Note: Descriptions are shown in the official language in which they were submitted.
CA 02202737 1997-04-15
X0614
Novel Atni~opolysiloxanes with Hindered
4-Amino-3,3-dimethylbutyi Groups
Background
It is known to treat fibers and fabrics, both natural and synthetic, with.
organopolysiloxanes to impart tactile properties such as flexibility,
smoothness and
"hand". Among organopolysiloxanes, aminofunctional organopolysiloxanes have
been
recognized to provide the most desirable hand. Several examples of such
aminoorganopolysiloxane can be found in the prior art.
U.S. Patent No. 4,247,592 to Kalinowski teaches treating synthetic
textiles with triorganosiloxy endblocked polydiorganosiloxanes having diamino
groups
attached through a tower alkylene to a mono or difunctional siloxy units. U.S.
Patent
No. 4,661,577 to Lane discloses aminopotysiloxanes with trialkylsiloxy
terminal groups
having at least one amino, diamino or substituted amino group linked to at
least one
trifunctional siloxy unit through an alkylene bridge, which may also contain
heteroatoms. U.S. Patent No. 5,073,275 to Ona discloses a compos~'~on and
method
for treating organic fibers with a different type of aminoorganosiloxane, one
modified
with the SiC bonded N-cyclohexylaminoalkyl radicals.
CA 02202737 1997-04-15
Surnm of the Invention
The present invention provides novel aminofunctionai polysilvxanes
particularly
useful in the treatment of textiles. These novel polysiloxanes contain
hindered,
4-amino- 3,3-dimethylbutyl groups and can be reactive fluids with hydroxy,
alkoxy or
4-amino- 3,3-dimethylbutyl terminal functionality or non-reactive, terminated
with
trialkylsitoxy groups. The potysifoxanes of the present invention contain
hindered
neohexytamino groups, which are less prone to oxidation and therefore cause
less
discoloration of any treated textiles. The present invention also provides
methods for
treating textiles with the aforesaid aminofunetionat silicone compositions.
The present invention is directed to polysiloxanes of general formula (I}
Q2RSi0- (SiR20),~(SiRR'O)y-SiRQa (I)
wherein
R is selected from the group consisting of monovatent hydrocarbon groups
having 1 to 10 carbon atoms including alkyl, aryl and aratkyl groups. The R
groups may be the same or different from one another and are illustrated by
methyl, ethyl, butyl, hexyl, phenyl, benzyl and phenethyl. Of these, lower
alkyl
groups (C,-Ca} are preferred. Most preferably R is methyl.
R' is CH2CH2C(CH3)2CH?N(R2)2, where each RZ is the same or different and
each is hydrogen, an alkyl of C,-Cs, an alkyl amine of C,-Cs (i,e. a C,-Cs
alkyl
group substituted with -NH2) or an alkanolamine of C,-Cs (i.e. a C~-Cs alkyl
group
substituted with -OH and with -NH2). Specific RZ groups include propylamine,
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CA 02202737 2002-05-15
propanolamine, methyl, and most preferably, hydrogen.
The amino group on R1 may be protonated or quaternized.
Q is R, R1, hydroxyl, or an alkoxy of C1-C4. Preferably,
the alkoxy group is methoxy or etlaoxy. Most preferably
Q is methyl.
"x" can be zero or an integers "y" is an integer greater
than zero (with the understanding that for an overall
polysiloxane composition, x and y represent average numbers),
with x + y being less than 1,100. Preferably x ranges from 20
to 1000 and y ranges from 1 to 50; most preferably x ranges
from 50 to 800 or 50 to 500 and y ranges from 1 to 20.
Detailed Description of the Invention
Aminopolysiloxanes of the present invention are
prepared, for example, by processes analogous to those
disclosed in U.S. Patent Nos. 3,033,815, 3,146,250 and
4,247,592 by hydrolyzing the corresponding dialkoxy 4-amino-
3,3-dimethylbutyl modified silane (which can be prepared
according to U.S. Patent No 5,353,880 to Pepe) in. excess water
or water-solvent such as tetrahydrofuran mixture, at 10 to
50°C, preferably, room temperature, for 2 to 5 hours followed
by vacuum strip and equilibrating the resulting hydrolyzate
with di(alkyl, aralkyl or aryl)cyclopolysiloxane (source of
R25i0 groups) and hexamethyldisiloxane, decamethyltetra-
siloxane, or other reactants to serve as the source of the
terminal RQ2Si0 groups as defined by Formula 1) in the presence
of a base catalyst, such as KOH, with heating at about 130 to
150°C for about 5 to 12 hours. A reactive aminopolysiloxane
having hydroxy or alkoxy terminal
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groups can be prepared in a similar and well known manner from
the amine containing silane and cyclopolysiloxane.
