USOO81 01045B2

(12) United States Patent (10) Patent No.: US 8,101,045 B2

Furman et al. (45) Date of Patent: Jan. 24, 2012

(54) MODIFYINGAGENT FORYANKEE 5,374,334. A 12/1994 Sommese et al.

COATINGS 5,382.323 A 1/1995 Furman, Jr. et al.
5,660,687 A 8, 1997 Allen et al.
5,833,806 A * 1 1/1998 Allen et al. ................... 162,111
(75) Inventors: Gary S. Furman, St. Charles, IL (US); 6,277,242 B1 8, 2001 Archer et al.
Xiaojin Harry Li, Palatine, IL (US); 2005/0241786 A1* 11/2005 Edwards et al. .............. 162/109
Winston Su, Naperville, IL (US); 2007/0054986 A1* 3/2007 Nguyen .......................... 524/35
Vladimir A. Grigoriev, Atlanta, GA 2007/0151684 A1* 7/2007 Grigoriev et al. ... 162,111
(US) s s 2008/O105394 A1* 5/2008 Kokko .......................... 162,111
2009, O130006 A1 5/2009 Wang et al.
2009/0133846 A1* 5/2009 Grigoriev et al. ............. 162/112
(73) Assignee: Nalco Company, Naperville, IL (US) 2011/0092743 A1* 4/2011 Li et al. .............. 568/679
2011/0162811 A1* 7, 2011 Furman et al. ................ 162,111
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS
U.S.C. 154(b) by 187 days. EP 5050O2 A2 * 9, 1992
WO WO 2007O924O7 A2 * 8, 2007
(21) Appl. No.: 12/6.52,059 * cited by examiner
(22) Filed: Jan. 5, 2010
Primary Examiner — Jose A Fortuna
(65) Prior Publication Data (74) Attorney, Agent, or Firm — Benjamin E. Carlsen;
US 2011 FO162811 A1 Jul. 7, 2011 Michael B. Martin

(51) Int. Cl.

B3F L/12 (2006.01) (57) ABSTRACT
(52) U.S. Cl. ..................... 162/112: 162/164.1: 156/183:
264/283 The invention provides a composition of matter useful for
(58) Field of Classification Search .......... 162/111113, producing very soft high grades of tissue paper. The compo
162/158, 1641, 1643, 168.1. 168.3: 156/183: sition of matter comprises an adhesive composition that
s s 264/282284. 428/195.1 includes a glycerol-based polyol. The glycerol-based polyol
See application file for complete search history. prevents the composition from becoming brittle and is non
volatile. This allows the composition to become rewetted
(56) References Cited after creping and allows for strong levels of adhesion even at
high temperatures.
U.S. PATENT DOCUMENTS
5,179,150 A 1/1993 Furman, Jr. et al.
5, 187.219 A 2/1993 Furman, Jr. 14 Claims, 5 Drawing Sheets
U.S. Patent Jan. 24, 2012 Sheet 1 of 5 US 8,101,045 B2
U.S. Patent Jan. 24, 2012 Sheet 2 of 5 US 8,101,045 B2

