U.S. patent application number 15/478203 was filed with the patent office on 2017-07-20 for creping adhesives and methods for making and using same.
This patent application is currently assigned to Georgia-Pacific Chemicals LLC. The applicant listed for this patent is Georgia-Pacific Chemicals LLC. Invention is credited to Karla D. Favors, Cornel Hagiopol, Clay E. Ringold, David F. Townsend, Thomas L. Wright.
Application Number | 20170204565 15/478203 |
Document ID | / |
Family ID | 53006123 |
Filed Date | 2017-07-20 |
United States Patent
Application |
20170204565 |
Kind Code |
A1 |
Ringold; Clay E. ; et
al. |
July 20, 2017 |
CREPING ADHESIVES AND METHODS FOR MAKING AND USING SAME
Abstract
Creping adhesives and methods for making and using same are
provided. The creping adhesive can include a first thermosetting
polyamidoamine-epihalohydrin resin that includes a reaction product
of a first epihalohydrin and a first polyamidoamine containing one
or more secondary amine groups, a first thermoplastic
polyamidoamine-epihalohydrin resin that includes a reaction product
of a second epihalohydrin and a second polyamidoamine containing
one or more secondary amine groups, and one or more re-wetting
agents. The first thermosetting polyamidoamine-epihalohydrin resin
can have a weight average molecular weight of about 800,000 to
about 1,200,000 and a molar ratio of the first epihalohydrin to the
secondary amine groups of about 0.002:1 to about 0.1:1. The first
thermoplastic polyamidoamine-epihalohydrin resin can have a weight
average molecular weight of about 40,000 to about 200,000 and a
molar ratio of the second epihalohydrin to the secondary amine
groups of about 0.001:1 to about 0.1:1.
Inventors: |
Ringold; Clay E.; (Decatur,
GA) ; Townsend; David F.; (Grayson, GA) ;
Hagiopol; Cornel; (Lilburn, GA) ; Favors; Karla
D.; (Atlanta, GA) ; Wright; Thomas L.;
(Oxford, GA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Georgia-Pacific Chemicals LLC |
Atlanta |
GA |
US |
|
|
Assignee: |
Georgia-Pacific Chemicals
LLC
Atlanta
GA
|
Family ID: |
53006123 |
Appl. No.: |
15/478203 |
Filed: |
April 3, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14535320 |
Nov 7, 2014 |
9611590 |
|
|
15478203 |
|
|
|
|
61901094 |
Nov 7, 2013 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/0286 20130101;
D21H 17/15 20130101; D21H 17/72 20130101; C08L 79/02 20130101; D21H
21/146 20130101; C09J 179/02 20130101; D21H 17/07 20130101; C09J
2479/02 20130101; D21H 17/56 20130101; C09J 179/02 20130101; C08L
79/02 20130101 |
International
Class: |
D21H 21/14 20060101
D21H021/14; D21H 17/56 20060101 D21H017/56; C08G 73/02 20060101
C08G073/02; D21H 17/15 20060101 D21H017/15; C09J 179/02 20060101
C09J179/02; D21H 17/00 20060101 D21H017/00; D21H 17/07 20060101
D21H017/07 |
Claims
1. A creping adhesive, comprising: a thermosetting
polyamidoamine-epihalohydrin resin comprising a reaction product of
a first epihalohydrin and a first polyamidoamine containing one or
more secondary amine groups; and a thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups.
2. The creping adhesive of claim 1, wherein the thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 800,000 to about 1,200,000, and wherein the
thermoplastic polyamidoamine-epihalohydrin resin has a weight
average molecular weight of about 40,000 to about 200,000.
3. The creping adhesive of claim 1, wherein a molar ratio of the
first polyamidoamine to the first epihalohydrin is about 0.75:1 to
about 1.8:1, and wherein a molar ratio of the second polyamidoamine
to the second epihalohydrin is about 2:1 to about 100:1.
4. The creping adhesive of claim 1, wherein: the first
epihalohydrin and the second epihalohydrin comprise
epichlorohydrin, the first polyamidoamine comprises a reaction
product of a first polyamine and at least one of a first
dicarboxylic acid and a first ester of a dicarboxylic acid, and the
second polyamidoamine comprises a reaction product of a second
polyamine and at least one of a second dicarboxylic acid and a
second ester of a dicarboxylic acid.
5. The creping adhesive of claim 4, wherein: the first dicarboxylic
acid and the second dicarboxylic acid, if present, comprise adipic
acid, glutaric acid, or a mixture thereof, the first ester of a
dicarboxylic acid and the second ester of a dicarboxylic acid, if
present, comprise dimethyl glutarate, diethyl glutarate, dimethyl
adipate, diethyl adipate, or a mixture thereof, and the first
polyamine and the second polyamine each comprise
diethylenetriamine, triethylenetetramine, tripropylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, methyl
bis(3-aminopropyl)-amine, dipropylenetriamine,
bis(hexamethylene)triamine, bis-2-hydroxyethyl ethylenediamine, or
a mixture thereof.
6. The creping adhesive of claim 1, further comprising a re-wetting
agent.
7. The creping adhesive of claim 6, wherein the re-wetting agent
comprises a protonated amine, a protonated polyamine, a quaternary
ammonium salt, glycerin, a salt of a polycarboxylic acids
neutralized with triethanolamine, or any mixture thereof.
8. The creping adhesive of claim 6, wherein the re-wetting agent
comprises a poly-quaternary ammonium salt.
9. The creping adhesive of claim 6, wherein the creping adhesive
comprises about 5 wt % to about 80 wt % of the thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the thermoplastic polyamidoamine-epihalohydrin resin, and about
0.1 wt % to about 30 wt % of the re-wetting agent, and wherein all
weight percent values are based on a combined weight of the
thermosetting polyamidoamine-epihalohydrin resin, the thermoplastic
polyamidoamine-epihalohydrin resin, and the re-wetting agent.
10. The creping adhesive of claim 6, further comprising polyvinyl
alcohol, hemicellulose, polyvinyl amine, polyacrylamide, or a
mixture thereof.
11. A method for creping a cellulosic fiber web, comprising:
applying a creping adhesive to a drying surface, wherein the
creping adhesive comprises: a thermosetting
polyamidoamine-epihalohydrin resin comprising a reaction product of
a first epihalohydrin and a first polyamidoamine containing one or
more secondary amine groups; and a thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups; adhering a cellulosic fiber web to
the drying surface with the creping adhesive; and dislodging the
adhered cellulosic fiber web from the drying surface.
12. The method of claim 11, wherein the thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 800,000 to about 1,200,000, and wherein the
thermoplastic polyamidoamine-epihalohydrin resin has a weight
average molecular weight of about 40,000 to about 200,000.
13. The method of claim 11, wherein a molar ratio of the first
polyamidoamine to the first epihalohydrin is about 0.75:1 to about
1.8:1, and wherein a molar ratio of the second polyamidoamine to
the second epihalohydrin is about 2:1 to about 100:1.
14. The method of claim 11, wherein the creping adhesive further
comprises a re-wetting agent comprising a protonated amine, a
protonated polyamine, a quaternary ammonium salt, glycerin, a salt
of a polycarboxylic acids neutralized with triethanolamine, or any
mixture thereof.
15. The method of claim 14, wherein the creping adhesive comprises
about 5 wt % to about 80 wt % of the thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the thermoplastic polyamidoamine-epihalohydrin resin, and about
0.1 wt % to about 30 wt % of the re-wetting agent, and wherein all
weight percent values are based on a combined weight of the
thermosetting polyamidoamine-epihalohydrin resin, the thermoplastic
polyamidoamine-epihalohydrin resin, and the re-wetting agent.
16. A creped product, comprising: a creped cellulosic fiber web;
and an at least partially cured creping adhesive, wherein, prior to
curing, the creping adhesive comprises: a thermosetting
polyamidoamine-epihalohydrin resin comprising a reaction product of
a first epihalohydrin and a first polyamidoamine containing one or
more secondary amine groups; and a thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups.
17. The creped product of claim 16, wherein the thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 800,000 to about 1,200,000, and wherein the
thermoplastic polyamidoamine-epihalohydrin resin has a weight
average molecular weight of about 40,000 to about 200,000.
18. The creped product of claim 16, wherein a molar ratio of the
first polyamidoamine to the first epihalohydrin is about 0.75:1 to
about 1.8:1, and wherein a molar ratio of the second polyamidoamine
to the second epihalohydrin is about 2:1 to about 100:1.
19. The creped product of claim 16, wherein, prior to curing, the
creping adhesive further comprises a re-wetting agent.
20. The creped product of claim 19, wherein the creping adhesive
comprises about 5 wt % to about 80 wt % of the first thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the first thermoplastic polyamidoamine-epihalohydrin resin, and
about 0.1 wt % to about 30 wt % of the re-wetting agent, and
wherein all weight percent values are based on the combined weight
of the thermosetting polyamidoamine-epihalohydrin resin, the
thermoplastic polyamidoamine-epihalohydrin resin, and the
re-wetting agent.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of co-pending patent
application Ser. No. 14/535,320, filed on Nov. 7, 2014, which
claims priority to U.S. Provisional Patent Application No.
61/901,094, filed on Nov. 7, 2013, which are both incorporated by
reference herein.
BACKGROUND
[0002] Field
[0003] Embodiments described generally relate to creping adhesives
and methods for making and using same. More particularly, such
embodiments relate to creping adhesives that include one or more
thermosetting polyamidoamine-epihalohydrin resins and one or more
thermoplastic polyamidoamine-epihalohydrin resins and methods for
making and using same.
[0004] Description of the Related Art
[0005] The manufacture of paper is generally carried out by
producing an aqueous slurry of cellulosic fibers and a variety of
chemicals and subsequently removing most of the water to form a
thin paper web. The structural integrity of the paper arises in
large part from the mechanical entanglement of the cellulosic
fibers in the web and hydrogen bonds that form between the
cellulosic fibers. With paper intended for use as tissue and towel
products such as facial tissue, bathroom tissue, paper towels, and
napkins, the level of structural integrity arising from the
paper-making process conflicts somewhat with the degree of
perceived softness that is necessary for consumer acceptance of
such products. The most common method of increasing the perceived
softness of tissue and towel products is to "crepe" the paper. The
creping action can impart a fine, rippled texture to the sheet,
increase the bulk of the sheet, improve softness of the sheet,
and/or improve absorbency of the sheet. Creping can be accomplished
by affixing the moist, cellulosic paper web to a rotating thermal
drum commonly known as a Yankee dryer, by applying the web onto the
surface of the dryer, which has been sprayed with a creping
adhesive, generally in the form of an aqueous solution, emulsion,
or dispersion. The surface of the Yankee dryer is continuously
sprayed with the creping adhesive while the cellulosic web is
applied and dried by hot air impinging on the exposed side of the
paper and conductive heat is transferred from the drum. As the
paper dries, hydrogen bonds form between the fibers creating a flat
and dense web morphology. The paper is then scraped backwardly upon
itself and off of the Yankee dryer by means of a flexible blade,
called a "doctor" blade or a "creping" blade. This creping process
causes a substantial number of inter-fiber bonds to break, altering
the physical-chemical characteristics of the web and increasing the
perceived softness of the resulting creped product.
[0006] The art of obtaining good crepe quality relies on
maintaining the proper level of adhesion between the paper web and
the surface of the Yankee dryer. Inadequate adhesion can result in
poor or non-existing creping or require lower speed operation due
to slow drying, while excessive adhesion can lead to poor sheet
quality or cause the sheet to break. Cellulosic webs that are
insufficiently adhered to the Yankee dryer can impact the control
of the web as it travels between the creping blade and the winder
upon which a roll of the paper is being formed, causing problems in
forming a uniform roll of paper. For example, a loose sheet between
the creping blade and the roll can cause wrinkles, foldovers, and
weaving of the edges of the sheet in the rolled-up paper, adversely
affecting subsequent operations of paper manufacture. Release aids
can alter the properties of the adhesive and further provide
lubrication to the doctor blade, and influence the release of the
paper web from the Yankee dryer, all of which can affect the
properties of the creped product. Considerable effort has been
spent trying to adjust the balance between the adhesion and the
release of the web, while maintaining other conventional parameters
that influence the creping process, such as web wetness and creping
blade angle. A significant drawback with the existing creping
adhesives is that the formulations of the creping adhesives
generally need to be changed or adjusted when the wet end chemistry
is changed (pH, reactive chemicals, debounders, etc.), the
temperature profile is modified, or the residual moisture in the
paper web is modified.
[0007] There is a need, therefore, for improved creping adhesives
that can provide more control over the adhesion/release balance of
the paper web to/from the surface of the dryer and methods for
making and using same.
SUMMARY
[0008] Creping adhesives and methods for making and using same are
provided. In at least one specific embodiment, the creping adhesive
can include a first thermosetting polyamidoamine-epihalohydrin
resin that includes a reaction product of a first epihalohydrin and
a first polyamidoamine containing one or more secondary amine
groups, a first thermoplastic polyamidoamine-epihalohydrin resin
that includes a reaction product of a second epihalohydrin and a
second polyamidoamine containing one or more secondary amine
groups, and one or more re-wetting agents. The first thermosetting
polyamidoamine-epihalohydrin resin can have a weight average
molecular weight of about 800,000 to about 1,200,000, about 2 moles
to about 500 moles of reactive groups per mole of the first
thermosetting polyamidoamine-epihalohydrin resin, and a molar ratio
of the first epihalohydrin to the secondary amine groups in the
first polyamidoamine of about 0.002:1 to about 0.1:1. The reactive
groups of the first thermosetting polyamidoamine-epihalohydrin
resin be azetidinium groups, pendant halo-groups, or both. The
first thermoplastic polyamidoamine-epihalohydrin resin can have a
weight average molecular weight of about 40,000 to about 200,000
and a molar ratio of the second epihalohydrin to the secondary
amine groups in the second polyamidoamine of about 0.001:1 to about
0.1:1. The creping adhesive can include about 5 wt % to about 80 wt
% of the first thermosetting polyamidoamine-epihalohydrin resin,
about 15 wt % to about 90 wt % of the first thermoplastic
polyamidoamine-epihalohydrin resin, and about 0.1 wt % to about 30
wt % of the one or more re-wetting agents, where all weight percent
values are based on the combined weight of the first thermosetting
polyamidoamine-epihalohydrin resin, the first thermoplastic
polyamidoamine-epihalohydrin resin, and the one or more re-wetting
agents.
[0009] In at least one specific embodiment, the method for creping
a cellulosic fiber web can include applying the creping adhesive to
a drying surface. The method can also include adhering a cellulosic
fiber web to the drying surface with the creping adhesive. The
method can further include dislodging the adhered cellulosic fiber
web from the drying surface.
[0010] In at least one specific embodiment, a creped product can
include the creping adhesive. The creping adhesive can be an
adhesive that has been at least partially cured.