The protonated form of the polysiloxanes can be
prepared by adding a protonic acid in an amount calculated to
achieve the desired degree of protonation, that is, complete
or less than complete if the amount of acid added: is less than
stoichiometric. The quaternized form of the polysiloxane can
be prepared by reacting it with a suitable quaternizing agent,
such as methyl chloride, benzyl chloride, dimethyl sulfate, or
diethyl sulfate. Preferred quaternary substituents include
methyl, ethyl, and benzyl. The quaternary forms of the
polysiloxane will be in ionic neutrality with a stoichiometric
amount of an anion such as chloride, methylsulfate or
ethylsulfate.
While the aminopolysiloxanes of the present invention
can be used neat, for ease of the application, they are usually
applied dissolved, dispersed or emulsified in a suitable liquid
medium. Preferably, the aminopolysiloxanes of the present
invention can be applied from an aqueous solution, emulsion or
dispersion. The aminopolysiloxanes may also be applied as a
solution in a non-aqueous solvent such as isopropanol and
hexane, or in a liquid in which the aminopolysiloxane is
miscible, such as toluene. Most preferably, the
aminopolysiloxane is applied to the textile as an aqueous
emulsion.
The preparation of aqueous emulsions of
aminopolysiloxanes is well known to those skilled in the art.
One such preparation is described, for example, in U.S. Patent
No. 5,039,738. To prepare an aqueous emulsion, an
aminopolysiloxane is optionally combined with emulsifiers known
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CA 02202737 1997-04-15
in the art and diluted to the desired polymer level with water. The polymer
content of
the aminopolysiloxane emulsion of the present invention ranges from about 10
to 80
percent, preferably 20 to 40 percent.
The emulsion of the aminopolysiloxane of the present invention can be
applied to the surface of any desired substrate, such as by spraying, dipping,
or kiss
roll application. The polysiloxane shoult~ be applied so that the amount of
polysiloxane
is 0-1 to 5.0, preferably 0.2 to 2.5, weight percent of the textile.
Substrates which can be treated with the aminopolysiloxanes of the
present invention include textiles (both woven and nonwoven), hair, and paper.
Textiles are exemplified by (1) natural fibers such as cotton, flax, wool and
silk; (ii)
synthetic fibers such as polyester, polyamide, polyacrylonitrile,
polyethylene,
polypropylene and polyurethane; (iii) inorganic fibers such as glass and
carbon fiber; or
(iv) biends of any of the above-mentioned fibers.
Optionally, other additives typically employed in treating the textile or
other substrate Can be included with the emulsion or applied separately to the
substrate. Such additives can include a durable press resin, curing catalyst,
preservatives and biocides, pigments or dyes, fragrances, fillers, pH buffers,
antifoamer
and defoamers.
Textiles and other substrates treated with the aminopoiysiloxane of the
present invention are dried either at room temperature or by heat and cured at
a
temperature less than the melting or decomposition temperature of the
substrate.
Heating can be accomplished by any suitable method, but preferably is done by
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CA 02202737 1997-04-15
passing the substrate through a hot air oven. The resulting treated substrate,
thus, has
properties such as amine-like hand and whiteness.
Moreover, compositions including the amino polysiloxanes of the present
invention may be used in personal care formulations, including lotions,
creams, shaving
cream, hair sprays, conditioners, shampoos, deodorants, moisturizers, and
sunblocks,
and in adhesive and sealant formulations. Additionally, said aminpolysiloxanes
may be
used in car wax formulations.
s
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Exampf_~s
The following specific examples are set forth for illustration only and are
not to be
construed as limiting of the present invention.
In the examples, the test fabric and test procedures used were as follows:
Fabrics Identification (Test Fabrics inc.. Middlesex NJ) - Bleached Cotton
interlock
Knit, Style 460; Bleached Desized Cott6h Print Cloth, Style 400.