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 US 8,101,045 B2
1. 2
MODIFYINGAGENT FORYANKEE ticular forming and drying strategies, creping the fibersheets,
COATINGS and by using wet-end or topical application of softening
agents. Creping the paper sheet when it has a very low sheet
CROSS-REFERENCE TO RELATED moisture level (<3%) is a very effective way of achieving
APPLICATIONS desired levels of high softness and bulk. At low moisture
levels, the sheet and the coating tend to adhere to each other
None. more strongly which causes the sheet to debond in the Z-di
STATEMENT REGARDING FEDERALLY
rection more efficiently thereby generating greater bulk and
SPONSORED RESEARCH ORDEVELOPMENT 10
softness. Low moisture levels can be achieved by increasing
the temperature of the Yankee dryer and hoods.
Not Applicable. Despite the benefits for tissue softness, low moisture cre
ping is not being widely practiced due in part to coating
BACKGROUND OF THE INVENTION runnability issues. Conventional creping adhesives typically
15 develop a hard coating which is less rewettable after under
This invention relates to compositions of matter and meth going the high temperatures and extensive drying that is
ods of using them to improve the physical properties of manu required for low moisture creping. This hard and brittle coat
factured paper, in particular making soft tissue paper. Typi ing results in a loss of adhesion and also results in blade
cally, tissue paper obtains its characteristic properties of vibration (chatter), which can cause non-uniform creping,
softness, bulk, absorbency, and ability to stretch, by a process blade wear, and, in extreme cases, damage to the Yankee dryer
involving a Yankee Dryer apparatus. In conventional tissue cylinder Surface.
making the tissue is fed to the Yankee Dryer apparatus as a wet One attempted method of addressing these problems is by
fiber web. The wet fiber web is significantly dewatered at a using humectants to plasticize the adhesive and thereby coun
pressure roll nip where the sheet is transferred to the surface teract many of the consequences of high Yankee Dryer tem
of a Yankee Dryer cylinder. At this point, the paper web 25 peratures. One Such humectant is glycerol (see for example
typically has 35-40% consistency (it is 65-60% water). The U.S. Pat. Nos. 5,187.219 and 5,660,687). Glycerol has been
sheet is further dried by the steam-heated Yankee Dryer cyl shown to alter the Viscoelastic properties of a coating film. In
inder and hot air impingement hoods to 90-98% consistency addition, it decreases the glass transition temperature and
and removed with a doctor blade. The mechanical action of shear modulus of the film, making it softer and more rewet
the blade results in a disruption of the fiber-fiber bonds, which 30 table in both high and low temperature conditions. Unfortu
forms a microfold structure that gives the tissue paper its nately when in dilute aqueous form, as is the case when
characteristic properties. This process is referred to as crep applied to Yankee dryers, the volatility of glycerol/water mix
1ng. tures limits glycerol's effectiveness as a plasticizer. Because
In order to properly crepe a paper web to make soft tissue water is also common in Yankee Dryer environments there is
paper, the paper web has to adhere to the surface of the Yankee 35 a great demand for a modifying agent that placticizes the film
dryer cylinder. When the paper web then collides with the but is not as Volatile as glycerol.
doctor blade, microfolds are formed in the machine direction
by the compressing, or shortening action, while at the same BRIEF SUMMARY OF THE INVENTION
time the web is separated from the drying cylinder. This
adhesion is facilitated by the application of an adhesive to the 40 At least one embodiment of the invention is directed
surface of the dryer cylinder. In addition, wet-end furnish towards a method of creping a paper web comprising the steps
components can also contribute to the adhesion that occurs. of:
Commonly used Yankee adhesives are synthetic polymers a) applying to a rotating creping cylinder a coating composi
Such as polyaminoamide-epichlorohydrin (PAE) resins, tion, the coating composition comprising at least one adhe
polyamine-epichlorohydrin resins, polyvinyl alcohols, poly 45 sive agent, at least one release agent, and at least one polyg
vinyl acetates, polyacrylamides, polyamines, polyviny lycerol:
lamines, polyamides, polyvinylpyrrolidones, polyethers, b) pressing the paper web against the creping cylinder to
polyethyleneimines, crosslinked vinyl alcohol copolymers, effect adhesion of the paper web to the creping cylinder; and
and others described in U.S. Pat. No. 5,374,334. Other natural c) dislodging the paper web from the creping cylinder with a
and derivitized natural polymers may also be employed 50 doctor blade.
including starch, guar gum, carboxymethyl cellulose, The coating composition can remain plasticized at a tem
hydroxyethylcellulose, hydroxypropyl cellulose and the like. perature beyond the volatility limit of glycerol. The polyg
Various lower molecular weight compounds, release agents, lycerol can be between 1 and 70% of the coating composition.
oils and Surfactants, are used to modify the properties of these The coating composition can have a glass transition tempera
adhesives. 55 ture of less than 100° C. The coating composition can be
The tissue industry has a continuing interest in manufac readily rewettable after the paper has been dislodged from the
turing premium grade tissues, which are tissues with high creping cylinder.
levels of softness and bulk. Improvements in softness can be The polyglycerols can be selected from the group consist
obtained by modifying the fiber source, implementing par ing of polyglycerol according to the formula:
 US 8,101,045 B2

