Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02226943 1998-O1-09
WO 97/04173 PCT/US96/11719
TISSUE PRODUCTS CONTAINING SOFTENERS
AND SILICONE GLYCOL
Background of the Invention
In the fields of facial and bath tissues, efforts are continually
being made to improve upon the various properties of the tissues in order
to provide better products for the consumer. Among the tissue properties
constantly sought to be improved is softness.
Hence there is a need for new methods for increasing the softness of
tissue products.
Summary of the Invention
It has now been discovered that bulk and exceptional softness can be
imparted to tissues by incorporating into the tissue a combination of a
silicone glycol with one or more softener/debonders. As used herein,
"softener/debonders" are chemical compounds selected from the group
consisting of quaternary ammonium compounds, quaternized protein
compounds, phospholipids, silicone quaternaries and organoreactive
polysiloxanes, all hereinafter further described. More specifically, it
has been found that the presence of quaternary softener/debonders enhance
the effectiveness of the silicone glycol by increasing the retention of
the silicone glycol on the fibers.
Hence, in one aspect, the invention resides in a soft tissue
comprising papermaking fibers and from about 0.01 to about 6 percent
active matter, based on the weight of the fiber, of one or more
softeners/debonders selected from the group consisting of quaternary
ammonium compounds, quaternized protein compounds, phospholipids,
~ silicone quaternaries and organoreactive polysiloxanes, and from about
0.0001 to about 3 percent active matter, based on the weight of the
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fiber, of silicone glycol. More specifically, the amount of the
softener/debonder can be from about 0.1 to about 3 percent active matter,
based on the weight of the fiber, and the amount of silicone glycol can
be from about 0.005 to about 1 percent active matter, based on the weight ,
of the fiber.
In another aspect, the invention resides in a method for making a .
soft tissue comprising: (a) adding one or more softener/debonders and a
silicone glycol to an aqueous suspension of papermaking fibers, either
separately or as a combined aqueous mixture, wherein the amount of
softener/debonder is from about 0.01 to about 6 percent active matter,
based on the weight of fiber, more specifically from about 0.1 to about 3
percent active matter, based on the weight of fiber, and wherein the
amount of silicone glycol is from about 0.0001 to about 3 percent active
matter, based on the weight of fiber, more specifically from about 0.005
to about 1 percent active matter, based on the weight of fiber; (b)
depositing the aqueous suspension of papermaking fibers onto a forming
fabric to form a tissue web; and (c) dewatering and drying the web. The
amount of the silicone glycol and the softener/debonder added will depend
largely on the extent to which the silicone glycol and the
softener/debonder are retained by the fibers, rather than passing through
the system with the water, and the costs of the materials.
Suitable silicone glycols include, without limitation, those having
the following structure:
CH3 CH3 CH3 CH3
CH3-Si-0-(Si-0)x-(Si-0)Y-Si-CH3
CH3 CH3 R CH3
0
(CHZ-CHZ-0)
(CHZ-CH2-0)~-R~
CH3
wherein R = alkyl group, C~ - C6; .
R~= acetate or hydroxyl group;
x = 1 to 1000;
y = 1 to 50;
m = 1 to 30; and
n = 1 to 30.
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In addition to the silicone glycols, other nonionic surfactants can
also be added to the tissue. Examples of useful classes of nonionic
surfactants include alkylphenol ethoxylates; aliphatic alcohol
ethoxylates (the alkyl chain of the aliphatic alcohol may be either
straight or branched, primary or secondary); fatty acid alkoxylates (the
fatty acids may be saturated or unsaturated); fatty alcohol alkoxylates;
block copolymers of ethylene oxide and propylene oxide; condensation
products of ethylene oxide with the product resulting from the reaction
of propylene oxide and ethylenediamine; condensation products of
propylene oxide with the product of the reaction of ethylene oxide and
ethylenediamine; semipolar nonionic surfactants, including water soluble
amine oxides; alkylpolysaccharides, including alkylpolyglycosides; and
fatty acid amide surfactants.
Also, in addition to the silicone glycol and other nonionic
I5 surfactants, polyhydroxy compounds can also advantageously be included.
Examples of useful polyhydroxy compounds include glycerol, and
polyethylene glycols and polypropylene glycols having a weight average
molecular weight of from about 200 to about 4,000, preferably from about
Z00 to about 1,000, most preferably from about 200 to about 600.