Test Procedures
~ Conditioning Textiles for Testing, ASTM Method D-i 776-79
~ Absorbency of Bleached Textiles, AATCC Method 79-1992
~ Softness evaluation was done by the hand panel and the tested fabrics were
rated
on the scale from 1 to 10, where 1 is very harsh 10 is very soft. Each hand
panel
involved at least five panelists and reported results are average values.
To evaluate discoloration of the treated textiles caused by the
aminopolysiloxanes,
whitenesslreflectance data were generated using Colorquest Colorimeter from
Hunter I-abs.
~ Reflectance of the fabrics scorched in the curing oven at 200°C for
100 seconds
was measured to determine resistance of the aminosilicone finishes to
prolonged
heating.
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Example 1. Preparation of Aminopolysiioxanes Emulsions
The aminopolysitoxanes set forth in Table 1 were prepared in accordance
with the procedure disclosed in U.S. Patent No. 2,247,592, using 4-amino-3,3-
dimethylbutylmethyldimethoxysitane as a source of aminofunctionatity, and
formulated
into emulsions. To form an emulsion, 40 parts of the aminopolysiloxane was
mixed in a
vessel with a surfactant blend of 3.6 parts of TERGfTOL~ 15-S-3 surfactant,
2.4 parts
of TERGITOL~ 15-S-15 surfactant and 12 parts water to form a premix. The
premix
was homogenized with a laboratory mixer at 500 to 800 rpm. The remaining water
(42
parts) was added slowly white mixing.
Table 1. 4-Amino-3,3-dimethytbutyl Modified Poiysiioxanes
besignattv Forrriula ~ . Visco Amore Content.
n " >ity (cps).
, , , : ; 2tS VVf. ./a
',. . s ; ' NH2 a.
AminopofysiloxaneMD~D'2M 105 0.82
t
4minopofysiloxaneMb,~D*~M 21 fi 0.42
1l
P.minopofysifoxaneMD~oD*sM 1404 0.43
lil
AminopolysitoxaneMD~QO',of~ 1056 0.88
IV
nminopol;~siloxaneMD~D'3M 4632 0.15
V
hmino e!~ siloxaneAAD~~D*.M ~ 3690 0.29
~!!
' M = O,r2Si(CH3)3 ; D = OSi(CHs)2; D* = OSiCH2CH2C(CH3)aCHzNHa
2 ~1.~,1n~ n~,r,~',W rlnrnrminnl~ by litrwt~~~
1 1111 11~ 11~ V~e~VI ~..
These polysiloxanes were applied to 100% cotton, knit and woven, with and
without
durable press resin at 1.0 weight percent of polysitoxane. The polysiloxanes
improved
the hand of the fabric with minimal yellowing after curing.
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Example 2. Softness and Discoloration of 100% Cotton Knit Treated with 4-Amino-
3,3-
dimethylbutyi Modified Polysiloxanes
Aminopolysiloxanes I-vt as set forth in Table 1, and two control softeners
MAGNASOFT~ Ultra and MAGNASOFTb PLUS ( commercial premium amino
softeners modified with 3-(2-(aminoethyl)aminopropyl pendant groups, having
amine
content of 0.8% and 0.25% as NH2, respectively) were padded onto 100% cotton
knit
in combination with a durable press resin (methylated
dimethyloldihydroxyethyleneurea, which is commercially available) and curing
catalyst
(magnesium chloride) to simulate typical textile finishing procedure. The
softener
concentration in the finishing composition was such that the effective actives
add-on
levels on the fabric were 1.0°/s (BOWF, i.e., based on the weight of
the fabric); curing
conditions were 171°C for 1.5 minutes. Softness and reflectance data
are provided in
Table 2.
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Tabie 2 Softness and Reflectance of 100% Cotton Knit Treated
with ~i-Amino-3,3-dimeihyioutyi i4iodified Poiysiioxatte.~
. . . . : ::~: -: :. i > . Reflectance:
v Softness l~a~ :v. ,.: ;
Des~gnat~ont Amitieng
.; ,.
Lori : . x.:____~ . _ , .
~ _. .. ,
teat as Nw
Magnasoft~ Ultra 9.0 64.4
(0.8%)
Maonasoftc9 Plus 7.8 72.5
J
(0.25/)
Aminopofysiloxane 3.0 72.6
!
(0.82i)
A.r,,inopoly si!oxane6.5 74.2
!!
(0.42l0)
~' miriG('.rOlySiloxane7.3 75.3
I!!