DETAILED DESCRIPTION
[0011] It has been has been surprisingly and unexpectedly
discovered that mixtures of one or more thermosetting
polyamidoamine-epihalohydrin resins or "thermosetting PAE resins,"
one or more thermoplastic polyamidoamine-epicholorohydrin resins or
"thermoplastic PAE resins," and one or more re-wetting agents can
provide or produce a creping adhesive that can significantly
improve heat transfer to the paper web and lubrication between the
doctor blade and/or the surface of the Yankee dryer, and/or exhibit
a significantly improved durability and/or re-wettability. The
creping adhesive, when applied to the surface of the dryer, can
also develop significantly higher levels of both wet tack and dry
tack. Durability is a characteristic of how stable the creping
adhesive coating is on the surface of the Yankee dryer,
particularly at the pressure nip. If the coating is easily washed
off, it does not protect the creping cylinder and leads to
excessive creping blade wear. A soft, but durable coating is
preferred. Re-wettability of the creping adhesive refers to how
well the residual coating of the creping adhesive on the surface of
the Yankee dryer accepts water without washing off. For example,
the creping adhesive can be used for a wide range of wet end
chemistry conditions (pH, reactive chemicals, debounders, etc.), a
wide range of temperature profiles, and/or a wide range of residual
moisture encountered during a creping operation without requiring
an adjustment or change in the composition of the creping
adhesive.
[0012] The creping adhesive can have a swelling index from a low of
about 5 grams water per gram crosslinked polymer, about 15 grams
water per gram crosslinked polymer, about 25 grams water per gram
crosslinked polymer or about 50 grams water per gram crosslinked
polymer to a high of about 100 grams water per gram crosslinked
polymer, about 150 grams water per gram crosslinked polymer, about
200 grams water per gram crosslinked polymer or about 250 grams
water per gram crosslinked polymer, as measured after extraction in
a Soxhlet extractor with boiling water for 75 minutes. For example,
the creping adhesive can have a swelling index of about 10 grams
water per gram crosslinked polymer to about 75 grams water per gram
crosslinked polymer, about 30 grams water per gram crosslinked
polymer to about 120 grams water per gram crosslinked polymer about
60 grams water per gram crosslinked polymer to about 160 grams
water per gram crosslinked polymer, about 110 grams water per gram
crosslinked polymer to about 175 grams water per gram crosslinked
polymer, or about 160 grams water per gram crosslinked polymer to
about 240 grams water per gram crosslinked polymer, as measured
after extraction in a Soxhlet extractor with boiling water for 75
minutes. In another example, the creping adhesive can have a
swelling index of at least 5 grams water per gram crosslinked
polymer, at least 20 grams water per gram crosslinked polymer, at
least 40 grams water per gram crosslinked polymer, at least 60
grams water per gram crosslinked polymer, at least 80 grams water
per gram crosslinked polymer, at least 100 grams water per gram
crosslinked polymer, or at least 120 grams water per gram
crosslinked polymer to about 250 grams water per gram crosslinked
polymer, as measured after extraction in a Soxhlet extractor with
boiling water for 75 minutes.
[0013] The creping adhesive can have a total solids concentration
(also referred to as insoluble material or crosslinked polymer)
from a low of about 1 wt %, about 10 wt %, about 20 wt %, about 30
wt %, about 40 wt %, about 50 wt %, or about 65 wt % to a high of
about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about
95 wt %, or about 100 wt %. In another example, the creping
adhesive can have a total solids concentration from about 5 wt % to
about 25 wt %, about 10 wt % to about 20 wt %, about 20 wt % to
about 30 wt %, about 15 wt % to about 25 wt %, about 20 wt % to
about 50 wt %, about 35 wt % to about 60 wt %, about 45 wt % to
about 85 wt %, or about 60 wt % to about 90 wt %. As understood by
those skilled in the art, the solids content of the creping
adhesive can be measured by determining the weight loss upon
heating a small sample, e.g., 1-5 grams of the creping adhesive, to
a suitable temperature, e.g., 120.degree. C., and a time
sufficient, e.g., 2 hours, to remove liquid therefrom.
[0014] The creping adhesive can have a pH from a low of about 2,
about 2.5, about 3, about 3.5, or about 4 to a high of about 6,
about 6.5, about 7, about 7.5, about 8, or about 9. For example,
the creping adhesive can have a pH of about 2 to about 8.5, about 2
to about 8, about 2.3 to about 5.5, about 3.5 to about 4.5, about 4
to about 6, about 4 to about 8, about 3 to about 7, or about 5 to
about 7. In another example, the creping adhesive can have a pH of
less than 8, less than 7.5, less than 7, less than 6.5, less than
6, less than 5.5, less than 5, or less than 4.5. One or more
mineral acids and/or one or more organic acids can be mixed or
otherwise combined with the creping adhesive to adjust the pH
thereof. Illustrative acids can include, but are not limited to,
hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric
acid, formic acid, phosphoric acid, acetic acid, citric acid,
lactic acid, lactobionic acid, or any mixture thereof. The
re-wetting properties of the first thermosetting PAE resin can be
modified by the amount and the particular type of acid used to
stabilize the first thermosetting PAE resin.
[0015] Suitable thermosetting PAE resins can be prepared by
reacting one or more polyamidoamines and one or more
epihalohydrins. The thermosetting PAE resin can also be referred to
as the "first thermosetting PAE resin." If the creping adhesive
includes additional thermosetting PAE resins, the additional
thermosetting PAE resin(s) can be sequentially referred to as the
"second thermosetting PAE resin," the "third thermosetting PAE
resin," and so on. The first polyamidoamine can be prepared by
reacting (1) one or more first dicarboxylic acids and/or one or
more first esters of a dicarboxylic acid and (2) one or more first
polyamines. The first polyamine can include secondary and/or
tertiary amine groups. The first dicarboxylic acid can be a
saturated aliphatic dibasic carboxylic acid, often containing from
about 3 to about 10 carbon atoms and mixtures thereof. Dicarboxylic
acids containing from 4 to 8 carbon atoms chains can be used, such
as adipic acid and/or glutaric acid. Illustrative first
dicarboxylic acids can include, but are not limited to, malonic
acid, succinic acid, glutaric acid, adipic acid, suberic acid,
sebacic acid, or any mixture thereof. Illustrative first esters of
dicarboxylic acids can include, but are not limited to, dimethyl
glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, or
any mixture thereof. Illustrative first epihalohydrins can include,
but are not limited to, epichlorohydrin, epibromohydrin,
epifluorohydrin, epiiodohydrin, or any mixture thereof.
[0016] The first polyamine reacted with the first dicarboxylic acid
and/or first ester of a dicarboxylic acid to produce the
polyamidoamine can include, but is not limited to, one or more
polyalkylene polyamines. The polyalkylene polyamines can include
compounds of Formula (I).
H.sub.2N[(CH.sub.2).sub.xNH].sub.yH (I)
[0017] where x and y are integers independently selected from 2 to
10. Specific examples polyalkylene polyamine can include,
diethylenetriamine (x=2, y=2), triethylenetetramine (x=2, y=3),
tripropylenetetramine (x=3, y=3) tetraethylenepentamine (x=2, y=4),
and pentaethylenehexamine (x=2, y=5). Other examples of polyamines
can include methyl bis(3-aminopropyl)-amine, dipropylenetriamine,
bis(hexamethylene)triamine, bis-2-hydroxyethyl ethylenediamine. The
polyamidoamine can include one or more secondary amine groups. For
example, the polyamidoamine can include one or more secondary amine
groups derived from a polyalkylene polyamine.
[0018] The first polyamine can be or include a mixture of two or
more polyamines. If the first polyamine includes two or more
polyamines, each polyamine can be present in the same concentration
or different concentrations with respect to one another. For
example, the first polyamine can include two polyamines at a weight
ratio of about 99:1, about 90:10, about 80:20, about 70:30, about
60:40, about 50:50, about 40:60, about 30:70, about 20:80, about
10:90, or about 1:99 with respect to one another. Similarly, if
three or more polyamines are mixed, the three or more polyamines
can be present in any ratio with respect to one another.
[0019] The polyamidoamine of the first dicarboxylic acid and the
first polyamine can be prepared by heating a mixture of the
reactants to a temperature of about 110.degree. C. to about
250.degree. C. For example, the mixture of the dicarboxylic acid
and the polyamine can be heated to a temperature from a low of
about 110.degree. C., about 125.degree. C., about 140.degree. C. to
a high of about 160.degree. C., about 175.degree. C., about
190.degree. C., or about 200.degree. C. at atmospheric
pressure.
[0020] In carrying out the reaction between the first polyamine and
the first dicarboxylic acid, the amount of the first dicarboxylic
acid can be sufficient to react substantially completely with the
primary amine groups of the polyalkylene polyamine but insufficient
to substantially react with the secondary amine groups of the
polyamine. The molar ratio of the first polyamine to the first
dicarboxylic acid can be from a low of about 0.8:1, about 0.85:1,
about 0.9:1, about 0.95:1, or about 1:1 to a high of about 1:1,
about 1.05:1, about 1.1:1, about 1.2:1, about 1.3:1, or about
1.4:1. For example, the molar ratio of the first polyamine to the
first dicarboxylic acid can be about 0.8:1 to about 1.4:1, about
0.9:1 to about 1.2:1, about 0.9:1 to about 1:1, about 1:0.95 to
about 1:1.05, about 1:0.9 to about 1:1.1, about 1:0.85 to about
1:1.1, or about 0.95:1 to about 1.05:1.
[0021] If the reaction between the first polyamine and the first
dicarboxylic acid is carried out under a reduced pressure the
reaction temperature can be reduced to about 75.degree. C. to
150.degree. C. The time of reaction can depend, at least in part,
on the temperature and/or pressure and can generally be from about
0.5 hours to about 4 hours. The reaction can be continued to
substantial completion. The reaction between the first polyamine
and the first dicarboxylic acid can produce water as a byproduct,
which can be removed by distillation. At the end of the reaction,
the resulting product can be dissolved or dispersed in water to
provide any desired concentration such as an aqueous polyamidoamine
resin having about 50 wt % total resin solids.
[0022] When a first ester of a dicarboxylic acid is used instead of
dicarboxylic acid for reaction with the polyamine, the
prepolymerization can be conducted at a lower temperature, such as
about 100.degree. C. to about 175.degree. C. at atmospheric
pressure. In this case, the byproduct can be an alcohol, the type
of alcohol depending upon the identity of the diester. For example,
if a dimethyl ester is used as a reactant, the alcohol byproduct
can be methanol. In another example, if a diethyl ester is used as
a reactant, the alcohol byproduct can be ethanol. The molar ratio
between the first polyamine and the first diester can be the same
as the ratio between the first polyamine and the first dicarboxylic
acid. If the reaction between the polyalkylene polyamine and the
diester is carried out under a reduced pressure the reaction
temperature can be reduced to about 75.degree. C. to about
150.degree. C.
[0023] The first polyamidoamine that can be used for producing the
first thermosetting PAE resin can be produced under conditions
leading to the formation of a pre-polymer composition having a
weight average molecular weight (in Daltons) of about 10,000 and up
to about 300,000. For example, the polyamidoamine can have a weight
average molecular weight from a low of about 10,000, about 20,000,
about 25,000, about 30,000, about 40,000, or about 50,000 to a high
of about 65,000, about 75,000, about 100,000, about 200,000, about
250,000, about 275,000, or about 300,000.
[0024] As known by those skilled in the art, resin molecular
weights, e.g., weight average molecular weight, number average
molecular weight, and z-average molecular weight, can be determined
using Gel Permeation Chromatography (GPC). A suitable GPC method
can use tetrahydrofuran as a solvent/diluent and a system of two
mixed C chromatographic columns preceding a 500 Angstroms PL gel
column, all available from Resin Laboratories (now part of Varian,
Inc.). The column arrangement can be calibrated using a range of
polystyrene standards. For determining the molecular weight of a
particular resin sample, the sample can be injected along with
polystyrene having a molecular weight of 250,000 and toluene as an
internal standard. A Model 759A Absorbance Detector from Applied
Biosystems can be used to monitor the column output and assist the
molecular weight determination. The method of determining the
molecular weight of a resin sample is well understood by those
skilled in the art and other configurations and reference materials
can conveniently be used.
[0025] To produce the first thermosetting PAE resin, the amount of
the first epihalohydrin reacted with the first polyamidoamine can
be controlled or limited. For example, the molar ratio of the first
polyamidoamine to the first epihalohydrin can be from a low of
about 0.75:1, about 0.8:1, about 0.85:1, about 0.9:1, about 0.95:1,
or about 1:1 to a high of about 1.2:1, about 1.4:1, about 1.6:1,
about 1.8:1, or about 2:1. In another example, the molar ratio of
the first polyamidoamine to the first epihalohydrin can be from
about 0.75:1 to about 2:1, about 0.9:1 to about 1.1:1, about 0.8:1
to about 1.5:1, about 1.1:1 to about 1.7:1, about 1.4:1 to about
1.9:1, or about 0.95:1 to about 1.7:1.
[0026] The first thermosetting PAE resin can have a molar ratio of
the first epihalohydrin to the secondary amine groups in the first
polyamidoamine (moles epihalohydrin to moles secondary amine
groups) from a low of about 0.002:1, about 0.004:1, about 0.006:1
about 0.008:1, or about 0.01:1 to a high of about 0.03:1, about
0.05:1, about 0.07:1, about 0.08:1, or about 0.1:1. For example,
the first thermosetting PAE resin can have a molar ratio of the
first epihalohydrin to the secondary amine groups in the
polyamidoamine from about 0.002:1 to about 0.1:1, about 0.03:1 to
about 0.007:1, about 0.005:1 to about 0.06:1, about 0.008:1 to
about 0.015:1, about 0.009:1 to about 0.09:1. In another example,
the first thermosetting PAE resin can have a molar ratio of the
first epihalohydrin to the secondary amine groups in the first
polyamidoamine of at least 0.002:, at least 0.003:1, at least
0.004:1, at least 0.005:1, at least 0.006:1, at least 0.007:1, at
least 0.008:1, at least 0.009:1, at least 0.01:1, at least 0.015:1,
at least 0.02:1, at least 0.025:1, or at least 0.03:1 and up to
about 0.05:1, about 0.07:1, about 0.09:1, or about 0.1:1.
[0027] The first polyamidoamine can be reacted with the first
epihalohydrin at a temperature from a low of about 0.degree. C.,
about 10.degree. C., about 20.degree. C., about 25.degree. C.,
about 30.degree. C., or about 35.degree. C. to a high of about
60.degree. C., about 70.degree. C., about 80.degree. C., about
90.degree. C., or about 100.degree. C. The reaction between the
first polyamidoamine and the first epihalohydrin can be carried out
in as an aqueous solution to moderate or otherwise control the
reaction. Although not necessary, pH adjustment can be done to
increase or decrease the rate of residual crosslinking.
[0028] The reaction between the first polyamidoamine and the first
epihalohydrin can be carried out until a viscosity of about C or
higher on the Gardener-Holdt scale of a 20% solids solution at a
temperature of 25.degree. C. is reached. The extent of reaction
between the first polyamidoamine and the first epihalohydrin can be
controlled so that the polyamidoamine is only partially reacted
with the epihalohydrin. The viscosity, measured using a Brookfield
viscometer, for a 15 wt % solids solution generally can be limited
so as not to exceed about 150 centipoise (cP) (about FG on the
Gardner Holdt scale) at a temperature of 25.degree. C. The
Brookfield viscosity of the 15 wt % solids solution can be at least
5 cP (a viscosity of about A4 on the Gardner Holdt scale) at a
temperature of 25.degree. C. For example, the Brookfield viscosity
of the 15 wt % solids solution can be between about 10 cP and about
60 cP (a viscosity of about A3 to AB on the Gardner Holdt scale) at
a temperature of 25.degree. C. In another example, the Brookfield
viscosity of the 15 wt % solids solution can be about 12 cP to
about 25 cP (a viscosity of about A3 to A2 on the Gardner Holdt
scale) at a temperature of about 25.degree. C. Preferably, the
reaction can be controlled such that it does not progress beyond
the point where the viscosity, measured using a Brookfield
viscometer, of a 20% solids solution at a temperature of about
25.degree. C. reaches about 25 cP to about 45 cP (a viscosity of
about A2 to Ala on the Gardner Holdt scale). In another example the
reaction can be controlled such that a 20% solids solution at a
temperature of about 25.degree. C. has a viscosity of about 35 cP
or less, or 30 cP or less, or 25 cP or less (a viscosity of about
A2-A1 on the Gardner Holdt scale).