Polyethylene glycols having a weight average molecular weight from about
200 to about 600 are especially preferred.
Suitable quaternary ammonium compounds include, without limitation,
those having the following structures:
CH3 +
CH3-N-R X-
R
wherein X = chloride, methyl sulfate, or other compatible counterion; and
R = aliphatic, saturated or unsaturated Cs - CZZ;
and
CH3 +
R-N-R~ X-
~ 35 R
wherein X = chloride, methyl sulfate, or other compatible counterion;
R = aliphatic, saturated or unsaturated C8 - C22; and
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R~= benzyl or epoxy group;
and
'
CH3 +
/ N CHz
R _ C\ ~ X_
N CHz
CHz-CHz-NH-C-R
wherein X = chloride, methyl sulfate, or other compatible counterion; and
R = aliphatic, saturated or unsaturated C8-Cz2;
and
0 +
R-C-NH-CHz-CHz CH3
v i
N X_
R-C-NH-CHz-CHz~R~
0
wherein X = methyl sulfate, chloride, or other compatible counterion;
R = aliphatic, normal, saturated or unsaturated, C8 - Czz; and
R~ = 2-hydroxyethyl or 2-hydroxypropyl;
and
CH3 +
R'n-N-R'n X'
wherein R = aliphatic, normal or branched, saturated or unsaturated, C8 -
Czz
X = chloride, methyl sulfate, ethyl sulfate, or other compatible
counterion;
R'= 2-hydroxyethyl or polyethoxyethanol; and
n = 1 to 50;
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and
0 CH3 j0 +
R-C-0-CHZ-CHZ-~!-CH2-CHZ-0-CrR X-
CHZ
CH2-OH
wherein R = C$ - CZZ; and
X = methyl sulfate, chloride, or other compatible counterion;
and
CH3 +
i
CH3-N-R X-
CH3
wherein R = aliphatic, saturated or unsaturated, C8 - C22; or allyl-; or
R'-0-CH2-CHZ-CHZ. where R'= normal or branched, C4 - C~B; and
X = chloride, sulfate or any other compatible counterion;
and
R +
CH3-N-R X-
R
wherein R = aliphatic alkyl, normal or branched, saturated or
unsaturated, C8 - C2Z; and
X = chloride, methyl sulfate, or other compatible counterion.
Suitable quaternized protein compounds include, without limitation,
those having the following structures:
0 CH OH +
3
R~-C-NH-(CHZ)-N-CHZ-CH-CHZ-R2 X'
CHs
wherein R~ = fatty acid radical, saturated or unsaturated, C~2 -
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RZ = hydrolyzed soy protein, hydrolyzed silk protein, collagen,
keratin moiety, or hydrolyzed wheat protein; and
X = chloride, lactate, or other compatible counterion;
and
'
CH3 +
R~-N-CH2-iH-CHZ-Rz X-
CH3 OH
wherein = fatty radical,saturated or unsaturated,
R~ acid C~2 - C2z;
R2 = hydrolyzedcollagenor keratin moiety;
X = chloride,lactate,or other compatible counterion.