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o
HO

R
OH O OH O1 n1io
R

H 4- 4 N-N-N-N-N-N-
iii. pi p

OH
OH

wherein m, n, o, p, q, and rare equal to an integer from 0 to 25 15 FIG. 2 is an illustration of the structures of suitable repeat
polyglycerol formed by crosslinking glycerol with epichlo ing units, which may be used in the polyglycerols used in the
rohydrin, base condensation polyglycerols, polymerization inventive film.
of glycidol-based monomers, and any combination thereof. FIG. 3 is a graph showing the improved volatility proper
The polyglycerol structure can be selected from the group ties of the inventive modifiers.
consisting of linear, branched, hyperbranched, dendritic, FIG. 4 is a graph showing the improved resistance to
cyclic and any combination thereof. The polyglycerol can weight loss of the diluted modifiers.
have a molecular weightgreater than 100 g/mole. The coating FIG.5 is a graph showing the improved dry tack strength of
can further comprise polyaminoamide-epichlorohydrin the inventive film.
(PAE) resins, polyamine-epichlorohydrin resins, polyacryla
mides, polyvinylamines, polyvinylpyrrolidones, natural 25 DETAILED DESCRIPTION OF THE INVENTION
polymers, derivitized natural polymers, starch, guar gum,
carboxymethyl cellulose, hydroxyethyl cellulose, hydrox Definitions
ypropyl cellulose, functional additives, organic quaternary
salts having fatty chains of about 12 to about 22 carbonatoms, For purposes of this application the definition of these
dialkyl imidazolinium quaternary salts, dialkyl diamidoam 30 terms is as follows:
inequaternary salts, monoalkyl trimethylammonium quater "Dispersion' means a thermodynamically unstable mix
nary salts, dialkyl dimethylammonium quaternary salts, tri ture of extremely fine solid particles, typically of colloidal
alkyl monomethylammonium quaternary salts, ethoxylated size, which are highly dispersed throughout a continuous
quaternary salts, dialkyl and trialkyl ester quaternary salts, phase liquid that it is otherwise immiscible with. Dispersions
polysiloxanes, quaternary silicones, organoreactive polysi 35 can be at least temporarily stabilized by dispersing agents.
loxanes, amino-functional polydimethylsiloxanes, “Emulsion” means a thermodynamically unstable mixture
polyamines, polyamides, polyamidoamines, amidoamine of a dispersed phase liquid, which is highly dispersed as Small
epichlorohydrin polymers, polyethyleneimines, polyvinyl globules throughout a continuous phase liquid that it is oth
alcohol, vinyl alcohol copolymers, polyvinyl acetate, vinyl erwise immiscible with. Emulsions can be at least tempo
acetate copolymers, polyethers, polyacrylic acid, acrylic acid 40 rarily stabilized by surfactants and emulsifiers.
copolymers, cellulose derivatives, starches, starch deriva “Polymeric Polyol’ means a polymer in which the mono
tives, animal glue, crosslinked vinylamine/vinylalcohol poly mer repeating units comprising the polymer are at least in part
mers, glyoxalated acrylamide/dialyldimethyl acrylamide polyols and includes but is not limited to polyglycerols,
copolymers, halogen-free creping cylinder adhesives based polyglycerols derivatives, and a polymer consisting of at least
on cross-linked cationic polyaminoamide polymers, and any 45 one glycerol monomer unit and at least another monomer unit
combination thereof. The coating composition can further to other multiple monomers units regardless of the sequence
comprise lactic acid or lactate, can further comprise release of monomers unit arrangements and any combination thereof.
agents, other modifiers (including phosphates), and func “Polyol means a compound or polymer containing at least
tional additives, polyglycerols, polyglycerol derivatives, any two hydroxyl groups in which each of these at least two
other glycerol-based polyols, and any combination thereof. 50 hydroxyl groups are attached to separate carbon atoms of an
The release aid can comprise one item selected from the aliphatic skeleton, including but not limited to glycols, glyc
group consisting of release oils composed of naphthenic, erol, pentaerythritol, trimethylolethane, trimethylolpropane,
paraffinic, vegetable, mineral or synthetic oil and emulsifying 1.2.6-hexanetriol, Sorbitol, inositol, poly(vinyl alcohol) and
Surfactants, release aids formulated with one or more Surfac glycerol-based polyols.
tants such as fatty acids, alkoxylated alcohols, alkoxylated 55 “Placticizer” means a substance which when added to a
fatty acids, and any combination thereof. The coating com material causes an increase in the flexibility and workability
position can be applied as an aqueous Solution, an emulsion, of that material, often as a result of lowering the glass transi