[0029] When the desired viscosity is reached, sufficient water can
be added to adjust the solids content of the first thermosetting
PAE resin to a desired amount. For example, the first thermosetting
PAE resin can have a solids concentration from a low of about 5 wt
%, about 10 wt %, or about 15 wt % to a high of about 20 wt %,
about 30 wt %, about 40 wt %, about 60 wt %, about 80 wt %, about
90 wt %, or about 95 wt %. The first thermosetting PAE resin can be
cooled to a temperature of about 25.degree. C. In another example
the first thermosetting PAE resin can have a solids concentration
from a low of about 8 wt %, about 10 wt %, about 12 wt % or about
14 wt % to a high of about 22 wt %, about 25 wt %, about 27 wt %,
or about 30 wt %. In another example, the first thermosetting PAE
resin can be in the form of an aqueous dispersion, suspension, or
solution and have a solids concentration greater than about 20 wt %
to about 50 wt %.
[0030] The ability of the first thermosetting PAE resin (and any
other thermosetting PAE resins such as a second thermosetting PAE
resin) to resist gelation can be controlled by adding sufficient
acid to reduce the pH to less than 8, less than 7.5, less than 7,
less than 6.5, less than 6, less than 5.5, less than 5, less than
4.5, or less than 4. Illustrative acids can include, but are not
limited to, hydrochloric acid, sulfuric acid, methanesulfonic acid,
nitric acid, formic acid, phosphoric acid, acetic acid, or any
mixture thereof. The re-wetting properties of the first
thermosetting PAE resin can be modified by the amount and the
particular type of acid used to stabilized the first thermosetting
PAE resin.
[0031] The weight average molecular weight of the first
thermosetting PAE resin can be from a low of about 800,000, about
825,000, about 850,000, about 875,000, about 900,000, or about
950,000 to a high of about 1,000,000, about 1,050,000, about
1,100,000, about 1,150,000, or about 1,200,000. For example, the
weight average molecular weight of the thermosetting resin can be
about 800,000 to about 1,200,000, about 820,000 to about 1,100,000,
about 825,000 to about 975,000, about 900,000 to about 1,150,000,
about 1,000,000 to about 1,200,000, or about 850,000 to about
1,150,000. In another example, the first thermosetting PAE resin
can have a weight average molecular weight of at least 800,000, at
least 825,000, at least 850,000, at least 875,000, at least
900,000, at least 9,250,000, at least 950,000, at least 975,000, at
least 1,000,000, or at least 1,050,000 and up to about 1,100,000,
about 1,125,000, about 1,150,000, about 1,175,000, or about
1,200,000.
[0032] The reactivity of the first thermosetting PAE resin can be
expressed as the ratio of moles of reactive groups per mole of the
first thermosetting PAE resin. The reactive groups in the first
thermosetting PAE resin can be or include an azetidinium group,
pendant halo-groups such as chloro-groups, or both. The ratio of
the moles of reactive groups per mole of the first thermosetting
PAE resin can be from a low of about 2:1, about 5:1, about 10:1,
about 25:1, about 50:1, about 75:1, about 100:1, about 125:1, or
about 150:1 to a high of about 200:1, about 250:1, about 300:1,
about 350:1, about 400:1, about 450:1, about 475:1, or about 500:1.
For example, the ratio of the moles of reactive groups per mole of
the first thermosetting PAE resin can be from about 2:1 to about
500:1, about 40:1 to about 180:1, about 80:1 to about 260:1, about
120:1 to about 320:1, about 260:1 to about 380:1, about 320:1 to
about 440:1, about 360:1 to about 480:1, or about 410:1 to about
500:1. In another example, molar ratio of the reactive groups to
moles of the first thermosetting PAE resin can be at least 2:1, at
least 10:1, at least 30:1, at least 60:1, at least 80:1, at least
100:1, at least 120:1, at least 140:1, at least 160:1, at least
180:1, at least 200:1, at least 220:1, at least 240:1, or at least
260:1 and up to about 300:1, about 350:1, about 400:1, about 450:1,
or about 500:1.
[0033] The first thermosetting PAE resin can have a viscosity from
a low of about 5 cP, about 10 cP, about 20 cP, about 40 cP, or
about 60 cP to a high of about 100 cP, about 125 cP, about 150 cP,
about 175 cP, or about 200 cP at a temperature of about 25.degree.
C. For example, the first thermosetting PAE resin can have a
viscosity from a low of about 5 cP, about 10 cP, about 20 cP, about
40 cP, or about 60 cP to a high of about 100 cP, about 125 cP,
about 150 cP, about 175 cP, or about 200 cP at a temperature of
about 25.degree. C. and a solids concentration of about 15 wt %.
The viscosity of the first thermosetting PAE resin and other PAE
resins can be measured using a Brookfield Viscometer at a
temperature of 25.degree. C. For example, the Brookfield Viscometer
can be equipped with a small sample adapter such a 10 mL adapter
and the appropriate spindle to maximize torque such as a spindle
no. 31.
[0034] The first thermosetting PAE resin can have a measurable
covalent halogen and ionic halogen functionality and exhibit a
noticeable change in properties when heated to a temperature of
about 105.degree. C. to about 150.degree. C. In the first
thermosetting PAE resin, the epihalohydrin can be only partially
reacted such that one of the two reactive sites of the
epihalohydrin remains available for further reaction. In the
context of epichlorohydrin, the two reactive sites are the epoxide
moiety and the alkyl chloride moiety. In the first thermosetting
PAE resin there can be some crosslinks between resin chains and
some pendant reactive halohydrin residues along the backbone of the
first thermosetting PAE resin. For example, there can be a
measureable level of covalent halogen, such as chlorine, due to and
in proportion to the pendant halohydrin groups.
[0035] The first thermosetting PAE resin can have a latent level of
reactivity as a function of the pendant halohydrin functionality.
As the name implies, the first thermosetting PAE resin can be
self-crosslinkable or thermosetting without the need for any
catalyst, crosslinker, or other additional compound. The first
thermosetting PAE resin can generally include both secondary or
tertiary amine moieties and reactive halohydrin groups present in
the same molecule and/or in different molecules. The tertiary amine
moieties are found where there are existing crosslinks.
[0036] When the first thermosetting PAE resin is heated, pendant
halohydrin moieties can react with secondary amine moieties to
convert them to tertiary amines, thus increasing the molecular
weight of the resin. The aqueous solution of the first
thermosetting PAE resin can be treated with any number of organic
or inorganic acids to impart different water durability
characteristics to dried films of the resin. Typical acids employed
can include, but are not limited to, sulfuric, phosphoric, formic,
hydrochloric, or acetic acids, or any mixture thereof. Because of
its latent reactivity, the molecular weight of the first
thermosetting PAE resin can be modified in a controlled manner,
which can be used to adjust its water solubility and its adhesive
performance as part of the creping adhesive.
[0037] When the first epihalohydrin is epichlorohydrin, the first
thermosetting PAE resin can have a total chlorine concentration
from a low of about 0.1 wt %, about 0.5 wt %, about 1 wt %, about
1.5 wt %, about 2 wt %, about 2.5 wt %, or about 3 wt % to a high
of about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9
wt %, or about 10 wt % based on the solids content of the first
thermosetting PAE resin. The chlorine concentration can include
ionic chlorine (chlorine bound via crosslinks) and covalent
chlorine (pendant halohydrin).
[0038] When the first epihalohydrin is epichlorohydrin, the ratio
(either mole or weight basis) of the covalent chlorine (pendant
halohydrin) to the ionic chlorine (chlorine bound via crosslinks)
in the first thermosetting PAE resin can be from about 0.01:1 to
about 100:1. For example, the ratio of the covalent chlorine to the
ionic chlorine can be about 0.05:1 to about 10:1, about 0.05:1 to
about 7.5:1, about 0.05:1 to about 7:1, about 0.1:1 to about 6:1,
about 0.2:1 to about 5:1, about 0.25:1 to about 2.5:1, or about
0.5:1 to about 1.5:1.
[0039] When the first epihalohydrin is epichlorohydrin, the first
thermosetting PAE resin can have a covalent chlorine content from a
low of about 0.02 wt % about 0.05 wt %, about 0.1 wt %, about 0.5
wt %, about 1 wt %, about 1.5 wt %, about 2 wt %, about 2.5 wt %,
or about 3 wt % to a high of about 5 wt %, about 6 wt %, about 7 wt
%, about 8 wt %, about 9 wt %, or about 10 wt % based on the total
solids content of the first thermosetting PAE resin. For example,
the first thermosetting PAE resin can have a covalent chlorine
concentration from a low of about 0.01 wt %, about 0.05 wt %, about
0.1 wt %, about 0.3 wt %, or about 0.5 wt % to a high of about 1 wt
%, about 1.2 wt %, about 1.35 wt %, about 1.4 wt %, or about 1.5 wt
% based on the total solids content of the first thermosetting PAE
resin.
[0040] When the first epihalohydrin is epichlorohydrin, the first
thermosetting PAE resin can have a an ionic chlorine concentration
from a low of about 0.05 wt %, about 0.1 wt %, about 0.3 wt %,
about 0.5 wt %, or about 0.7 wt % to a high of about 1 wt %, about
1.2 wt %, about 1.35 wt %, about 1.4 wt %, or about to 1.5 wt %. In
one or more embodiments, the first thermosetting PAE resin can have
a total chlorine content of about 0.1 wt % to about 8 wt % and a
covalent chlorine content of about 0.1 wt % to about 6 wt % based
on the total solids content of the first thermosetting PAE
resin.
[0041] The first thermosetting PAE resin can be free from any
secondary amines. The first thermosetting PAE resin can have a
secondary amine concentration from a low of about 0.01 mmols, about
0.05 mmols, about 0.07 mmols, about 0.1 mmols, about 0.15 mmols,
about 0.2 mmols, about 0.3 mmols, about 0.4 mmols, about 0.5 mmols,
about 0.7 mmols, about 0.8 mmols, about 0.9 mmols, or about 1 mmol
to a high of about 2 mmols, about 2.5 mmols, about 3 mmols, about
3.5 mmols, about 4 mmols, about 4.5 mmols, or about 5 mmols per
gram of the first thermosetting PAE resin. For example, the first
thermosetting PAE resin can have a secondary amine concentration of
about 0.02 mmols to about 0.14 mmols, about 0.05 mmols to about 0.2
mmols, about 0.06 mmols to about 0.22 mmols, about 0.2 mmols to
about 0.3 mmols, about 0.14 mmols to about 0.38 mmols, about 0.32
mmols to about 0.6 mmols, about 0.5 mmols to about 1.5 mmols, about
1.3 mmols to about 2.8 mmols, about 1.6 mmols to about 3.4 mmols,
about 2.2 mmols to about 3.6 mmols, about 2.6 mmols to about 4.2
mmols, about 3.2 mmols to about 4.8 mmols, or about 0.01 mmols to
about 5 mmols per gram of the first thermosetting PAE resin.
[0042] The first thermosetting PAE resin can be made using any
desired method. For example, one can simply synthesize a single PAE
resin composition that itself constitutes the first thermosetting
PAE resin by using an appropriate amount of the first
polyamidoamine and the first epihalohydrin and allowing the
reaction to proceed until an intended balance of covalent chlorine
and ionic chlorine is reached in the first thermosetting PAE resin.
Alternatively, one can blend different PAE resins having different
levels of covalent chlorine and/or ionic chlorine to arrive at a
composition having the intended balance between covalent chlorine
and ionic chlorine. For example, one can blend a fully crosslinked
PAE resin in which the covalent chlorine and the ionic chlorine are
substantially the same, with a PAE resins that is lightly or not
fully crosslinked, if at all, where the total chlorine is
substantially or all due to ionic chlorine. Other options for
blending PAE resins within the spectrum of different levels of
crosslinking and different levels of reactivity will be apparent to
those of ordinary skill in the art in view of the present
disclosure.
[0043] The first thermosetting PAE resin can have an increase in
its glass transition temperature (T.sub.g) after every
heating/cooling cycle with a corresponding increase in film
adhesion (by Peel Adhesion) and an increase in its
non-water-soluble fraction. Also, mild heating of a sample of the
first thermosetting PAE resin can exhibit a substantial increase in
solution viscosity and/or resin molecular weight over time, which
does not occur with a non-reactive, fully crosslinked resin. As
such, the first thermosetting PAE resin can possess an adjustable
adhesion level and/or an adjustable water resistance. The use of
the thermoplastic PAE resin can significantly enhance the
adjustable adhesion level and/or the adjustable water resistance of
the first thermosetting PAE resin.
[0044] The first thermosetting PAE resin can exhibit sufficient
reactivity at about 0.02 moles to about 0.5 moles of reactive
groups per mol of repeating unit and a molecular weight between
800,000 and 1,200,000. The concentration of the secondary amine in
the thermosetting PAE resin can be about 0.1 mmols per gram to
about 5 mmol per gram of the thermosetting PAE resin.
[0045] The re-wettability of the film of the creping adhesive can
depend, at least in part, on the number of hydrophilic groups (such
as protonated amines per gram of resin) and how easy the water has
access to them. The water access can be designed through the length
and density of the resin branches. The number of hydrophilic groups
is set by the dicarboxylic acid used in polycondensation (adipic
and glutaric).
[0046] The thermoplastic PAE resin can also be referred to as the
"first thermoplastic PAE resin." If the creping adhesive includes
additional thermoplastic PAE resins, the additional thermoplastic
PAE resin(s) can be sequentially referred to as the "second
thermoplastic PAE resin," the "third thermoplastic PAE resin," and
so on. In contrast, to thermosetting PAE resins, the thermoplastic
PAE resin can be free from or not exhibit a substantial change in
properties when heated to a temperature of about 105.degree. C. to
about 150.degree. C. The glass transition point (T.sub.g) of the
first thermoplastic PAE resin can remain virtually unchanged after
repeated heating/cooling cycles. The properties of the first
thermoplastic PAE resin can be, at least in part, limited by its
molecular weight. The first thermoplastic PAE resin can essentially
have no pendant halohydrin groups and, when the epihalohydrin used
to make the first thermoplastic PAE resin is epichlorohydrin, all
of the titratable chloride can be ionic in nature. The first
thermoplastic PAE resin can have a ratio of covalent chlorine to
ionic chlorine of less than 0.1:1, less than 0.05:1, less than
0.01:1, or less than 0.005:1.