Suitable phospholipids include, without limitation, those having the
following structures:
R~ + 0
i
R-N-CH2-iH-CHZ-0 ~-(B)Y + xA + aM
RZ OH x
wherein x = 1 to 3;
x + y = 3;
a = 0 to 2;
B = 0- or OM;
A = an anion;
M = a cation; and
R, R~ 8~ R2 can be the same or different, are alkyl, substituted
alkyl, alkyl aryl or alkenyl groups of up to 16 carbon atoms and
the total carbon atoms of R + R~ + RZ = 10 to 24;
and
+ 0 '
R~-N-CHZ-CH-CH2-0 ~P-(B)y + xA + aM
R6 OH x '
wherein x = 1 to 3;
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x+y=3;
a = 0 to 2;
B = 0' or OM;
A - an anion;
M - a cation;
R5, R6 may be the same or different, are alkyl, hydroxyalkyl,
carboxyalkyl of up to C6, or polyoxyalkylene of up to Coo; or R5,
R6 and the nitrogen they are attached to may represent an N-
heterocycle; and
R~ - an amidoamine moiety of the formula:
0 R3
R4-C-N-(CH2)~_
wherein n = Z to 6;
R3 = hydrogen or alkyl, hydroxyalkyl or alkenyl
of up to 6 carbons; or cycloalkyl of up to
6 carbon atoms, or polyoxyalkylene of up to
10 carbon atoms; and
ZO R4 = alkyl, alkenyl, alkoxy or hydroxyalkyl, C5-
CZ~, or aryl or alkaryl of up to C2o;
and
R~ ++
R-N-CHZ-CH-CHZ-0-P-0-CHZ-CH-CHZ-N-R~ 2A
Rz OH OM OH RZ
wherein A - an anion;
M - a canon;
R, R~ & RZ can be the same or different, are alkyl, substituted
alkyl, alkyl aryl or altkenyl groups of up to 16 carbon atoms,
and the total carbon atoms of R + R~ + R2 = 10 to 24; and
R' is an amidoamine moiety of the structure:
0 R3
R8-C-N-(CH2)~-
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wherein n - 2 to 6;
R3 = hydrogen or alkyl, hydroxyalkyl or alkenyl
of up to 6 carbons; or cycloalkyl of up to 6
carbon atoms, or polyoxyalkylene of up to 10
carbon atoms; and
R$ has the following structure:
~ H3 ~H3 CH3 CH3
CH3-Si-0-( ,i-0)P-($~-0)q-Si - CH3
CH3 CH3 (CH2)~ CH3
N
=0
wherein n = 3 or greater;
p = 1 to 1000;
q = 1 to 25.
Suitable silicone quaternaries include, without limitation, those
having the following structure:
CH3 ~ H3 ~H3 ~H3 ++
R-N-Z-(S; -0)n-S'i-Z-N-R ZX-
CH3 CH3 CH3 CH3
wherein R = alkyl group, C~Z - C~8;
Z = -CHZ-CHZ-CHZ-0-(CH2)3-;
X = alkoxy, chloride or other compatible counterion; and
n = 1 to 50.
Suitable organoreactive polysiloxanes include, without limitation,
those having the following structures:
~ H3 ~ H3 CH3 CH3
CH3-Si-0-(Si-0)x-(~i-0)Y-Si-CH3
CH3 CH3 ~HCH3 CH3
CHz
R
and
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CH3 CH3 ~H3
R-(CH2)n-Si-0-(Si-0)x-~i-(CHZ)~- R
- CHs CH3 CH3
and
~H3 ~H3 ~H3
R-(CH2)~-Si-0-(~i-0)x-~i-CH3
CH3 CH3 CH3
wherein R = amine, carboxy, hydroxy, or epoxy;
n = 3 or greater;
x = 1 to 1000; and
y = 1 to 25.
x les
x m 1e
A one-ply, uncreped, through-air-dried tissue was made using a
layered headbox. The two outer layers contained bleached eucalyptus
hardwood kraft pulp processed through a Maule shaft disperser with a
power input of 80 kilowatts at a consistency of about 34 percent and at a
temperature of about 184'F. The two outer layers made up 70 percent of
the tissue sheet by weight of the fiber. The remaining 30 percent of the
tissue sheet constituted the inner layer consisting of northern softwood
kraft pulp. The total basis weight of the sheet was 33.9 grams per
square meter of air dried tissue. The inner layer was refined to obtain
sufficient dry strength in the final product. A wet strength agent,
Parez 631NC (glyoxalated polyacrylamide obtained from Cytec Industries,
Inc.) was metered into the inner layer at a rate of 5 kilograms active
matter per tonne of fiber. An aqueous softener blend comprising 4 weight
percent of a quaternary ammonium compound (methyl-1-oleyl amidoethyl-2-
oleyl imidazolinium methylsulfate) (Yarisoft 3690 from Witco Corporation,
90 percent active matter) and 1 weight percent silicone glycol (silicone
polyether identified as Dow Corning 190 from Dow Corning Corporation) was
premixed and added to the outer layers at the thick stock (2 percent
consistency). The thick stock of all layers was diluted to approximately
0.12 percent consistency prior to formation of the tissue web. The
resulting furnish contained 5.25 kilograms per tonne of Varisoft 3690
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(0.525 dry weight percent) and 1.32 kilograms per tonne of Dow Corning
190 (0.132 dry weight percent). The resulting tissue was softer to the
touch than similar tissue made with the quaternary compound but without
the silicone glycol.
