invention and a polyglycol ether. Preferred polyglycol ethers are those of the formula (IV) where the meanings for Y and n can be independent of those of the formula (I).
Preference is given to those brightener preparations containing
10-25% by weight of brightener of the formula (I)
20-60% by weight of polyglycol ether
15-70% by weight of water.
Salts may be present in addition.
When polyglycol ethers of the formula (IV) are used, polyethylene glycols (PEGs) having molecular weights of 1500 to 6000 g/mol can be used in addition. The latter can be present at 0 to 40% by weight, based on the preparation.
The compounds of the general formula (I) according to the invention are optical brighteners for various substrates. Particularly preferred substrates are those composed of natural cellulose such as cotton, paper and wood materials in fine dispersion or materials composed of regenerated cellulose, of wool or synthetic polyamides. The materials to be optically brightened can be present in a wide variety of processing stages such as raw material, intermediate article or finished article and in a wide variety of processing forms such as for example fibers, threads, wovens, formed-loop knits, webs and also films etc.
The compounds according to the invention can also have laundry detergent added to them. The solid and liquid laundry detergents used can contain the customary ingredients corresponding to the prior art.
The compounds of the invention can further be applied during the resin finishing of fiber materials in conjunction with synthetic resins and synthetic resin precondensates. The crosslinking of the synthetic resins can be carried out over a wide pH range, especially from pH 1 to pH 10, in a conventional manner. Thus, especially the compounds of the formula (I) according to the invention in which
Z is SO
3
M,
m is 1 or 2,
X is NH,
n is from 4 to 15, preferably from 5 to 15, especially from 7 to 15,
Y is hydrogen and
M is Na or K
are suitable for the optical brightening of cellulose materials from acidic crosslinking baths, as is customary for the wash and wear finishing of cellulose fibers.
The compounds according to the invention can further be used for raising the sun protection factor of textile materials. The use of diaminestilbenedisulfonic acid derivatives for raising the sun protection factor of textile materials is known and described for example in EP-A 728 749 ({circumflex over (=)}GB 9 503 474). Suitable for this use are in particular the compounds of the general formula (I) according to the invention where
Z represents COOR
1
, where R
1
is C
1
-C
3
-alkyl or M, or represents CONR
1
, SO
2
NHR
1
, NHCOR
1
, CO—R
3
, where R
3
is C
1
-C
3
-alkyl or phenyl, or represents CN,
m represents 1,
X represents NH,
n represents from 4 to 15, preferably from 5 to 15,especially from 7 to 15,
Y represents hydrogen or methyl,
M represents hydrogen, an alkali metal cation or an optionally substituted ammonium ion.
To raise the sun protection factor of textile materials, the textile material can be treated directly with the compounds of the invention, or else the effect is achieved as part of a normal domestic laundering process when the laundry detergent used contains the compound according to the invention.
The brighteners of the formula (I) according to the invention are suitable for brightening paper materials in papermaking, for example cellulose, chemical and mechanical pulp, and for brightening the coating compositions customarily used in the paper industry, specifically for brightening unpigmented but especially pigmented paper materials and coating compositions.
The binders in known coating compositions include polymer dispersions based on copolymers of butadiene-styrene, acrylonitrile-butadiene-styrene, acrylic esters, ethylene-vinyl chloride or ethylene-vinyl acetate or based on homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene, polyvinyl acetate or polyurethanes. A preferred binder consists of styrene-butyl acrylate or styrene butadiene-acrylic acid interpolymers. Further polymer latices are described, for example, in U.S. Pat. No. 3,265,654.
The coating compositions are customarily pigmented using aluminum silicates, such as china clay and kaolin, also barium sulfate, satin white,
Brockmann Rolf
Feldhues Ulrich
Gassen Karl-Rudolf
Roick Thomas
Vogt Uwe
Akorli Godfried R.
Balasubramanian Venkataraman
Bayer Aktiengesellschaft
Eyl Diderico van
Raymond Richard L.
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