[0047] Suitable first thermoplastic PAE resins can be produced by a
reaction between one or more second polyamidoamines and one or more
second epihalohydrins. The molar ratio of the second polyamidoamine
to the second epihalohydrin can be from a low of about 2:1, about
3:1, about 5:1, about 7:1, about 10:1, or about 15:1 to a high of
about 25:1, about 35:1, about 50:1, about 75:1, or about 100:1. In
another example, the molar ratio of the second polyamidoamine to
the second epihalohydrin can be from about 2:1 to about 100:1,
about 4:1 to about 20:1, about 10:1 to about 30:1, about 20:1 to
about 55:1, about 30:1 to about 65:1, or about 45:1 to about
85:1.
[0048] The reactants that can be used to produce the second
polyamidoamine can include those discussed and described above with
reference to the first thermosetting PAE resin. The second
polyamidoamine can be prepared by reacting (1) one or more second
dicarboxylic acids and/or one or more second esters of dicarboxylic
acids and (2) one or more second polyamines. The second polyamine
can include secondary and/or tertiary amine groups. The second
dicarboxylic acid, second ester of a dicarboxylic acid, and second
polyamines can include those discussed and described above with
reference to making the first thermosetting PAE resin. The first
and second dicarboxylic acids, the first and second esters of
dicarboxylic acids, and the first and second polyamines can be the
same or different with respect to one another. As such, the first
thermoplastic PAE resin can have a branched chemical structure
similar to the first thermosetting PAE resin, but the first
thermoplastic PAE resin can have a much lower molecular weight.
[0049] The weight average molecular weight of the first
thermoplastic PAE resin can be from a low of about 40,000, about
45,000, about 50,000, about 60,000, about 70,000, or about 80,000
to a high of about 100,000, about 120,000, about 140,000, about
150,000, about 160,000, about 170,000, about 180,000, about
190,000, or about 200,000. For example, the thermoplastic PAE resin
can have a weight average molecular weight form about 40,000 to
about 200,000, about 55,000 to about 120,000, about 65,000 to about
150,000, about 110,000 to about 180,000, or about 125,000 to about
190,000. In another example, the first thermoplastic PAE resin can
have a weight average molecular weight of at least 40,000, at least
45,000, at least 50,000, at least 55,000, at least 60,000, at least
70,000, or at least 80,000 and up to about 100,000, about 120,000,
about 140,000, about 150,000, about 160,000, about 170,000, about
180,000, about 190,000, or about 200,000.
[0050] The molar ratio of the second polyamine to the second
dicarboxylic acid and/or the second ester of a dicarboxylic acid in
the first thermoplastic PAE resin can be from a low of about 0.8:1,
about 0.85:1, about 0.9:1, about 0.95:1, or about 1:1 to a high of
about 1:1, about 1.05:1, about 1.1:1, about 1.2:1, about 1.3:1, or
about 1.4:1. For example, the molar ratio of the second polyamine
to the second dicarboxylic acid can be about 0.8:1 to about 1.4:1,
about 0.9:1 to about 1.2:1, about 0.9:1 to about 1:1, about 1:0.95
to about 1:1.05, about 1:0.9 to about 1:1.1, about 1:0.85 to about
1:1.1, or about 0.95:1 to about 1.05:1.
[0051] The first thermoplastic PAE resin can have a secondary amine
concentration from a low of about 3 mmols, about 4 mmols, about 4.3
mmols, about 4.5 mmols, about 4.7 mmols, about 5 mmols, about 5.3
mmols, or about 5.5 mmols to a high of about 6 mmols, about 6.3
mmols, about 6.5 mmols, about 6.7 mmols, about 7 mmols, about 7.5
mmols, about 8 mmols, or about 8.5 mmols per gram of the
thermoplastic PAE resin. For example, the first thermoplastic PAE
resin can have a secondary amine concentration of about 4 mmols to
about 5.4 mmols, about 4.6 mmols to about 6.2 mmols, about 5.2
mmols to about 6.6 mmols, about 5.8 mmols to about 7.2 mmols, about
6.4 mmols to about 8 mmols, or about 4 mmols to about 8 mmols per
gram of the first thermoplastic PAE resin.
[0052] In one or more embodiments, a ratio of the weight average
molecular weight of the first thermoplastic PAE resin to the weight
average molecular weight of the first thermosetting PAE resin can
be from a low of about 0.01:1, about 0.1:1, about 0.5:1, about 1:1,
about 3:1, about 5:1, about 10:1, or about 15:1 to a high of about
40:1, about 50:1, about 60:1, about 70:1, about 80:1, about 90:1,
or about 100:1. For example, the ratio of the weight average
molecular weight of the first thermoplastic PAE resin to the weight
average molecular weight of the first thermosetting PAE resin can
be from about 0.7:1 to about 10:1, about 4:1 to about 30:1, about
15:1 to about 45:1, about 35:1 to about 65:1, about 55:1 to about
80:1, about 65:1 to about 95:1, or about 10:1 to about 70:1.
[0053] The amount of first thermoplastic PAE resin that can be
combined with the first thermosetting PAE resin can be varied over
a wide range and can be selected to vary the properties of the
adhesive composition such as insolubility, re-wettability, density,
cross-linking, brittleness, and/or tackiness of the creping
adhesive. In this manner, the properties of the creping adhesive
can be adjusted so that the creping adhesive can be optimized for a
given drier and wood pulp composition. The ability to control these
physical properties allows the operator to more precisely control
the desired properties of the creping adhesive. In effect, the
operator can regulate the desired creping adhesive properties by
varying the amount of thermoplastic PAE resin relative to
thermosetting PAE resin. In general, for a constant degree of
cross-linking by the epihalohydrin, as the concentration of
thermoplastic PAE resin increases the insolubility, re-wettability,
density, and brittleness tend increase and the degree of tackiness
tends to decrease.
[0054] The first thermoplastic PAE resin can at least partially
attenuate, adjust, or otherwise control the alkylation process
(e.g., through the formation of crosslinks by reaction between
secondary amine moieties and pendant halohydrin moieties) by
reacting with covalent halogen (chlorine) from the first
thermosetting PAE resins. Thus, the first thermoplastic PAE resin
can be used to control the crosslinking process. Suitable first
thermoplastic PAE resins can be capable of reacting with pendant
halo groups on the first thermosetting PAE resin. Suitable first
thermoplastic PAE resins can also function as plasticizers for the
creping adhesive as well. The first thermoplastic PAE resin can be
mixed, blended, or otherwise combined with the first thermosetting
PAE resin, with a release aid, and/or or independently to the
surface of the dryer during the creping process. Blends of
different thermoplastic PAE resins also can be used. Other
plasticizers, such as diethanol amine, triethanol amine, glycerin,
and/or polyglycerin can also be used.
[0055] The one or more re-wetting agents can be or include, but are
not limited to, one or more protonated amines, one or more
protonated polyamines, one or more quaternary ammonium salts, one
or more poly-quaternary ammonium salts, glycerin, one or more salts
of a polycarboxylic acid neutralized with triethanolamine, one or
more phosphates, choline chloride, or any mixture thereof.
Illustrative protonated amines and protonated polyamines can
include, but are not limited to, amines and polyamines protonated
with one or more inorganic and/or one or more organic acids, such
as lactic acid, citric acid, lactobionic acid, or any mixture
thereof. Illustrative quaternary ammonium salts can include, but
are not limited to, diallyldimethylammonium chloride (DADMAC).
Illustrative poly-quaternary ammonium salts can include, but are
not limited to, poly-diallyldimethylammonium chloride
(poly-DADMAC). Illustrative phosphates can include, but are not
limited to, phosphoric acid and/or phosphate salts.
[0056] The amount of the first thermosetting PAE resin in the
creping adhesive can be from a low of about 1 wt %, about 3 wt %,
about 5 wt %, about 7 wt %, about 10 wt %, about 15 wt %, about 20
wt %, or about 30 wt % to a high of about 40 wt %, about 50 wt %,
about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about
75 wt %, or about 80 wt % based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, and the
re-wetting agent. For example, the creping adhesive can include the
first thermoplastic PAE resin in an amount of about 5 wt % to about
80 wt %, about 15 wt % to about 45 wt %, about 25 wt % to about 65
wt %, about 45 wt % to about 70 wt %, about 60 wt % to about 80 wt
%, or about 10 wt % to about 60 wt % based on the combined weight
of the first thermosetting PAE resin, the first thermoplastic PAE
resin, and the re-wetting agent.
[0057] The amount of the first thermoplastic PAE resin in the
creping adhesive can be from a low of about 1 wt %, about 3 wt %,
about 5 wt %, about 7 wt %, about 10 wt %, about 15 wt %, about 20
wt %, or about 30 wt % to a high of about 60 wt %, about 65 wt %,
about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, or
about 90 wt % based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, and the
re-wetting agent. For example, the creping adhesive can include the
first thermoplastic PAE resin in an amount of about 3 wt % to about
90 wt %, about 15 wt % to about 45 wt %, about 25 wt % to about 65
wt %, about 45 wt % to about 85 wt %, about 60 wt % to about 90 wt
%, or about 10 wt % to about 70 wt % based on the combined weight
of the first thermosetting PAE resin, the first thermoplastic PAE
resin, and the re-wetting agent.
[0058] The amount of the re-wetting agent in the creping adhesive
can be from a low of about 1 wt %, about 3 wt %, about 5 wt %, or
about 7 wt % to a high of about 15 wt %, about 20 wt %, about 25 wt
%, or about 30 wt %, based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, and the
re-wetting agent. For example, the creping adhesive can include
from about 1 wt % to about 30 wt %, about 5 wt % to about 15 wt %,
about 2 wt % to about 8 wt %, about 6 wt % to about 20 wt %, about
10 wt % to about 24 wt %, about 16 wt % to about 28 wt %, or about
18 wt % to about 30 wt % of the re-wetting agent, based on the
combined weight of the first thermosetting PAE resin, the first
thermoplastic PAE resin, and the re-wetting agent.
[0059] In one or more embodiments, the creping adhesive can include
the first thermosetting PAE resin, the first thermoplastic PAE
resin, and one or more additional PAE resins, where the additional
PAE resin(s) differs from the first thermosetting PAE resin and the
first thermoplastic PAE resin. For example, the first thermosetting
PAE resin differs from the first thermoplastic resin by having a
different weight average molecular weight and/or different
reactivity. The additional PAE resin(s) can also differ from the
first thermosetting PAE resin and the first thermoplastic PAE resin
by at least one of the weight average molecular weight and
reactivity.
[0060] In at least one specific embodiment, the creping adhesive
can include the first thermosetting PAE resin, the first
thermoplastic PAE resin, and a third PAE resin. The third PAE resin
can be a thermosetting PAE resin or a thermoplastic PAE resin. For
example, the creping adhesive can include the first thermosetting
PAE resin, the first thermoplastic resin, and a second
thermosetting PAE resin. The second thermosetting PAE resin can
have a different reactivity, molecular weight, or both relative to
the first thermosetting PAE resin. As such, a bi-modal distribution
of the reactive groups (based on the moles of reactive groups per
mol of PAE resin) can be present. In another example, the creping
adhesive can include the first thermosetting PAE resin, the first
thermoplastic PAE resin, and a second thermoplastic PAE resin. In
still another example, the creping adhesive can include the first
thermosetting PAE resin, the first thermoplastic PAE resin, a
second thermosetting PAE resin, and a second thermoplastic PAE
resin. In yet another example, the creping adhesive can include the
first thermosetting PAE resin, the first thermoplastic PAE resin,
the second thermosetting PAE resin, the second thermoplastic PAE
resin, and a third thermosetting PAE resin.
[0061] The second thermosetting PAE resin can be the reaction
product of a third polyamidoamine and a third epihalohydrin. The
third polyamidoamine can be a reaction product of a third polyamine
and a third dicarboxylic acid. The third epihalohydrin, the third
polyamine, and the third dicarboxylic acid (and/or third ester of a
dicarboxylic acid) can include those discussed and described above
with reference to the first thermosetting PAE resin. The relative
amounts of the third epihalohydrin, the third polyamine, and the
third dicarboxylic acid (and/or third ester of dicarboxylic acid)
can be similar to the amounts discussed and described above with
respect to the first thermosetting PAE resin. The particular
amounts of the reactants used to make the second thermosetting PAE
resin can depend, at least in part, on the desired properties of
the second thermosetting PAE resin.
[0062] The molar ratio of the third polyamine to the third
dicarboxylic acid and/or the third ester of a dicarboxylic acid in
the third PAE resin can be from a low of about 0.8:1, about 0.85:1,
about 0.9:1, about 0.95:1, or about 1:1 to a high of about 1:1,
about 1.05:1, about 1.1:1, about 1.2:1, about 1.3:1, or about
1.4:1. For example, the molar ratio of the third polyamine to the
third dicarboxylic acid can be about 0.8:1 to about 1.4:1, about
0.9:1 to about 1.2:1, about 0.9:1 to about 1:1, about 1:0.95 to
about 1:1.05, about 1:0.9 to about 1:1.1, about 1:0.85 to about
1:1.1, or about 0.95:1 to about 1.05:1.
[0063] The second thermosetting PAE resin can have a secondary
amine concentration from a low of about 4 mmols, about 4.3 mmols,
about 4.5 mmols, about 4.7 mmols, about 5 mmols, about 5.3 mmols,
or about 5.5 mmols to a high of about 6 mmols, about 6.3 mmols,
about 6.5 mmols, about 6.7 mmols, about 7 mmols, about 7.5 mmols,
or about 8 mmols per gram of the second thermosetting PAE resin.
For example, the second thermosetting PAE resin can have a
secondary amine concentration of about 4 mmols to about 5.4 mmols,
about 4.6 mmols to about 6.2 mmols, about 5.2 mmols to about 6.6
mmols, about 5.8 mmols to about 7.2 mmols, about 6.4 mmols to about
8 mmols, or about 4 mmols to about 8 mmols per gram of the second
thermosetting PAE resin.
[0064] The weight average molecular weight of the second
thermosetting PAE resin can be from a low of about 150,000, about
155,000, about 160,000, about 165,000, about 170,000, or about
180,000 to a high of about 200,000, about 210,000, about 220,000,
about 230,000, about 240,000, about 250,000, about 300,000, about
350,000, about 400,000, about 450,000, about 500,000, about
550,000, about 600,000, about 650,000, about 700,000, about
750,000, or about 800,000. For example, the weight average
molecular weight of the second thermosetting resin can be about
150,000 to about 250,000, about 155,000 to about 185,000, about
175,000 to about 210,000, about 165,000 to about 225,000, about
195,000 to about 235,000, about 210,000 to about 245,000, about
225,000 to about 425,000, about 325,000 to about 575,000, about
410,000 to about 625,000, about 475,000 to about 740,000, about
525,000 to about 675,000, about 625,000 to about 775,000, or about
675,000 to about 800,000. In another example, the second
thermosetting PAE resin can have a weight average molecular weight
of at least 150,000, at least 155,000, at least 160,000, at least
165,000, at least 170,000, at least 175,000, at least 180,000, at
least 190,000, at least 200,000, at least 210,000, at least
225,000, or at least 240,000 and up to about 250,000, about
300,000, about 400,000, about 500,000, about 600,000, about
700,000, or about 800,000.
[0065] The second thermosetting PAE resin can have a molar ratio of
the third epihalohydrin to the secondary amine groups in the third
polyamidoamine (moles epihalohydrin to moles secondary amine
groups) from a low of about 0.5:1, about 0.53:1, about 0.55:1,
about 0.57:1, or about 0.6:1 to a high of about 0.65:1, about
0.66:1, about 0.67:1, about 0.68:1, about 0.69:1, or about 0.7:1.