or a dispersion. Creped paper can be prepared according to tion temperature of that material.
the inventive method. In the event that the above definitions or a definition stated
60 elsewhere in this application is inconsistent with a meaning
BRIEF DESCRIPTION OF THE DRAWINGS (explicitor implicit) which is commonly used, in a dictionary,
or stated in a source incorporated by reference into this appli
A detailed description of the invention is hereafter cation, the application and the claim terms in particular are
described with specific reference being made to the drawings understood to be construed according to the definition in this
in which: 65 application, and not according to the common definition,
FIG. 1 is an illustration of the structure of suitable polyg dictionary definition, or the definition that was incorporated
lycerols for use in the inventive film. by reference.
 US 8,101,045 B2
5 6
At least one embodiment of the invention is directed embodiment, the polymers of the invention are included in the
towards a Yankee Dryer coating composition comprising an aqueous solution in a concentration of from about 0.05 to
adhesive, a release agent, and a modifying agent. The adhe about 5.0 weight percent. In another embodiment, the poly
sive binds a paper mat to the drum surface of the Yankee mers of the invention are included in the aqueous Solution in
Dryer. The invention encompasses applications to paper mats a concentration of from about 0.1 to about 1.0 weight percent.
comprising cellulosic fibers, synthetics fibers, and any com Those skilled in the art of creping adhesives will appreciate
bination thereof. The release agent reduces the strength of the that the reason for Such a larger percentage of water in the
adhesive to allow a doctor blade to remove the dried papermat admixture is in part based on the need to only deposit a very
from the drum. The modifying agent plasticizes the coating thin layer of adhesive on the creping cylinder, which, in one
composition, keeping it soft, and allowing it to become rewet 10 embodiment, is most easily accomplished with a spray boom.
ted and to maintain the adhesion while in the presence of high In at least one embodiment the spraying applications
temperature. A description of Yankee Dryer coating compo described above may be further improved by a variety of
sitions is given in U.S. patent application Ser. No. 12/273, means, for example by using spraybooms designed for double
217. or triple coverage, by oscillating the sprayboom and by recir
In at least one embodiment the modifying agent is a com 15 culation of the diluted release aid composition from the outlet
position that comprises glycerol-based polymeric polyol. of the sprayboom to improve mixing and reduce the possibil
including polyglycerols, polyglycerol derivatives, and a poly ity of separation.
mer consisting of at least one glycerol monomer unit and at In at least one embodiment a release aid that is also in
least another monomer unit to other multiple monomers units aqueous form is applied to the Yankee dryer along with the
regardless of the sequence of monomers unit arrangements. polymer adhesive. The release aid provides lubrication
Suitable glycerol-based polymeric polyol include but are not between the Yankee dryer surface and the doctor blade used to
limited to those described in U.S. patent application Ser. No. crepe the tissue paper from the Yankee dryer. The release aid
12/582,827 and US Published Patent Application 2009/ also allows the tissue paper to release from the adhesive
0.130006. In at least one embodiment the polymeric polyol during the creping process. Representative release aids
has a molecular weight of more than 100. 25 include release oils composed of naphthenic, paraffinic, Veg
In at least one embodiment the modifying agent is a com etable, mineral or synthetic oil and emulsifying Surfactants.
position that comprises polyglycerols. Suitable polyglycerols In order to form stable aqueous dispersions the release aid is
include but are not limited to those described in U.S. patent typically formulated with one or more surfactants such as
application Ser. No. 12/582,827 and US Published Patent fatty acids, alkoxylated alcohols, alkoxylated fatty acids, and
Application 2009/0130006. In at least one embodiment the 30 the like. The release aid may be applied to the creping cylin
polyglycerol has a molecular weight of more than 100. der before or after the adhesive composition, or may be added
Although it is known that glycerol does have some use as a together with the adhesive for application to the creping cyl