(0.43~/0)
Amir~opoiysiioxane 5.3 72.8
!V
(o.ss~,o)
AfriinOpoiysiioxane6.1 vQ.1
V
(0. i 5l)
An~inopoiysiioxane 6.8 %9.6~
vi
0.29l0
Resin Onl 1.0 83-0
dated on the scale 1-10, where 1 is harsh and 10 is very soft
Z? higher numbers mean lower discoloration
A!f 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less
discoloration o!
the textile substrate than aminopolysiloxanes modified with
3-(2-aminoethy!)aminvpropyl groups.
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Example 3. Softness and Discoloration of 100°!° Cotton
Woven Treated with
4-Amino-3,3-dimethylbutyl Modified Polysiloxancs
Aminopolysiloxanes I-VI, as set forth in Table 1, and two control sotteners
MAGNASOFT~ Ultra and MAGNASOFT~ PLUS ( commercial premium amino
softeners modified with 3-(2-aminoethyl)aminopropyl pendant groups, having
amine
content of 0.8% and 0.25% as NHZ, respectively) were padded onto 100% cotton
print
cloth in combination with a durable press resin (methylated
dimethyloidihydroxyethyleneurea, which is commercially available} and Curing
catalyst
(magnesium chloride) to simulate typical textile finishing procedure. The
softener
concentration in the finishing composition was such that the effective actives
add-on
levels on the fabric were 1.0% (BOWF}; curing conditions were 171°C for
1.5 minutes.
Softness and reflectance data ace given in Table 3..
20 ._
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Table 3. Softness and Retiectaace of 10a% Cotton Print Cloth Treated with
4-Amino-3,3-dimethylbutyi ~ilodil'fed Polyaiioxanes
Deslgnariortl~lm~ne';~oftriessR$ting.Ref(eCtat~ce~__
~
Core to . z . . ; : . . .
. ~ , . ,;
nt as fVH ~ ,
MagnasoftC~ Ultra 6.6 53.0
(~.$%~
Magnasoft~ Plus 8.0, 58.4
(0.25, ;
Aminnpolysiloxane 8.2 56.4
I
(0.82%)
prninn ? .~
,n,QlycilnYana I,I 1, ,7
4
~ . ~
(0.42%) . .
Amirnnnlwe~ilnvnr~~5_3 60.0
111
m l ~ wlrvy amvnm
(0.43,0)
At l ~SiiG~'IV;yjilviiqivr.~ v~.v
ie I~~ ~
(a.sa~i~
111111rIV~Ul51S11I~XQ11C0~2 V3.G'
Y ~
(0.55%}
Aminopolysiioxane b.4 62.4
vi
0.29%
Resin Onl 1.0 64.2
'' rated on the scale 1-10, where 1 is harsh and 10 is very soft
2' higher numbers mean lower discoloration
All 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less
discoloration of
the textile substrate than aminopofysiloxanes modified with
3-(2-aminoethyl)aminopropyl groups.
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~xampie 4. Reflectance of the Scorched 100% Cotton Print Cloth Fabrics Treated
v~rith 4-Amino-3,3-dimethylbutyl Modified Polysi4oxar~es
Reflectance of the treated fabrics from Example 3, exposed to scorch
Conditions
at 200°C for 100 seconds, has been measured to determine yellowing
tendency of the
inventive potysiloxanes under prolonged heat. Results are summarized in Table
4.
Table 4. Reflectance of the Scorched 100% Print Cloth Treated with
with 4-Amino-3,3-dimethylbutyl Modified Polysiloxanes
De~ignationlAmi~e.::Reflectance after
. ~
;
, ;:...
vcritEnt a~:rZ~-iv-:':...scQ~chin ~)
Magnasoft~ Ultra 2&.7
{0.8%)
Magnasoftc~ Plus 35.7
(0.25%)
Aminopolysiloxane 32.0
I
(0.82%)
Aminopolysiloxane 33.5
II
(0.42%)
Aminopolysiloxane . 32.6
III
(0.43%)
Aminopolysiloxane 31.8
IV
{0.88%)
Aminopolysiloxan2 3$,1'
V
(0.15%)
Aminopolysiloxane 37.4
VI
0.29%
Resin Only 39.5 -
'~highes nuraberj mean lower di$~loration
At the equivalent amine content, 4-amino-3,3-dimethylbutyl modified
polysiloxanes
caused less discoloration of the textile substrate than aminopolysiloxanes
modified with
3-{2-aminoethyl)aminopropyl groups.
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