For example, the second thermosetting PAE resin can have a molar
ratio of the third epihalohydrin to the secondary amine groups in
the third polyamidoamine from about 0.5:1 to about 0.7:1, about
0.55:1 to about 0.65:1, about 0.6:1 to about 0.7:1, about 0.58:1 to
about 0.64:1, or about 0.58:1 to about 0.67:1. In another example,
the second thermosetting PAE resin can have a molar ratio of the
third epihalohydrin to the secondary amine groups in the third
polyamidoamine of at least 0.5:1, at least 0.53:1, at least 0.55:1,
at least 0.57:1, or at least 0.6:1 and up to about 0.62:1, about
0.64:1, about 0.66:1, about 0.68:1, or about 0.7:1.
[0066] The reactivity of the second thermosetting PAE resin can be
expressed as the ratio of moles of reactive groups per mole of the
second thermosetting PAE resin. The ratio of the moles of reactive
groups per mole of the second thermosetting PAE resin can be from a
low of about 500:1, about 510:1, about 520:1, about 530:1, about
540:1, about 550:1, about 560:1, about 570:1, or about 580:1 to a
high of about 610:1, about 620:1, about 640:1, about 650:1, about
665:1, about 675:1, about 685:1, or about 700:1. For example, the
ratio of the moles of reactive groups per mole of the second
thermosetting PAE resin can be from about 500:1 to about 700:1,
about 525:1 to about 615:1, about 545:1 to about 635:1, about 565:1
to about 600:1, about 515:1 to about 585:1, about 575:1 to about
680:1, about 615:1 to about 680:1, or about 590:1 to about 670:1.
In another example, molar ratio of the reactive groups to moles of
the first thermosetting PAE resin can be at least 500:1, at least
515:1, at least 535:1, at least 555:1, at least 565:1, at least
580:1, at least 590:1, at least 600:1, at least 610:1, at least
615:1, at least 620:1, at least 630:1, at least 640:1, or at least
650:1 and up to about 660:1, about 670:1, about 680:1, about 690:1,
or about 700:1. The reactive groups in the first thermosetting PAE
resin can be or include an azetidinium group, pendant halo-groups
such as chloro-groups, or both.
[0067] The second thermosetting PAE resin can have a viscosity from
a low of about 5 cP, about 10 cP, about 20 cP, about 40 cP, or
about 60 cP to a high of about 100 cP, about 125 cP, about 150 cP,
about 175 cP, or about 200 cP at a temperature of about 25.degree.
C. For example, the second thermosetting PAE resin can have a
viscosity from a low of about 5 cP, about 10 cP, about 20 cP, about
40 cP, or about 60 cP to a high of about 100 cP, about 125 cP,
about 150 cP, about 175 cP, or about 200 cP at a temperature of
about 25.degree. C. and a solids concentration of about 15 wt
%.
[0068] The second thermosetting PAE resin can have a pH from a low
of about 2.5, about 3, about 3.5, or about 4 to a high of about
4.5, about 5, about 5.5, about 6, about 6.5, about 7, or about 8.
Illustrative acids that can be used to adjust the pH of the second
thermosetting PAE resin can include, but are not limited to,
hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric
acid, formic acid, phosphoric acid, acetic acid, or any mixture
thereof. The re-wetting properties of the second thermosetting PAE
resin can be modified by the amount and the particular type of acid
used to stabilized the second thermosetting PAE resin
[0069] The amount of the second thermosetting PAE resin in the
creping adhesive can be from a low of about 1 wt %, about 3 wt %,
about 5 wt %, about 7 wt %, about 10 wt %, about 15 wt %, about 20
wt %, or about 30 wt % to a high of about 40 wt %, about 50 wt %,
about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about
75 wt %, or about 80 wt %, based on the combined weight of the
first thermosetting PAE resin, the first thermoplastic PAE resin,
the re-wetting agent, and the second thermosetting PAE resin.
[0070] The second thermoplastic PAE resin can be the reaction
product of a fourth polyamidoamine and a fourth epihalohydrin. The
fourth polyamidoamine can be a reaction product of a fourth
polyamine and a fourth dicarboxylic acid. The fourth epihalohydrin,
the fourth polyamine, and the fourth dicarboxylic acid (and/or
fourth ester of a dicarboxylic acid) can include those discussed
and described above with reference to the first thermosetting PAE
resin. When the creping adhesive includes the first thermoplastic
PAE and the second thermoplastic PAE, the creping adhesive can have
a bi-modal distribution of the molecular weight of the
thermoplastic component.
[0071] The second thermoplastic PAE resin can have a weight average
molecular weight from a low of about 200,000, about 250,000, about
300,000, about 350,000, about 400,000, about 450,000, or about
500,000 to a high of about 1,000,000, about 1,250,000, about
1,500,000, about 1,750,000, about 2,000,00, about 2,250,000, about
2,500,000, about 2,750,000, or about 3,000,000. For example, the
second thermoplastic PAE resin can have a weight average molecular
weight of about 200,000 to about 3,000,000, about 275,000 to about
1,300,000, about 475,000 to about 975,000, about 550,000 to about
1,200,000, about 825,000 to about 1,700,000, about 1,400,000 to
about 2,300,000, about 1,800,000 to about 2,600,000, about
1,950,000 to about 2,850,000, or about 2,300,000 to about
3,000,000. In another example, the second thermoplastic PAE resin
can have a weight average molecular weight of at least 200,000, at
least 250,000, at least 300,000, at least 350,000, at least
400,000, at least 450,000, or at least 500,000 and up to about
1,000,000, about 1,250,000, about 1,500,000, about 1,750,000, about
2,000,000, about 2,250,000, about 2,500,000, about 2,750,000, or
about 3,000,000.
[0072] The molar ratio of the fourth polyamine to the fourth
dicarboxylic acid and/or the fourth ester of a dicarboxylic acid in
the fourth PAE resin can be from a low of about 0.8:1, about
0.85:1, about 0.9:1, about 0.95:1, or about 1:1 to a high of about
1:1, about 1.05:1, about 1.1:1, about 1.2:1, about 1.3:1, or about
1.4:1. For example, the molar ratio of the fourth polyamine to the
third dicarboxylic acid can be about 0.8:1 to about 1.4:1, about
0.9:1 to about 1.2:1, about 0.9:1 to about 1:1, about 1:0.95 to
about 1:1.05, about 1:0.9 to about 1:1.1, about 1:0.85 to about
1:1.1, or about 0.95:1 to about 1.05:1.
[0073] The second thermoplastic PAE resin can have a secondary
amine concentration from a low of about 4 mmols, about 4.3 mmols,
about 4.5 mmols, about 4.7 mmols, about 5 mmols, about 5.3 mmols,
or about 5.5 mmols to a high of about 6 mmols, about 6.3 mmols,
about 6.5 mmols, about 6.7 mmols, about 7 mmols, about 7.5 mmols,
or about 8 mmols per gram of the second thermoplastic PAE resin.
For example, the second thermoplastic PAE resin can have a
secondary amine concentration of about 4 mmols to about 5.4 mmols,
about 4.6 mmols to about 6.2 mmols, about 5.2 mmols to about 6.6
mmols, about 5.8 mmols to about 7.2 mmols, about 6.4 mmols to about
8 mmols, or about 4 mmols to about 8 mmols per gram of the second
thermoplastic PAE resin.
[0074] The amount of the second thermoplastic PAE resin in the
creping adhesive can be from a low of about 1 wt %, about 3 wt %,
about 5 wt %, about 7 wt %, about 10 wt %, about 15 wt %, about 20
wt %, or about 30 wt % to a high of about 60 wt %, about 65 wt %,
about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, or
about 90 wt %, based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, the
re-wetting agent, and the second thermoplastic resin.
[0075] The third thermosetting PAE resin can be the reaction
product of a fifth polyamidoamine and a fifth epihalohydrin. The
fifth polyamidoamine can be a reaction product of a fifth polyamine
and a fifth dicarboxylic acid. The fifth epihalohydrin, the fifth
polyamine, and the fifth dicarboxylic acid (and/or fifth ester of a
dicarboxylic acid) can include those discussed and described above
with reference to the first thermosetting PAE resin. The relative
amounts of the fifth epihalohydrin, the fifth polyamine, and the
fifth dicarboxylic acid (and/or fifth ester of dicarboxylic acid)
can be similar to the amounts discussed and described above with
respect to the first thermosetting PAE resin. The particular
amounts of the reactants used to make the third thermosetting PAE
resin can depend, at least in part, on the desired properties of
the third thermosetting PAE resin.
[0076] The molar ratio of the fifth polyamine to the fifth
dicarboxylic acid and/or the fifth ester of a dicarboxylic acid in
the third thermosetting PAE resin can be from a low of about 0.8:1,
about 0.85:1, about 0.9:1, about 0.95:1, or about 1:1 to a high of
about 1.1:1, about 1.15:1, about 1.2:1, about 1.25:1, about 1.3:1,
or about 1.4:1. For example, the molar ratio of the fifth polyamine
to the fifth dicarboxylic acid can be about 0.83:1 to about 0.97:1,
about 0.88:1 to about 1.06:1, about 0.92:1 to about 1.15:1, about
0.95:1.3 to about 1.2:1.35, about 1.17:1 to about 1.28:1, or about
0.9 to about 1.1.
[0077] The weight average molecular weight of the third
thermosetting PAE resin can be from a low of about 600,000, about
650,000, about 700,000, about 750,000, about 800,000, about
900,000, about 950,000, about 1,000,000, about 1,050,000, or about
1,100,000 to a high of about 1,200,000, about 1,250,000, about
1,300,000, about 1,400,000, about 1,500,000, about 1,600,000, about
1,700,000, or about 1,800,000. For example, the weight average
molecular weight of the third thermosetting PAE resin can be about
675,000 to about 975,000, about 750,000 to about 950,000, about
800,000 to about 900,000, about 825,000 to about 875,000, about
825,000 to about 860,000, about 840,000 to about 875,000, about
900,000 to about 1,350,000, about 1,150,000 to about 1,650,000,
about 1,250,000 to about 1,550,000, about 1,350,000 to about
1,750,000, or about 1,650,000 to about 1,800,000. In another
example, the third thermosetting PAE resin can have a weight
average molecular weight of at least 700,000, at least 750,000, at
least 800,000, at least 850,000, at least 900,000, at least
950,000, at least 1,000,000, at least 1,050,000, at least
1,100,000, or at least 1,200,000 and up to about 1,400,000, about
1,500,000, about 1,600,000, about 1,700,000, or about
1,800,000.
[0078] The third thermosetting PAE resin can have a molar ratio of
the fifth epihalohydrin to the secondary amine groups in the fifth
polyamidoamine (moles epihalohydrin to moles secondary amine
groups) from a low of about 0.2:1, about 0.25:1, about 0.3:1, about
0.35:1, or about 0.4:1to a high of about 0.5:1, about 0.6:1, about
0.65:1, about 0.7:1, about 0.75:1, or about 0.8:1. For example, the
third thermosetting PAE resin can have a molar ratio of the fifth
epihalohydrin to the secondary amine groups in the fifth
polyamidoamine from about 0.2:1 to about 0.55:1, about 0.3:1 to
about 0.45:1, about 0.35:1 to about 0.68:1, about 0.4:1 to about
0.75:1, or about 0.45:1 to about 0.7:1. In another example, the
third thermosetting PAE resin can have a molar ratio of the fifth
epihalohydrin to the secondary amine groups in the fifth
polyamidoamine of at least 0.3:1, at least 0.35:1, at least 0.4:1,
at least 0.45:1, or at least 0.5:1 and up to about0.6:1, about
0.65:1, about 0.7:1, about 0.75:1, or about 0.8:1.
[0079] The third thermosetting PAE resin can be free from any
secondary amines. The third thermosetting PAE resin can have a
secondary amine concentration from a low of about 0.01 mmols, about
0.05 mmols, about 0.07 mmols, about 0.1 mmols, about 0.13 mmols,
about 0.15 mmols, or about 0.15 mmols to a high of about 0.17
mmols, about 0.2 mmols, about 0.23 mmols, about 0.25 mmols, about
0.27 mmols, or about 0.3 mmols per gram of the third thermosetting
PAE resin. For example, the third thermosetting PAE resin can have
a secondary amine concentration of about 0.05 mmols to about 0.14
mmols, about 0.05 mmols to about 0.2 mmols, about 0.08 mmols to
about 0.22 mmols, about 0.1 mmols to about 0.22 mmols, about 0.14
mmols to about 0.26 mmols, about 0.18 mmols to about 0.28 mmols,
about 0.2 mmols to about 0.3 mmols, about 0.14 mmols to about 0.28
mmols, or about 0.05 mmols to about 0.3 mmols per gram of the third
thermosetting PAE resin.
[0080] The reactivity of the third thermosetting PAE resin can be
expressed as the ratio of moles of reactive groups per mole of the
third thermosetting PAE resin. The ratio of the moles of reactive
groups per mole of the third thermosetting PAE resin can be from a
low of about 0.02:1, about 0.04:1, about 0.06:1, about 0.08:1,
about 0.1:1, about 0.13:1, about 0.17:1, about 0.2:1, or about
0.24:1 to a high of about 0.3:1, about 0.34:1, about 0.38:1, about
0.44:1, about 0.48:1, about 0.52:1, about 0.56:1, or about 0.6:1.
For example, the ratio of the moles of reactive groups per mole of
the third thermosetting PAE resin can be from about 0.025:1 to
about 0.1:1, about 0.07:1 to about 0.15:1, about 0.1:1 to about
0.3:1, about 0.1:1 to about 0.5:1, about 0.15:1 to about 0.4:1,
about 0.2:1 to about 0.45:1, about 0.3:1 to about 0.46:1, or about
0.5:1 to about 0.6:1. In another example, molar ratio of the
reactive groups to moles of the first thermosetting PAE resin can
be at least 0.02:1, at least 0.1:1, at least 0.15:1, at least
0.2:1, at least 0.25:1, at least0.3:1, at least 0.35:1, or at least
0.4:1 and up to about 0.45:1, about 0.5:1, about 0.55:1, or about
0.6:1. The reactive groups in the first thermosetting PAE resin can
be or include an azetidinium group, pendant halo-groups such as
chloro-groups, or both.
[0081] The third thermosetting PAE resin can have a viscosity from
a low of about 30 cP, about 40 cP, about 50 cP, about 60 cP, or
about 70 cP to a high of about 100 cP, about 110 cP, about 120 cP,
about 130 cP, or about 140 cP at a temperature of about 25.degree.
C. For example, the third thermosetting PAE resin can have a
viscosity from a low of about 30 cP, about 40 cP, about 50 cP,
about 60 cP, or about 70 cP to a high of about 100 cP, about 110
cP, about 120 cP, about 130 cP, or about 140 cP at a temperature of
about 25.degree. C. and a solids concentration of about 15 wt
%.
[0082] The third thermosetting PAE resin can have a pH from a low
of about 2.5, about 3, about 3.5, or about 4 to a high of about
4.5, about 5, about 5.5, about 6, about 6.5, about 7, or about 8.
Illustrative acids that can be used to adjust the pH of the third
thermosetting PAE resin can include, but are not limited to,
hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric
acid, formic acid, phosphoric acid, acetic acid, or any mixture
thereof. The re-wetting properties of the third thermosetting PAE
resin can be modified by the amount and the particular type of acid
used to stabilized the third thermosetting PAE resin.