plasticizer in other materials, for example as described in U.S. inder.
Pat. No. 5,187.219, it has not been previously attempted to In at least one embodiment the adhesive compositions of
use polyglercerol in Yankee dryer coatings. 35 this invention may also be used in combination with func
In at least one embodiment, the polyglycerol is one tional additives used in the art to improve the softness of the
selected from the list consisting of diglycerol, triglycerol, and tissue or towel. Representative functional additives include
higher analogs, as specified by the structure illustrated in FIG. organic quaternary salts having fatty chains of about 12 to
1. The polyglycerols may be prepared by crosslinking with about 22 carbon atoms including dialkyl imidazolinium qua
epichlorohydrin, through the condensation of glycerol, by 40 ternary salts, dialkyl diamidoamine quaternary salts,
polymerization of glycidol-based monomers, or any combi monoalkyl trimethylammonium quaternary salts, dialkyl
nation thereof. dimethylammonium quaternary salts, trialkyl monomethy
In at least one embodiment, the polyglycerol may have a lammonium quaternary salts, ethoxylated quaternary salts,
structure as illustrated in FIG.1. The polyglycerol comprises dialkyl and trialkyl ester quaternary salts, and the like. Addi
a structure including at least two repeating units selecting 45 tional Suitable functional additives include polysiloxanes,
from at least one of the structures listed in FIG. 2 including quaternary silicones, organoreactive polysiloxanes, amino
but not limited to linear structures I and II, branched, hyper functional polydimethylsiloxanes, and the like.
branched or dendritic structures III, IV, and VIII, cyclic struc In at least one embodiment the creping adhesives for pre
tures V, VI and VII and any combination thereof. Any struc paring creped paper include, but are not limited to, the fol
ture in FIG. 2 can be combined with any structure or 50 lowing: polyamines, polyamides, polyamidoamines, ami
structures including itself through any free hydroxyl group doamine-epichlorohydrin polymers, polyethyleneimines,
functionality in the structure. The cyclic linkages of any basic polyvinyl alcohol, vinyl alcohol copolymers, polyvinyl
cyclic structures in FIG.2 may contain any structure or struc acetate, vinyl acetate copolymers, polyethers, polyacrylic
tures as a part or parts of linkages. In FIG. 1 and FIG. 2 the acid, acrylic acid copolymers, cellulose derivatives, starches,
numbers m, n, n', o, p, q and r in each structure can indepen 55 starch derivatives, animal glue, crosslinked vinylamine/viny
dently be any numeric number 0, 1, 2, ... 25. In FIG. 1 Rand lalcohol polymers as described in U.S. Pat. No. 5,374,334.
R" are (CH), and n can independently be 1 or 0. glyoxalated acrylamide/diallyldimethyl acrylamide copoly
In at least one embodiment the modifying agent forYankee mers; the polymers described and claimed in U.S. Pat. No.
coatings comprises polyglycerol derivatives. The derivatives 5,179,150; the polymers described and claimed in U.S. Pat.
can be obtained by derivatization of polyglycerols with 1 to 60 No. 5,187.219; an admixture of from about 0.1 to about 50
22 carbonatoms. The modification includes but not is limited weight percent of a first polyamide-epihalohydrin resin and
to alkylation, alkoxylation, esterification and the like. from about 99.9 to about 50 weight percent of a second
In at least one embodiment the adhesive compositions of polyamide-epihalohydrin resin, as described and claimed in
the present invention are applied to the Surface of a creping U.S. Pat. No. 6,277,242B1 and halogen-free creping cylinder
cylinder as a dilute aqueous solution. In an embodiment, the 65 adhesives based on cross-linked cationic polyaminoamide
aqueous solution includes from about 0.01 to about 10.0 polymers as described and claimed in U.S. Pat. No. 5,382,
weight percent of the polymers of the invention. In another 323.
 US 8,101,045 B2
7 8
EXAMPLES than glycerol. About 20-40 mg of samples were analyzed by
TGA (TA Instruments, New castle, DE) at a heating rate of
The foregoing may be better understood by reference to the 10°C/min in an air atmosphere (flow rate: 90 ml/min).
following examples, which are presented for purposes of
illustration and are not intended to limit the scope of the 5 TABLE 2
invention. 5% weight-loss temperature determined by TGA
Various polyglycerol samples were characterized to deter
mine their bulk viscosity and molecular weight including, Sample Temperature (C.)
commercially available Diglycerol and Polyglycerol-3 from 10 Glycerol 162
Solvay Chemical International (Belgium) and synthesized Diglycerol 235