Example 2
A two-ply, uncreped, through-air-dried tissue was made using a
layered headbox. Each ply contained three layers. Two layers contained
dispersed bleached eucalyptus hardwood kraft pulp and made up 58 percent
of the tissue web by weight of fiber. The remaining 42 percent of the
tissue web, consisting of bleached northern softwood kraft pulp, was
formed on top of the two eucalyptus layers. The basis weight of each ply
was 15.25 grams per square meter of air-dried. tissue. The softwood layer
was refined to obtain sufficient dry strength in the final product. A
wet strength agent, Parez 631NC, was metered into the softwood layer at a
rate of 5 kilograms of active matter per tonne of fiber. An aqueous
softener blend comprising 4 weight percent' of a quaternary ammonium
compound (Yarisoft 3690) and 1 weight percent silicone glycol (Dow
Corning 190) was pre-mixed and added to both eucalyptus layers at the
thick stock (2 percent consistency). The thick stock of all layers was
diluted to approximately 0.10 percent consistency prior to forming the
tissue web. The resulting furnish contained 4.35 kilograms per tonne of
Uarisoft 3690 (0.435 dry weight percent) and 1.09 kilograms per tonne of
Dow Corning 190 (0.109 dry weight percent). The dried tissue webs were
plied together in such a way so that the eucalyptus furnish was on the
outside. The resulting tissue was softer to the touch than similar
tissue made with the quaternary compound without silicone glycol.
Example 3
A layered, one-ply, creped, through-air-dried tissue was made using
a three-layered headbox. The first stock layer (which was positioned
against the Yankee dryer during drying) and third stock layer were the
two outer layers and contained bleached southern hardwood kraft and
bleached eucalyptus hardwood kraft pulp, respectively. The second stock
layer, which was the inner layer, consisted of bleached northern softwood
kraft pulp and broke. The two outer layers each made up 25 percent of
the tissue web by weight. The inner layer constituted the remaining 50
percent of the tissue sheet. The total basis weight of the tissue web
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_ was 28.0 grams per square meter of air dried tissue. A wet strength
agent (Parez 631NC) was metered into the inner layer at the rate of 1.24
TM
kilograms of active matter per tonne of fiber. Redi-Bond 2005 starch
(obtained from National Starch and Chemical Company) was also added to
the same layer at a rate of 13 kilograms of active matter per tonne of
fiber to deliver adequate dry strength. The same softening blend as
described in Examples 1 and 2 was pre-mixed and added to the eucalyptus
layer via the thick stock (2 percent consistency). The thick stock of
all layers was diluted to 0.12 percent consistency prior to forming the
tissue web. The resulting furnish contained 1.79 kilograms per tonne of
fiber of Yarisoft 3690 (0.179 dry weight percent) and 0.45 kilograms per
tonne of fiber of Dow Corning 190 (0.045 dry weight percent). The
resulting tissue had a soft, silky feel.
ExamulP'
A two-ply soft tissue was made by combining two wet-pressed, creped
basesheets produced with two layers using a layered headbox. The first
stock layer contained eucalyptus hardwood fiber and made up 60 percent of
the tissue sheet by weight of the fiber. The remaining 40 percent of the
tissue sheet was provided via a second stock layer consisting of northern
softwood kraft pulp. The total basis weight per ply of creped tissue was
15.2 grams per square meter air-dried. Two strength agents were used:
KymeneM557 LX (Hercules, Inc.) and Parez 631NC. Kymene 557 LX was
blended into the softwood layer at the ratio of 0.19 percent active
matter by weight of fiber and into the hardwood layer at the ratio of
0.05 percent active matter by the weight of the fiber. Parez 631NC was
metered into the softwood layer at the ratio of 0.4J percent active
matter by weight of the fiber. A blend of 10 weight percent silicone
glycol (Dow Corning 190) and 90 weight percent organoreactive
polysiloxane softener/debonder (methylaminopropyl siloxane, hydroxy-
terminated, 20 percent active, identified as Dow Corning 2-8676 emulsion)
was prepared and diluted with water to a final concentration of 10 weight
percent of Dow Corning 2-8676 and 1.11 weight percent of Dow Corning 190.