[0083] The amount of the third thermosetting PAE resin in the
creping adhesive can be from a low of about 2 wt %, about 5 wt %,
about 10 wt %, about 12 wt %, about or about 15 wt % to a high of
about 30 wt %, about 35 wt %, about 37 wt %, about 40 wt %, about
43 wt %, or about 45 wt %, based on the combined weight of the
first thermosetting PAE resin, the first thermoplastic PAE resin,
the re-wetting agent, and the third thermosetting PAE resin. The
amount of the third thermosetting PAE resin in the creping adhesive
can be from a low of about 2 wt %, about 5 wt %, about 10 wt %,
about 12 wt %, about or about 15 wt % to a high of about 30 wt %,
about 35 wt %, about 37 wt %, about 40 wt %, about 43 wt %, or
about 45 wt %, based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, the
re-wetting agent, and the third thermosetting PAE resin.
[0084] When the creping adhesive includes the first and second
thermosetting PAE resins and the first and second thermoplastic PAE
resins, the amount of the first thermosetting PAE resin can be
about 5 wt % to about 80 wt %, the amount of the first
thermoplastic PAE resin can be about 15 wt % to about 90 wt %, the
amount of the second thermosetting PAE resin can be about 1 wt % to
about 80 wt %, and the amount of the second thermoplastic PAE resin
can be about 1wt % to about 90 wt %, based on the combined weight
of the first and second thermosetting PAE resins, the first and
second thermoplastic PAE resins, and the one or more re-wetting
agents. For example, when the creping adhesive includes the first
and second thermosetting PAE resins and the first and second
thermoplastic PAE resins, the amount of the first thermosetting PAE
resin can be about 3 wt %, about 5 wt %, about 10 wt %, about 15 wt
%, or about 20 wt % to about 50 wt %, about 60 wt %, about 70 wt %,
or about 80 wt %, the amount of the first thermoplastic PAE resin
can be about 10 wt %, about 20 wt %, about 30 wt %, or about 40 wt
% to about 60 wt %, about 70 wt %, about 80 wt %, or about 90 wt %,
the amount of the second thermosetting PAE resin can be about 10 wt
%, about 20 wt %, or about 30 wt % to about 50 wt %, about 60 wt %,
or about 70 wt % and the amount of the second thermoplastic PAE
resin can be about 10 wt %, about 20 wt %, or about 30 wt % to
about 50 wt %, about 60 wt %, or about 70 wt %, based on the
combined weight of the first and second thermosetting PAE resins,
the first and second thermoplastic PAE resins, and the one or more
rewetting agents.
[0085] When the creping adhesive includes the first, second, and
third thermosetting PAE resins and the first and second
thermoplastic PAE resins, the amount of the first thermosetting PAE
resin can be about 5 wt % to about 70 wt %, the amount of the first
thermoplastic PAE resin can be about 15 wt % to about 80 wt %, the
amount of the second thermosetting PAE resin can be about 25 wt %
to about 60 wt %, the amount of the second thermoplastic PAE resin
can be about 20 wt % to about 65 wt %, and the amount of the third
thermosetting PAE resin can be about 2 wt % to about 45 wt %, based
on the combined weight of the first, second, and third
thermosetting PAE resins, the first and second thermoplastic PAE
resins, and the one or more re-wetting agents. For example, when
the creping adhesive includes the first, second, and third
thermosetting PAE resins and the first and second thermoplastic PAE
resins, the amount of the first thermosetting PAE resin can be
about 5 wt %, about 10 wt %, about 15 wt %, or about 20 wt % to
about 50 wt %, about 60 wt %, about 65 wt %, or about 70 wt %, the
amount of the first thermoplastic PAE resin can be about 15 wt %,
about 20 wt %, about 30 wt %, or about 40 wt % to about 60 wt %,
about 70 wt %, about 75 wt %, or about 80 wt %, the amount of the
second thermosetting PAE resin can be about 25 wt %, about 30 wt %,
or about 35 wt % to about 50 wt %, about 55 wt %, or about 60 wt %,
the amount of the second thermoplastic PAE resin can be about 20 wt
%, about 25 wt %, or about 30 wt % to about 50 wt %, about 60 wt %,
or about 65 wt %, and the amount of the third thermoplastic PAE
resin can be about 2 wt %, about 3 wt %, about 5 wt %, or about 10
wt % to about 25 wt %, about 35 wt %, or about 45 wt %, based on
the combined weight of the first, second, and third thermosetting
PAE resins, the first and second thermoplastic PAE resins, and the
one or more re-wetting agents.
[0086] Suitable methods for making polyamidoamine-epihalohydrin
resins can include those discussed and described in, for example,
U.S. Pat. Nos. 2,926,116; 3,058,873; 3,772,076; 5,338,807; EP
Patent No.: EP 0488767; Canadian Patent Application Publication
No.: CA 979,579; and GB Patent Application Publication No.: GB
865,727(A).
[0087] In one or more embodiments, the various components of the
creping adhesive can be dissolved, dispersed, suspended,
emulsified, or otherwise added or mixed with water. For example,
the amount of water in the creping adhesive can be from a low of
about 0.1 wt %, about 1 wt %, about 5 wt %, about 10 wt %, or about
20 wt % to a high of about 50 wt %, about 60 wt %, or about 70 wt
%, based on the combined weight of the thermosetting PAE resin, the
thermoplastic PAE resin, the re-wetting agent, and water. In
another example, the creping adhesive can include about 0.1 wt % to
about 5 wt %, about 5 wt % to about 15 wt %, about 8 wt % to about
25 wt %, about 15 wt % to about 25 wt %, about 15 wt % to about 30
wt %, about 10 wt % to about 25 wt %, about 20 wt % to about 35 wt
%, about 20 wt % to about 25 wt %, about 35 wt % to about 55 wt %,
about 50 wt % to about 70 wt %, about 55 wt % to about 65 wt %,
about 60 wt % to about 65 wt %, about 65 wt % to about 80 wt %,
about 70 wt % to about 85 wt %, about 75 wt % to about 90 wt %,
about 80 wt % to about 90 wt %, about 85 wt % to about 90 wt %, or
about 80 wt % to about 95 wt % of water, based on the combined
weight of all thermosetting PAE resins, all thermoplastic PAE
resins, the one or more re-wetting agents, and water.
[0088] In one or more embodiments, the creping adhesive can
optionally include one or more additional polymers. The additional
polymer can be natural, synthetic, or derived from a natural
source. Illustrative additional polymers that can be included in
the creping adhesive can include, but are not limited to, polyvinyl
alcohol, hemicellulose, polyvinyl amine, polyacrylamide, or any
mixture thereof. If the creping adhesive includes the additional
polymer(s), the amount of the additional polymer present in the
creping adhesive can be from a low of about 1 wt % to a high of
about 90 wt %, based on the combined weight of the first
thermosetting PAE resin, the first thermoplastic PAE resin, the
re-wetting agent, and the additional polymer(s).
[0089] In one or more embodiments, the creping adhesive can further
include one or more release aids. Suitable release aids can be
based on a quaternary imidazoline (e.g., methyl and ethyl sulfate
salts of quaternary imidazoline derived from fatty acids), one or
more mineral oils, one or more vegetable oils, one or more silicon
oils, one or more surfactants, one or more soaps, one or more
polyols, glycols, glycerol, sorbitol, polyglycerine, polyethylene
glycol, sugars, oligosaccharides, hydrocarbon oils, or any mixture
thereof. The quaternary imidazoline release aid can be supplied as
a mixture containing about 90 wt % imidazoline and about 10 wt %
diethylene glycol, which can be dissolved in a high boiling point
solvent. For example, about 20 wt % to about 80 wt % of the
quaternary imidazoline can be dissolved in about 80 wt % to about
20 wt % of a solvent. The release aid can also include one or more
mineral oils, vegetable oils, or a mixture thereof. In one or more
embodiments, the release aid can be an oil-based dispersion of
paraffinic oil, naphthenic oil, a vegetable oil, or any mixture
thereof. The imidazoline-based release aid itself can have an
adjustable viscosity that can be varied by using a mixture of high
boiling compounds as a solvent for the quaternized imidazoline.
Other suitable release aids can include those discussed and
described in U.S. Pat. Nos. 5,660,687 and 5,833,806.
[0090] The creping adhesive can also include one or more additional
additives. Illustrative additional additives can include, but are
not limited to, tackifiers, surfactants, dispersants, salts which
are effective to adjust water hardness, acids or bases for
adjusting pH of the creping adhesive.
[0091] In one or more embodiments, the creping adhesive can be
applied to a drying surface. A cellulosic fiber web can be placed,
contacted, disposed, or otherwise located onto the drying surface.
The cellulosic fiber web can be adhered to the drying surface via
the creping adhesive. The cellulosic fiber web can be at least
partially dried. The at least partially dried cellulosic fiber web
can be dislodged or otherwise removed from the drying surface to
provide a creped paper product. In one or more embodiments, the
drying surface can be the surface of a Yankee dryer.
[0092] In one or more embodiments, the creping adhesive can be
formed on the drying surface. For example, a creping adhesive that
includes the first thermosetting PAE resin, the first thermoplastic
PAE resin, and the re-wetting agent can be applied to the drying
surface as a mixture. In another example, the creping adhesive that
includes the first thermosetting PAE resin, the first thermoplastic
PAE resin, and the re-wetting agent can be applied separately to
the drying surface such that the creping adhesive can be formed on
the surface. If any two or more components of the creping adhesive
are separately applied to the drying surface, the two or more
components can be applied in any order or sequence with respect to
one another or at the same time with respect to one another. For
example, a mixture of the first thermosetting PAE resin and the
re-wetting agent can be applied to the surface and the first
thermoplastic PAE resin can be applied to the surface, before,
after, or simultaneously with respect to the mixture of the first
thermosetting PAE resin and the re-wetting agent, to form the
creping adhesive on the drying surface as opposed for forming the
creping adhesive prior to application to the surface. In another
example a creping adhesive that includes the first, second, and
third PAE resins, the first and second thermoplastic PAE resins,
and the re-wetting agent, the creping adhesive can be applied as a
mixture, as individual components, or as multiple mixtures, where
each of the multiple mixtures is free from at least one of the
components. For example, a mixture of the first and second
thermosetting PAE resin, the first and second thermoplastic PAE
resins, and the re-wetting agent can be applied to the drying
surface as a mixture and the third PAE resin can be applied
separately from the mixture to the drying surface to form the
creping adhesive on the surface that can include the first, second,
and third thermosetting PAE resins, the first and second
thermoplastic PAE resins, and the re-wetting agent.
[0093] A Yankee dryer is a large diameter cylinder. For example,
the Yankee dryer can be a cylinder having an internal diameter from
about 8 feet to about 20 feet. The drum can be heated with high
pressure steam or other heated medium to provide a hot or heated
surface. For example, the surface of the dryer can be heated to a
temperature from a low of about 20.degree. C., about 30.degree. C.,
or about 40.degree. C. to a high of about 60.degree. C., about
80.degree. C., about 100.degree. C., about 120.degree. C., about
140.degree. C., about 160.degree. C., about 180.degree. C., about
200.degree. C., or about 220.degree. C. In another example, the
surface of the dryer can be heated to a temperature of at least
60.degree. C., at least 80.degree. C., at least 100.degree. C., at
least 130.degree. C., at least 150.degree. C., at least 155.degree.
C., at least 160.degree. C., at least 165.degree. C., at least
170.degree. C., at least 175.degree. C., at least 180.degree. C.,
at least 185.degree. C., or at least 190.degree. C. In another
example, the surface of the dryer can be heated to a temperature
from a low of about 20.degree. C., about 30.degree. C., or about
40.degree. C. to a high of about 60.degree. C., about 80.degree.
C., about 100.degree. C., about 130.degree. C., about 150.degree.
C., about 170.degree. C., or about 195.degree. C. The heated
surface can act to dry the cellulosic fiber web to produce the
creped paper product. The cellulosic fiber web can be heated on the
drying surface for a time of about 10 seconds to about 5 minutes.
The cellulosic fiber web can be heated to a temperature of about
20.degree. C., about 30.degree. C., or about 40.degree. C. to about
60.degree. C., about 80.degree. C., about 100.degree. C., about
120.degree. C., about 140.degree. C., about 160.degree. C., or
about 180.degree. C. when adhered to the surface of the dryer.
[0094] Prior to encountering the Yankee dryer, the paper web,
formed by dewatering the cellulosic fiber slurry, can be
transferred to a felt or fabric substrate in a so-called press
section where de-watering can be continued to increase the
consistency of the paper, usually to about 40% to about 80%, either
by mechanically compacting the paper or by some other de-watering
method such as through-air-drying with hot air before feeding the
Yankee dryer. Thereafter, the paper web can be transferred in this
partially dry, high solids condition to the surface of the Yankee
dryer.
[0095] The adhesion properties of the creping adhesive can be
modified during production of the creped paper product by varying
the amount of crosslinking that can occur when the first
thermosetting PAE resin, the second thermosetting PAE resin, and/or
the third thermosetting PAE resin dry. By varying the amount of
crosslinking that can occur in the first thermosetting PAE resin,
the second thermosetting PAE resin, and/or the third thermosetting
PAE resin, the level of adhesion of the fibrous substrate onto the
dryer surface can be adjusted or otherwise controlled. The amount
of crosslinking can be varied by altering the preparation of a
given thermosetting PAE resin, i.e., the extent by which the
thermosetting PAE resin is crosslinked during its preparation,
and/or by altering the type and/or amount of the given
thermosetting PAE resin included in the creping composition.
[0096] The first thermoplastic PAE resin and/or the second
thermoplastic PAE resin can react with the first thermosetting PAE
resin, the second thermosetting PAE resin, and/or the third
thermosetting PAE resin to attenuate or otherwise control the
reactivity of the resin. The reactive (nucleophilic) modifiers can
react with a halohydrin, e.g., a chlorohydrin group, of a given
thermosetting PAE resin to effectively reduce the amount of
available halohydrin groups and thus reduce the degree of
crosslinking that is available in the given thermosetting PAE resin
and provide greater control of the crosslinking reaction on the
surface of the dryer.
[0097] The thermosetting or crosslinking process can be allowed to
develop on the surface of the dryer under controlled conditions.
The controllability of the creping adhesive can create the ability
to obtain good tissue and towel creping properties under a wide
range of operating conditions. The creping adhesive can provide
good creping performance under the highly demanding conditions of
the Through-Air-Drying (TAD) process, which generally employs high
drum temperatures and low moisture content. In addition, the
coating can be controlled to provide good creping performance under
high moisture conditions of conventional creping processes.
[0098] As used herein, the terms "cellulosic fiber web," "fibrous
web," "tissue paper web," "paper web," "web," and "cellulosic fiber
product" all refer to sheets of paper made by a process that
includes forming an aqueous papermaking furnish, depositing the
furnish onto a foraminous surface to form a wet cellulosic web,
removing at least a portion of the water from the web to provide a
partially dried web, e.g., by gravity or vacuum-assisted drainage,
with or without pressing, and by evaporation, adhering the
partially dried web to a heated drying surface, e.g., a drying
surface of a Yankee Dryer, removing at least a portion of the water
by evaporation to provide a dried web, removing the dried web by a
creping blade such as a doctor blade to provide a creped product.