materials PG-1, and PG-2 available from Nalco Company Polyglycerol-3 255
PG-1 192
(Naperville, Ill.). A description of these samples is provided PG-2 204
in Table 1 and shows all of the samples had a higher viscosity
and molecular weight than glycerol (MW=92 g/mole). The 15
bulk viscosity of samples was measured by a Rheometer
AR2000 (TA Instruments, New Castle, Del.). The measure Example 3
ments were performed in a rotational mode at a shear rate of The lower volatility of polyglycerol compared to glycerol
5s' and 40°C. A 60 mm parallel plate was used with a gap in dilute aqueous solutions is illustrated in FIG. 4. As the
of 2000 um. For molecular weight measurements, all samples modifier concentration becomes more dilute, the advantage
were analyzed with a SEC method (size exclusion chroma of polyglycerol over glycerol becomes more apparent. At 1%
tography) and the reported molecular weights (MW) were modifier concentration, practically 100% of the glycerol
weight average molecular weights based on calibration of modifier is lost after drying at 105° C. for 16.5 hours. In
PEG/PEO standards. Base condensation prepared polyglyc contrast only 10% of the polyglycerol modifier is lost.
erols can contain lactic acid or lactate.
25
Example 4
TABLE 1.
Descriptions and molecular weight characterizations
The plasticizing properties of polyglycerol, when formu
of polyglycerol Samples lated as part of a Yankee dryer composition, was demon
30
strated from glass transition temperature (Tg) and shear stor
Type of Viscosity age modulus (G) measurements. The polymer Tg was
Sample Polyglycerol (Pas) Mw: measured by Differential Scanning Calorimetry, and the G' of
Glycerol O.26 92 the polymer film was measured by rheometer. Table 3 shows
Diglycerol Epi-crosslinked 2.3 140 the effect of modifiers on the Tg and G' of PAE-based film.
Polyglycerol-3 Epi-crosslinked 6.6 2OO The results demonstrate that polyglycerol is as an effective
PG-1 Base Condensation 35 32O 35 plasticizer as glycerol. Polyglycerol reduced the Tg in a simi
PG-2 Base Condensation 130 S4O lar fashion as glycerol, and the polyglycerol-modified PAE
*Excludes glycerol monomer film is a softer film compared to the unmodified film. ATA
Q200 Differential Scanning Calorimeter (TA Instruments,
New Castle, Del.) was used for Tg measurement. Polymer
Example 1 40 samples were prepared by casting films in a polypropylene
dish. The samples were dried at 105°C. in an oven overnight.
General procedure for the production of polyglycerols: A About 10-15 mg of sample was sealed in a DSC pan with lid.
reaction mixture of glycerol (500.0 parts) and NaOH or KOH The sample was heated at a rate of 10°C./min Tg was deter
solution (3 to 10% by weight of active relative to the total mined from the second scan using a halfheight method. The
weight of reaction solids) was stirred and gradually heated up 45 shear storage modulus G' was measured by a rheometor
to 230 to 260 degrees Celsius under particular inert gas flow AR2000 (TA Instruments, New Castle, Del.). Polymer films
were prepared by casting from a 5% (w/w) solution. The film
rates. The reaction mixture was stirred at this temperature for was dried in an oven at 95°C. overnight. The dry film was
a desired reaction time (in hours), and in-process samples punched with a die (8 mm in diameter). The 8 mm disc was
were drawn after two hours and every one or two hours further dried in a vacuum oven at 110° C. for two hours. The
thereafter for product characterizations. Nitrogen flow rates 50
shear storage modulus G' was measured using 8 mm parallel
at 0.2 to 8 mol of nitrogen per hour for each mol of glycerol or plate at 110° C. and 1 Hz.
vacuum pressures less than 760 mm Hg were applied starting
from reaction time between 0 to 4 hours to the end of the
TABLE 3
reaction. The polyglycerol products were used for the appli
cation directly or after dilution with water, with or without pH 55 Effects of modifiers on the glass transition temperature
adjustment. and shear storage modulus of PAE resin
Example 2 Sampale Tg (C.) G' (kPa)
PAE 76 1SOO
The volatility of polyglycerol samples was determined by 60 PAE + Glycerol
PAE - PG-2
55
57
510
770
thermogravimetry (TGA). FIG. 3 is the overlay of TGA
weight-loss curves for glycerol and various polyglycerol
samples. Table 2 lists the temperature at which 5% weight
loss occurs in the samples. The 5% weight-loss of glycerol Example 5
occurs at 162°C., whereas the 5% weight-loss of polyglyc 65
erol samples occurs at significantly higher temperatures. This In order to compare the effect of polyglycerols and glycerol
indicates that all of the polyglycerol samples are less Volatile on adhesion, a dry tack peel test was performed. This test