The diluted mixture was metered into the hardwood thick stock (2 percent
consistency) so that the final furnish contained 0.05 dry weight percent
active matter of Dow Corning 2-8676 and 0.01 dry weight percent active
matter of Dow Corning 190. The resulting tissue was softer and slicker
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to the touch than similar tissue produced with the polysiloxane
softener/debonder but without the silicone glycol.
Examul-a 5
A tissue was made using the same basesheet as in Example 4, except
the blend of silicone glycol and softener/debonder consisted of 90 weight
percent of an organoreactive polysiloxane (aminoethylaminopropyl dimethyl
siloxane, identified as Oow Corning 108) and 10 weight percent of Oow
Corning 190 (silicone glycol). The mixture was metered into the hardwood
thick stock (2 percent consistency) to produce furnish containing 0.1 dry
weight percent active matter of Dow Corning 108 and 0.01 dry weight
percent active matter of Dow Corning 190. The resulting tissue was
softer and slicker (less abrasive) to the touch than tissue made with the
polysiloxane softener/debonder but without the silicone glycol.
Example 6
A soft two-ply, wet-pressed creped.tissue was made using a layered
headbox. The first stock layer contained eucalyptus hardwood fiber and
made up 60 percent of the tissue sheet by weight of the fiber. The
remaining 40 percent of the tissue sheet was provided via a second stock
layer consisting of northern softwood kraft pulp. The basis weight of
the sheet was 15.2 grams per square meter of air-dried tissue. Kymene
557 LX was used as the strength agent and was blended into the softwood
layer at the ratio of 0.23 percent active matter by the weight of the
fiber. The blend of silicone glycol and softener/debonder comprised 4.5
weight percent active matter of llarisoft 3690 (quaternary ammonium
compound), 1.05 weight percent of Dow Corning 190 (silicone glycol) and
94.95 weight percent of water. The blend was added at the hardwood thick
stock (2 percent consistency) to produce a tissue furnish containing
about 0.1 to 0.2 dry weight percent of llarisoft 3690 and about 0.02 to
0.04 dry weight percent of Dow Corning 190. The resulting tissue was
softer and slicker to the touch compared to similar tissue made with the
quaternary compound but without the silicone glycol.
Example 7
A tissue was made with the same basesheet as in Example 5, except
the blend of silicone glycol and softener/debonder comprised 4.5 weight
percent active matter of Harisoft 3690 (quaternary ammonium compound),
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0.53 weight percent active matter of Dow Corning 2-8676 emulsion
(organoreactive polysiloxane), and 0.53 weight percent active matter of
Dow Corning 190 (silicone glycol). The blend was added at the thick
stock of the conventional wet press tissue machine to make a furnish
containing about 0.1 to 0.2 dry weight percent of Varisoft 3690 and about
0.01 to 0.02 dry weight percent each of the Dow Corning 2-8676 and Dow
Corning 190. The resulting tissue was softer and slicker to the touch
compared to similar tissue made with the Quaternary compound and
organoreactive polysiloxane but without the silicone glycol.
l0
Exampl a 8
A tissue was made using the same basesheet as in Example 5. The
blend of the silicone glycol and the softener/debonder comprised 4.5
weight percent active matter of Varisoft 3690 (quaternary ammonium
compound), 1.05 weight percent active matter of a silicone-modified
phospholipid (Mona Industries, Inc., Code ~Y54146, Lot 2426, 30 percent
active), and 0.53 weight percent active matter of Dow Corning 190
(silicone glycol). The blend was added at the thick stock (2 percent
consistency) of the conventional wet press tissue machine to make a
tissue furnish containing about 0.1 to 0.2 dry weight percent of Varisoft
3690, about 0.02 to 0.04 dry weight percent of silicone-phospholipid and
about 0.01 to 0.02 dry weight percent of Dow Corning 190, based on the
weight of the fiber. The resulting tissue was softer and slicker to the
touch than similar tissue made with the quaternary compound and silicone
phospholipid but without silicone glycol.
It will be appreciated that the foregoing examples, given for
purposes of illustration, are not to be construed as limiting the scope
of this invention, which is defined by the following claims and all
equivalents thereto.
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