The creped product can be wound onto a reel. The moisture content
of the at least partially dried web delivered to the creping
equipment can be between about 5 wt % and about 85 wt %. The web
can be comprised of various types of natural and recycled fibers
including wood pulps of chemical and mechanical types. The web can
be composed of up to 100% recycled fibers. The fibers can comprise
hardwood, softwood and cotton fibers. The tissue web can also
contain particulate fillers, fines, as well as process chemicals
used in the paper-making process such as strength additives,
softeners, surfactants and organic resins.
[0099] The creping adhesive can be applied to the surface of the
dryer at a rate, relative to the rate of dryer surface rotation,
which can provide an adequate amount of adhesion or tack to hold
the web to the surface of the dryer during drying yet release the
dried web upon completion of drying. Conventional creping adhesive
coverage rates and weights can be used as are known to those
skilled in the art. For example, the creping adhesive can be
applied to the surface of the dryer in an amount from a low of
about 0.01 mg/m.sup.2, about 0.1 mg/m.sup.2, about 1 mg/m.sup.2,
about 5 mg/m.sup.2, about 10 mg/m.sup.2, about 25 mg/m.sup.2, or
about 50 mg/m.sup.2, to a high of about 100 mg/m.sup.2, about 200
mg/m.sup.2, about 300 mg/m.sup.2, about 400 mg/m.sup.2, or about
500 mg/m.sup.2, based on the solids weight of the creping adhesive.
Low application rates of about 0.01 mg/m.sup.2 to about 10
mg/m.sup.2, based on the solids weight of the creping adhesive, are
surprisingly effective. Indeed, the creping adhesive of the present
invention can exhibit good adhesion and creping performance at very
low application rates such as about 0.01 mg/m.sup.2 to about 2
mg/m.sup.2.
[0100] The creping adhesive applied to the surface of the dryer can
form a layer, film, or coating on the surface of the dryer having a
thickness of at least 0.01 .mu.m, at least 0.1 .mu.m, at least 1
.mu.m, at least 10 .mu.m, at least 50 .mu.m, at least 100 .mu.m, at
least 500 .mu.m, at least 1 mm, at least 2 mm, at least 3 mm, at
least 4 mm, at least 5 mm, at least 6 mm, at least 7 mm, at least 8
mm, at least 9 mm, or at least 10 mm. For example, creping adhesive
applied to the surface of the dryer can form a layer, film, or
coating on the surface of the dryer having a thickness of about 1
.mu.m to about 100 .mu.m, about 50 .mu.m to about 300 .mu.m, about
200 .mu.m to about 800 .mu.m about 400 .mu.m to about 1 mm, about
700 .mu.m to about 2 mm, about 1 mm to about 2.5 mm, about 1.5 mm
to about 4 mm, about 3 mm to about 7 mm, about 4.5 mm to about 9.5
mm, about 5.5 mm to about 11 mm, about 6.5 mm to about 12 mm, about
7.5 mm to about 9 mm, or about 8 mm to about 10.5 mm.
[0101] The creped product can have a basis weight between about 10
g/m.sup.2 and about 50 g/m.sup.2 and, more usually, between about
10 g/m.sup.2 and about 30 g/m.sup.2. The density of the creped
product can be about 0.03 g/m.sup.3 and about 0.6 g/cm.sup.3 such
as about 0.05 g/cm.sup.3 and 0.2 g/cm.sup.3.
[0102] The creping adhesive can be applied onto the drying surface,
e.g., a surface of a Yankee dryer, to provide a coating that can
develop a crepe ratio of least -2, at least -1, at least 1, at
least 2, at least 3, at least 4, at least 5, at least 6, or at
least 7. For example, creping adhesive can be applied onto the
drying surface, e.g., a surface of a Yankee dryer, to provide a
coating that can develop a crepe ratio of about -2 to about 2,
about -2 to about 7, about -1 to about 1, about 0 to about 1, about
0.5 to about 3, about 1.5 to about 4, about 2 to about 5, about 2.5
to about 5, about 3 to about 6, about 3.5 to about 5, about 4 to
about 7, about 4.5 to about 6, about 5 to about 7, about 5.5 to
about 6.5, about 6 to about 7, or about 3 to about 7.
[0103] Suitable methods for applying the creping adhesive and
creping cellulosic webs can include those discussed and described
in U.S. Pat. Nos. 3,640,841; 4,304,625; 4,440,898; 4,788,243;
4,994,146; 5,025,046; 5,187,219; 5,326,434; 5,246,544; 5,370,773;
5,487,813; 5,490,903; 5,633,309; 5,660,687; 5,846,380; 4,300,981;
4,063,995; 4,501,640; 4,528,316; 4,886,579; 5,179,150; 5,234,547;
5,374,334; 5,382,323; 5,468,796; 5,902,862; 5,942,085; 5,944,954;
3,879,257; 4,684,439; 3,926,716; 4,883,564; and 5,437,766.
EXAMPLES
[0104] In order to provide a better understanding of the foregoing
discussion, the following non-limiting examples are offered.
Although the examples can be directed to specific embodiments, they
are not to be viewed as limiting the invention in any specific
respect.
Example 1
Preparation of Polyamidoamine Prepolymer I
[0105] A glass reactor with a 5-neck top and equipped with a
stainless steel stirring shaft, a reflux condenser, temperature
probe, and a hot oil bath was used to produce the polyamidoamine
prepolymer I. To the reactor was added about 500.5 grams of
diethylenetriamine (DETA). The stirrer was turned on and about 730
grams of adipic acid was added slowly to the reactor over a time
period of about 45 minutes with stirring. The reaction temperature
increased from about 25.degree. C. to about 145.degree. C. during
addition of the adipic acid. After the adipic acid addition was
complete, the reactor was immersed in a hot oil bath and heated to
a temperature of about 160.degree. C. At a temperature of about
150.degree. C. the reaction mixture began to reflux. The reflux
condenser was reconfigured for distillation and distillate was
collected in a separate receiver. The reaction mixture was sampled
at about 30 minute intervals. Each sample was diluted with water to
a solids concentration of about 45 wt % and the viscosity was
measured with Brookfield viscometer at a temperature of about
25.degree. C. When the sample reached a viscosity of about 290 cP
the distillation condenser was reconfigured to reflux. Water was
added slowly to the reaction mixture through the reflux condenser
to dilute and cool the reaction. Water was added to provide a final
solids concentration of 45 wt %. The viscosity of the
polyamidoamine prepolymer I was about 290 cP at a temperature of
about 25.degree. C., as measured by a Brookfield small sample
adapter at a temperature of about 25.degree. C. The weight average
molecular weight of the polyamidoamine prepolymer I was about
35,000 Daltons, as measured by to gel permeation
chromatography.
Example 2
Preparation of Polyamidoamine Prepolymer II
[0106] A glass reactor with a 5-neck top and equipped with a
stainless steel stirring shaft, a reflux condenser, temperature
probe, and a hot oil bath was used to produce the polyamidoamine
prepolymer II. To the reactor was added about 1,574.5 grams of
glutaric acid dimethyl ester (DBE-5). The stirrer was turned on and
about 1,038.9 grams of DETA was added to the reactor with stirring.
The reactor was immersed in a hot oil bath heated to a temperature
of about 100.degree. C. At a temperature of about 90.degree. C. the
reaction mixture began to reflux. The reflux condenser was
reconfigured for distillation and distillate was collected in a
separate receiver. The reaction mixture was sampled at about 30
minute intervals. Each sample was diluted with water to a solids
concentration of about 45 wt % and the viscosity was measured with
Brookfield viscometer at a temperature of about 25.degree. C. When
the sample reached a viscosity of about 220 cP the distillation
condenser was reconfigured to reflux. Water was added slowly to the
reaction mixture through the reflux condenser to dilute and cool
the reaction. Water was added to provide a final solids
concentration of about 45 wt %. The viscosity of the polyamidoamine
prepolymer II was about 220 cP at a temperature of about 25.degree.
C., as measured by a Brookfield small sample adapter at a
temperature of about 25.degree. C. The weight average molecular
weight of the polyamidoamine prepolymer II was about 25,000
Daltons, as measured by gel permeation chromatography.
Example 3
Preparation of Polyamidoamine Prepolymer III
[0107] A glass reactor with a 5-neck top and equipped with a
stainless steel stirring shaft, a reflux condenser, temperature
probe, and a hot oil bath was used to produce the polyamidoamine
prepolymer III. To the reactor was added about 1,563.9 grams of
glutaric acid dimethyl ester (DBE-5). The stirrer was turned on and
about 1,031.9 grams of DETA was added to the reactor with stirring.
The reactor was immersed in a hot oil bath heated to a temperature
of about 100.degree. C. At a temperature of about 90.degree. C. the
reaction mixture began to reflux. The reflux condenser was
reconfigured for distillation and distillate was collected in a
separate receiver. The reaction mixture was sampled at about 30
minute intervals. Each sample was diluted with water to a solids
concentration of about 45 wt % and the viscosity was measured with
Brookfield viscometer at a temperature of about 25.degree. C. When
the sample reached a viscosity of about 290 cP the distillation
condenser was reconfigured to reflux. Water was added slowly to the
reaction mixture through the reflux condenser to dilute and cool
the reaction. Water was added to obtain final solids of 45%. The
viscosity of the polyamidoamine prepolymer III was about 290 cP at
a temperature of about 25.degree. C., as measured by a Brookfield
small sample adapter at a temperature of about 25.degree. C. The
weight average molecular weight of the polyamidoamine prepolymer
III was about 35,000 Daltons, as measured by gel permeation
chromatography.
Example 4
Preparation of a First Thermosetting PAE Resin from Prepolymer
I
[0108] A glass reactor with a 5-neck top and equipped with a glass
stirring shaft, an equal-pressure addition funnel, a temperature
probe, a pH probe, a heating mantle, coiled stainless-steel tubing
for circulation of cooling water, and a vacuum-actuated sample tube
to allow for the removal and return of sample aliquots from the
reactor was used to produce a first thermosetting PAE resin from
prepolymer I. To the reactor about 680.3 grams of water followed by
about 295.2 grams of the prepolymer I were added. The mixture was
heated to a temperature of about 40.degree. C. and about 3.93 grams
of epichlorohydrin was added to produce a reaction mixture. The
reaction mixture was heated over a time period of about 15 minutes
to a temperature of about 75.degree. C. The reaction viscosity was
sampled at about 10 minute intervals until a Gardner-Holdt bubble
tube viscosity of about AlA was obtained. The viscosity was 15 cP,
as measured by a Brookfield small sample adapter at a temperature
of about 25.degree. C. About 1.07 grams of epichlorohydrin was
added to the reaction mixture heated to a temperature of about
75.degree. C. and a Gardner-Holdt bubble tube viscosity of about
AAB was obtained. The viscosity was about 20 cP, as measured by a
Brookfield small sample adapter at a temperature of about
25.degree. C. About 0.5 grams of epichlorohydrin was then added and
a Gardner-Holdt bubble tube viscosity of about ABB was obtained.
The viscosity was about 25 cP, as measured by a Brookfield small
sample adapter at a temperature of about 25.degree. C. At this
point epichlorohydrin was added drop wise to the reaction mixture
heated to a temperature of about 75.degree. C. until a
Gardner-Holdt bubble tube viscosity of about E. The reaction
mixture was then cooled to a temperature of about 35.degree. C.
rapidly in an ice water bath. About 13.4 grams of 93% sulfuric acid
was added, followed by about 3.64 grams of water. Additional
sulfuric acid was added to adjust the final pH to about 7.1 to
produce the first thermosetting PAE resin. The first thermosetting
PAE resin had a solids content of about 15 wt %, Gardner-Holdt
bubble tube viscosity of about EEF, and a viscosity of about 90 cP,
as measured by a Brookfield small sample adapter at a temperature
of about 25.degree. C. The first thermosetting PAE resin had a
number average molecular weight of about 53,800, a weight average
molecular weight of about 1,103,000, and z-average molecular weight
of about 14,465,000, as measured according to gel permeation
chromatography.
Example 5
Preparation of a First Thermoplastic Resin from Prepolymer I
[0109] A glass reactor with a 5-neck top and equipped with a glass
stirring shaft, an equal-pressure addition funnel, a temperature
probe, a pH probe, a heating mantle, coiled stainless-steel tubing
for circulation of cooling water, and a vacuum-actuated sample tube
to allow for the removal and return of sample aliquots from the
reactor was used to produce a first thermoplastic PAE resin from
prepolymer I. To the reactor about 265.7 grams of water, followed
by about 661.2 grams of prepolymer I were added. A small amount of
water was added to adjust the prepolymer concentration to about
30.5%. The mixture was heated to a temperature of about 40.degree.
C. and about 3.35 grams of epichlorohydrin was added to produce a
reaction mixture. The reaction mixture was heated over a time
period of about 20 minutes to a temperature of about 90.degree. C.
The reaction viscosity was sampled at about 10 minute intervals
until a Gardner-Holdt bubble tube viscosity of about F was
obtained. About 0.61 grams of epichlorohydrin was added to the
reaction mixture heated to a temperature of about 90.degree. C.
until a Gardner-Holdt bubble tube viscosity of about G was
obtained. Epichlorohydrin was then added drop wise until a
Gardner-Holdt bubble tube viscosity of about GH was obtained, and
the viscosity did not advance further. The reaction mixture was
then cooled to a temperature of about 30.degree. C. rapidly in an
ice water bath. At a temperature of about 30.degree. C., about 63
grams of 85% phosphoric acid was added, followed by about 5 grams
of water. Additional phosphoric acid was added to adjust the final
pH to about 7 to produce the first thermoplastic PAE resin. The
first thermoplastic PAE resin had a solids content of about 35 wt
%, a Gardner-Holdt bubble tube viscosity of about HI, and a
viscosity of about 150 cP, as measured by a Brookfield small sample
adapter at a temperature of about 25.degree. C. The first
thermoplastic PAE resin had a number average molecular weight of
about 38,500, a weight average molecular weight of about 90,490,
and a z-average molecular weight of about 261,000, as measured
according to gel permeation chromatography.
Example 6
Preparation of a Second Thermoplastic PAE Resin from Prepolymer
II
[0110] A glass reactor with a 5-neck top and equipped with a glass
stirring shaft, an equal-pressure addition funnel, a temperature
probe, a pH probe, a heating mantle, coiled stainless-steel tubing
for circulation of cooling water, and a vacuum-actuated sample tube
to allow for the removal and return of sample aliquots from the
reactor was used to produce a second thermoplastic PAE resin from
prepolymer II. To the reactor about 385.6 grams of water was added,
followed by about 247.8 grams of prepolymer II. A small amount of
water was added to adjust the prepolymer concentration to about
19.6%. The mixture was heated to a temperature of about 30.degree.
C. and about 5.57 grams of epichlorohydrin was added to produce a
reaction mixture. The reaction mixture was first stirred for a time
period of about 30 minutes at a temperature of about 30.degree. C.
and then heated over a time period of about 15 minutes to a
temperature of about 80.degree. C. The reaction viscosity was
sampled at about 10 minute intervals until a Gardner-Holdt bubble
tube viscosity of about BC was obtained. Epichlorohydrin was added
drop wise to the reaction mixture heated to a temperature of about
80.degree. C. until a Gardner-Holdt bubble tube viscosity of about
F was obtained. The reaction was then cooled to a temperature of
about 25.degree. C. while adding about 209.5 grams of water. While
continuing to cool the reaction mixture, about 64.6 grams of 31.5%
hydrochloric acid was added, followed by about 86 grams of water.