 US 8,101,045 B2
9 10
measured the force required to peel a cotton Strip adhered to All ranges and parameters disclosed herein are understood
a heated metal plate. First a PAE adhesive composition was to encompass any and all Subranges Subsumed therein, and
applied to the metal plate by a #40 coating rod. The adhesive every number between the endpoints. For example, a stated
applied to the plate had no more than 15% solids. The plate range of 1 to 10 should be considered to include any and all
was heated to 100° C. and a dry cotton strip was pressed Subranges between (and inclusive of) the minimum value of 1
against the plate by a 1.9 kg cylindrical roller. The metal plate and the maximum value of 10; that is, all Subranges beginning
was then heated to 105° C. and the strip was left to dry for 15 with a minimum value of 1 or more, (e.g. 1 to 6.1), end ending
minutes. The metal plate was then clamped to a testing appa with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4
ratus and the cloth was peeled off the plate at an angle of 180° to 7), and finally to each number 1, 2,3,4,5,6,7,8,9, and 10
at a constant speed. The results of the test shown in FIG. 5
10 contained within the range.
demonstrate the effectiveness of the invention. The sample This completes the description of the preferred and alter
nate embodiments of the invention. Those skilled in the art
with no modifier showed no dry tack adhesion because as the may recognize other equivalents to the specific embodiment
PAE adhesive film dried out, the film became brittle and too described herein which equivalents are intended to be encom
hard for the cotton strip to adhere to. While the glycerol 15 passed by the claims attached hereto.
modifier can make the film softer which increased the dry tack The invention claimed is:
adhesion, FIG.5 makes clear that the polyglycerol containing 1. A method of creping a paper web comprising the steps
films, had Superior dry tack adhesion when compared to films of:
containing glycerol as a modifier. a) applying to a rotating creping cylinder a coating com
This data also makes clear that because polyglycerol func position, the coating composition comprising at least
tions as Such an effective placticizer, even if in a rare circum one adhesive agent, at least one release agent, and at
stance, a residual amount of glycerol would be present in a least one polyglycerol;
sample of polyglycerol modified film, the residual glycerol b) pressing the paper web against the creping cylinder to
would not function effectively as a plasticizer for the polya effect adhesion of the paper web to the creping cylinder;
midoamine/epihalohydrin since the greater abundance and 25 and
effectiveness of the polyglycerol would overwhelm any effect c) dislodging the paper web from the creping cylinder with
from residual glycerol. Moreover FIG. 3 makes clear that a doctor blade
because polyglycerols are less Volatile under certain condi wherein the coating composition has Superior dry tack adhe
tions of use, (for example 100 to 162 degree environments) in sion properties and lower Volatility than a similarly consti
those conditions, glycerol is not an effective plasticizer for the 30 tuted coating composition which contains glycerol instead of
polyamidoamine/epihalohydrin resin because it vaporizes polyglycerol would.
away while the retained polyglycerols do function as placti 2. The method of claim 1 wherein the coating composition
cizers. remains plasticized at a temperature beyond the Volatility
While this invention may be embodied in many different limit of glycerol.
forms, there are shown in the drawings and described in detail 35 3. The method of claim 1 wherein the polyglycerol is
herein specific preferred embodiments of the invention. The between 1 and 70% of the coating composition.
present disclosure is an exemplification of the principles of 4. The method of claim 1 wherein the coating composition
the invention and is not intended to limit the invention to the has a glass transition temperature of less than 100° C.
particular embodiments illustrated. All patents, patent appli 5. The method of claim 1 wherein the coating composition
cations, scientific papers, and any other referenced materials 40 is readily rewettable after the paper has been dislodged from
mentioned herein are incorporated by reference in their the creping cylinder.
entirety. Furthermore, the invention encompasses any pos 6. The method of claim 1 wherein the polyglycerols is
sible combination of some or all of the various embodiments selected from the group consisting of polyglycerol according
described herein and incorporated herein. to the formula

H
o
HO

R
OH O OH O1 N1io

H 4- 4 N-N-N-N-N--R
iii. pi p

OH
OH

The above disclosure is intended to be illustrative and not

60
wherein m, n, o, p, q, and rare equal to an integer between
exhaustive. This description will suggest many variations and more than 0 and less than 25, polyglycerol formed by
alternatives to one of ordinary skill in this art. All these crosslinking glycerol with epichlorohydrin, base con
alternatives and variations are intended to be included within densation polyglycerols, polymerization of glycidol
the scope of the claims where the term "comprising” means based monomers, and any combination thereof.
“including, but not limited to’. Those familiar with the art 7. The method of claim 1 where the polyglycerol structure
may recognize other equivalents to the specific embodiments 65 is selected from the group consisting of linear, branched,
described herein which equivalents are also intended to be hyperbranched, dendritic, cyclic and any combination
encompassed by the claims. thereof.
 US 8,101,045 B2
11 12
8. The method of claim 1 wherein the polyglycerol has a gen-free creping cylinder adhesives based on cross-linked
molecular weight greater than 100 g/mole. cationic polyaminoamide polymers, and any combination
9. The method of claim 1 wherein the coating further com thereof.
prises one item selected from the group consisting of 10. The method of claim 1 wherein the coating composi
polyaminoamide-epichlorohydrin (PAE) resins, polyamine tion further comprises lactic acid or lactate salt.
epichlorohydrin resins, polyacrylamides, polyvinylamines, 11. The method of claim 1 wherein the coating further
polyvinylpyrrolidones, natural polymers, derivitized natural comprises one item selected from the group consisting of
polymers, starch, guar gum, carboxymethyl cellulose, release agents, phosphate based modifiers, and functional
hydroxyethyl cellulose, hydroxypropyl cellulose, functional additives.
additives, organic quaternary salts having fatty chains of 10 12. The method of claim 1 wherein the coating composi
about 12 to about 22 carbon atoms, dialkyl imidazolinium tion comprises one item selected from the group consisting of
quaternary salts, dialkyl diamidoamine quaternary salts, polyglycerols, polyglycerol derivatives, glycerol-based poly
monoalkyl trimethylammonium quaternary salts, dialkyl ols, and any combination thereof.
dimethylammonium quaternary salts, trialkyl monomethy 13. The method of claim 1 wherein the release aid com
lammonium quaternary salts, ethoxylated quaternary salts, 15 prises one selected from the group consisting of release oils
dialkyl and trialkyl ester quaternary salts, polysiloxanes, qua composed of naphthenic, paraffinic, vegetable, mineral or
ternary silicones, organoreactive polysiloxanes, amino-func synthetic oil and emulsifying Surfactants, release aids formu
tional polydimethylsiloxanes, polyamines, polyamides, lated with one or more Surfactants such as fatty acids, alkoxy
polyamidoamines, amidoamine-epichlorohydrin polymers, lated alcohols, alkoxylated fatty acids, and any combination
polyethyleneimines, polyvinyl alcohol, vinyl alcohol copoly thereof.
mers, polyvinyl acetate, vinyl acetate copolymers, poly 14. The method of claim 1 wherein the coating composi
ethers, polyacrylic acid, acrylic acid copolymers, cellulose tion is applied as an aqueous solution, an emulsion, or a
derivatives, starches, starch derivatives, animal glue, dispersion.
crosslinked vinylamine/vinylalcohol polymers, glyoxalated
acrylamide/diallyldimethyl acrylamide copolymers, halo