The pH was measured and additional hydrochloric acid was added to
produce the second thermoplastic PAE resin that had a pH of about
4. Water was added to adjust the final solids concentration of the
second thermoplastic PAE resin to about 15 wt %. The second
thermoplastic PAE resin had a viscosity of about 35 cP, as measured
by a Brookfield small sample adapter at a temperature of about
25.degree. C. The second thermoplastic resin had a number average
molecular weight of about of 26,450, a weight average molecular
weight of about 745,000, and a z-average molecular weight of about
10,920,000.
Example 7
Preparation of a Second Thermosetting PAE Resin from Prepolymer
II
[0111] A glass reactor with a 5-neck top and equipped with a glass
stirring shaft, an equal-pressure addition funnel, a temperature
probe, a pH probe, a heating mantle, coiled stainless-steel tubing
for circulation of cooling water, and a vacuum-actuated sample tube
to allow for the removal and return of sample aliquots from the
reactor was used to produce a second thermosetting PAE resin from
prepolymer II. To the reactor about 409.1 grams of water was added,
followed by about 236 grams of prepolymer II. A small amount of
water was added to adjust the prepolymer concentration to about
18.9%. The mixture was heated to a temperature of about 30.degree.
C. and about 11.64 grams of epichlorohydrin was added to produce a
reaction mixture. The reaction mixture was first stirred for a time
period of about 10 minutes at a temperature of about 30.degree. C.,
and was then heated over a time period of about 15 minutes to a
temperature of about 45.degree. C. The viscosity of the reaction
mixture was measured at about 15 minute intervals until a
Gardner-Holdt bubble tube viscosity of about A was obtained. The
reaction mixture was cooled to a temperature of about 32.degree. C.
The reaction was sampled at about 10 minute intervals until a
Gardner-Holdt viscosity of about E was obtained, whereupon about
260.1 grams of water was rapidly added. The reaction mixture was
cooled to a temperature of about 25.degree. C. while adding about
15.1 grams of 93% sulfuric acid to provide a Gardner-Holdt bubble
tube viscosity of about C, and a pH of about 7.2. The pH of the
mixture was adjusted to about 4 with additional 93% sulfuric acid.
About 66.3 grams of water was added to produce the second
thermosetting PAE resin that had a solids concentration of about 15
wt %. The second thermosetting PAE resin had a viscosity of about
37 cP, as measured by a Brookfield small sample adapter at a
temperature of about 25.degree. C. The second thermosetting PAE
resin had a number average molecular weight of about 27,100, a
weight average molecular weight of about 667,000, and a z-average
molecular weight of about 9,350,000.
Example 8
Preparation of a Third Thermosetting Resin from Prepolymer III
[0112] A glass reactor with a 5-neck top and equipped with a glass
stirring shaft, an equal-pressure addition funnel, a temperature
probe, a pH probe, a heating mantle, coiled stainless-steel tubing
for circulation of cooling water, and a vacuum-actuated sample tube
to allow for the removal and return of sample aliquots from the
reactor was used to produce a third thermosetting resin from the
prepolymer III. To the reactor about 350.4 grams of water was
added, followed by about 216.8 grams of Prepolymer III. The mixture
was heated to a temperature of about 30.degree. C. and about 17.4
grams of epichlorohydrin was added to produce a reaction mixture.
The reaction mixture was heated to a temperature of about
35.degree. C. over a time period of about 75 minutes. The viscosity
of the reaction mixture was measured at about 10 minute intervals
with a Brookfield small sample adapter at a temperature of about
25.degree. C. When the viscosity of the reaction mixture had
advanced to about 30 cP the mixture was cooled to a temperature of
about 23.degree. C. The reaction mixture was allowed to advance in
viscosity to about 70 cP as measured by Brookfield small sample
adapter at a temperature of about 25.degree. C., at which point the
reaction temperature was cooled to a temperature of about
15.degree. C. The reaction mixture was allowed to further advance
to an end-point viscosity of about 180 cP, and about 192.3 grams of
water was rapidly added thereto. About 29.54 grams of 85%
phosphoric acid as added to adjust the pH of the mixture to about
5.7. An additional 10.1 grams of 85% phosphoric acid was added to
the mixture to produce the third thermosetting PAE resin that had a
final pH of about 4.25. Water was added to adjust the solids
concentration of the third thermosetting PAE resin to about 15 wt
%. The third thermosetting PAE resin had a viscosity of about 85
cP, as measured by a Brookfield small sample adapter at a
temperature of about 25.degree. C. The third thermosetting PAE
resin had a number average molecular weight of about 25,500, a
weight average molecular weight of about 852,000, and a z-average
molecular weight of about 10,400,000.
Example 9
Preparation of a Blended Creping Adhesive
[0113] In a glass reactor equipped with a glass stirring shaft was
added the first thermosetting resin (about 4.53 wt %), the second
thermosetting resin (about 26.12 wt %), the first thermoplastic
resin (about 17.50 wt %), the second thermoplastic resin (about
28.21 wt %), and glycerin 100% (about 0.75 wt %), and water (about
22.88 wt %). The resulting mixture was stirred and stored in cool
environment. The blended adhesive had a viscosity of about 26 cP,
as measured by a Brookfield small sample adapter at a temperature
of about 25.degree. C., a pH of about 6, and a solids concentration
of about 15.8 wt %.
[0114] Embodiments of the present disclosure further relate to any
one or more of the following paragraphs:
[0115] 1. A creping adhesive, comprising: a first thermosetting
polyamidoamine-epihalohydrin resin comprising a reaction product of
a first epihalohydrin and a first polyamidoamine containing one or
more secondary amine groups, wherein the first thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 800,000 to about 1,200,000, comprises about 2 moles
to about 500 moles of reactive groups per mole of the first
thermosetting polyamidoamine-epihalohydrin resin, and has a molar
ratio of the first epihalohydrin to the secondary amine groups in
the first polyamidoamine of about 0.002:1 to about 0.1:1, and
wherein the reactive groups of the first thermosetting
polyamidoamine-epihalohydrin resin comprise azetidinium groups,
pendant halo-groups, or both; a first thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups, wherein the first thermoplastic
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 40,000 to about 200,000, and has a molar ratio of
the second epihalohydrin to the secondary amine groups in the
second polyamidoamine of about 0.001:1 to about 0.1:1; and one or
more re-wetting agents, wherein the creping adhesive comprises
about 5 wt % to about 80 wt % of the first thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the first thermoplastic polyamidoamine-epihalohydrin resin, and
about 0.1 wt % to about 30 wt % of the one or more re-wetting
agents, and wherein all weight percent values are based on the
combined weight of the first thermosetting
polyamidoamine-epihalohydrin resin, the first thermoplastic
polyamidoamine-epihalohydrin resin, and the one or more re-wetting
agents.
[0116] 2. A method for creping a cellulosic fiber web, comprising:
applying a creping adhesive to a drying surface, wherein the
creping adhesive comprises: a first thermosetting
polyamidoamine-epihalohydrin resin comprising a reaction product of
a first epihalohydrin and a first polyamidoamine containing one or
more secondary amine groups, wherein the first thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 800,000 to about 1,200,000, comprises about 2 moles
to about 500 moles of reactive groups per mole of the first
thermosetting polyamidoamine-epihalohydrin resin, and has a molar
ratio of the first epihalohydrin to the secondary amine groups in
the first polyamidoamine of about 0.002:1 to about 0.1:1, and
wherein the reactive groups of the first thermosetting
polyamidoamine-epihalohydrin resin comprise azetidinium groups,
pendant halo-groups, or both; a first thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups, wherein the first thermoplastic
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 40,000 to about 200,000, and has a molar ratio of
the second epihalohydrin to the secondary amine groups in the
second polyamidoamine of about 0.001:1 to about 0.1:1; and one or
more re-wetting agents, wherein the creping adhesive comprises
about 5 wt % to about 80 wt % of the first thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the first thermoplastic polyamidoamine-epihalohydrin resin, and
about 0.1 wt % to about 30 wt % of the one or more re-wetting
agents, and wherein all weight percent values are based on the
combined weight of the first thermosetting
polyamidoamine-epihalohydrin resin, the first thermoplastic
polyamidoamine-epihalohydrin resin, and the one or more re-wetting
agents; adhering a cellulosic fiber web to the drying surface with
the creping adhesive; and dislodging the adhered cellulosic fiber
web from the drying surface.
[0117] 3. A creped product, comprising: a creped cellulosic fiber
web; and an at least partially cured creping adhesive, wherein,
prior to curing, the creping adhesive comprises: a first
thermosetting polyamidoamine-epihalohydrin resin comprising a
reaction product of a first epihalohydrin and a first
polyamidoamine containing one or more secondary amine groups,
wherein the first thermosetting polyamidoamine-epihalohydrin resin
has a weight average molecular weight of about 800,000 to about
1,200,000, comprises about 2 moles to about 500 moles of reactive
groups per mole of the first thermosetting
polyamidoamine-epihalohydrin resin, and has a molar ratio of the
first epihalohydrin to the secondary amine groups in the first
polyamidoamine of about 0.002:1 to about 0.1:1, and wherein the
reactive groups of the first thermosetting
polyamidoamine-epihalohydrin resin comprise azetidinium groups,
pendant halo-groups, or both; a first thermoplastic
polyamidoamine-epihalohydrin resin comprising a reaction product of
a second epihalohydrin and a second polyamidoamine containing one
or more secondary amine groups, wherein the first thermoplastic
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 40,000 to about 200,000, and has a molar ratio of
the second epihalohydrin to the secondary amine groups in the
second polyamidoamine of about 0.001:1 to about 0.1:1; and one or
more re-wetting agents, wherein the creping adhesive comprises
about 5 wt % to about 80 wt % of the first thermosetting
polyamidoamine-epihalohydrin resin, about 15 wt % to about 90 wt %
of the first thermoplastic polyamidoamine-epihalohydrin resin, and
about 0.1 wt % to about 30 wt % of the one or more re-wetting
agents, and wherein all weight percent values are based on the
combined weight of the first thermosetting
polyamidoamine-epihalohydrin resin, the first thermoplastic
polyamidoamine-epihalohydrin resin, and the one or more re-wetting
agents.
[0118] 4. The creping adhesive, method, or product according to any
one of paragraphs 1 to 3, wherein the creping adhesive further
comprises a second thermosetting polyamidoamine-epihalohydrin resin
comprising a reaction product of a third epihalohydrin and a third
polyamidoamine containing one or more secondary amine groups,
wherein the second thermosetting polyamidoamine-epihalohydrin resin
has a weight average molecular weight of about 150,000 to about
800,000, comprises about 500 moles to about 700 moles of reactive
groups per mole of the second thermosetting
polyamidoamine-epihalohydrin resin, and has a molar ratio of the
third epihalohydrin to the secondary amine groups in the third
polyamidoamine of about 0.5:1 to about 0.7:1, wherein the reactive
groups of the second thermosetting polyamidoamine-epihalohydrin
resin comprise azetidinium groups, pendant halo-groups, or both,
wherein the creping adhesive comprises about 25 wt % to about 60 wt
% of the second thermosetting polyamidoamine-epihalohydrin resin,
and wherein all weight percent values are based on the combined
weight of the first thermosetting polyamidoamine-epihalohydrin
resin, the first thermoplastic polyamidoamine-epihalohydrin resin,
the second thermosetting polyamidoamine-epihalohydrin resin, and
the one or more re-wetting agents.
[0119] 5. The creping adhesive, method, or product according to any
one of paragraphs 1 to 4, wherein the creping adhesive further
comprises a second thermoplastic polyamidoamine-epihalohydrin resin
comprising a reaction product of a fourth epihalohydrin and a
fourth polyamidoamine containing one or more secondary amine
groups, wherein the second thermoplastic
polyamidoamine-epihalohydrin has a weight average molecular weight
of about 200,000 to about 3,000,000, and has a molar ratio of the
fourth epihalohydrin to the secondary amine groups in the fourth
polyamidoamine of about 0.001:1 to about 0.1:1, wherein the creping
adhesive comprises about 20 wt % to about 65 wt % of the second
thermoplastic polyamidoamine-epihalohydrin resin, and wherein all
weight percent values are based on the combined weight of the first
thermosetting polyamidoamine-epihalohydrin resin, the first
thermoplastic polyamidoamine-epihalohydrin resin, the second
thermosetting polyamidoamine-epihalohydrin resin, the second
thermoplastic polyamidoamine-epichlorohydrin resin, and the one or
more re-wetting agents.
[0120] 6. The creping adhesive, method, or product according to any
one of paragraphs 1 to 5, wherein the creping adhesive further
comprises a third thermosetting polyamidoamine-epihalohydrin resin
comprising a reaction product of a fifth epihalohydrin and a fifth
polyamidoamine containing one or more secondary amine groups,
wherein the third thermosetting polyamidoamine-epihalohydrin resin
has a weight average molecular weight of about 700,000 to about
1,500,000, comprises about 500 moles to about 700 moles of reactive
groups per mole of the third thermosetting
polyamidoamine-epihalohydrin resin, and has a molar ratio of the
fifth epihalohydrin to the secondary amine groups in the fifth
polyamidoamine of about 0.2:1 to about 0.6:1, wherein the reactive
groups comprise azetidinium groups, pendant halo-groups, or both,
wherein the creping adhesive comprises about 5 wt % to about 70 wt
% of the first thermosetting polyamidoamine-epihalohydrin resin,
about 15 wt % to about 80 wt % of the first thermoplastic
polyamidoamine-epihalohydrin resin, about 25 wt % to about 60 wt %
of the second thermosetting polyamidoamine-epihalohydrin resin,
about 20 wt % to about 65 wt % of the second thermoplastic
polyamidoamine-epihalohydrin resin, and about 2 wt % to about 65 wt
% of the third thermosetting polyamidoamine-epihalohydrin resin,
and wherein all weight percent values are based on the combined
weight of the first thermosetting polyamidoamine-epihalohydrin
resin, the first thermoplastic polyamidoamine-epihalohydrin resin,
the second thermosetting polyamidoamine-epihalohydrin resin, the
second thermoplastic polyamidoamine-epichlorohydrin resin, the
third thermosetting polyamidoamine-epichlorohydrin resin, and the
one or more re-wetting agents.
[0121] 7. The creping adhesive, method, or product according to
paragraph 4 to 6, wherein the first thermosetting
polyamidoamine-epihalohydrin resin comprises less than 500 moles of
reactive groups per mole of the first thermosetting
polyamidoamine-epihalohydrin resin, and wherein the second
thermosetting polyamidoamine-epihalohydrin resin comprises greater
than 500 moles of reactive groups per mole of the second
thermosetting polyamidoamine-epihalohydrin resin.
[0122] 8. The creping adhesive, method, or product according to any
one of paragraphs 4 to 7, wherein the first thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of greater than 800,000, and wherein the second
thermosetting polyamidoamine-epihalohydrin resin has a weight
average molecular weight of less than 800,000.
[0123] 9. The creping adhesive, method, or product according to any
one of paragraphs 5 to 8, wherein the first thermoplastic
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of less than 200,000, and wherein the second thermoplastic
polyamidoamine-epihalohydrin has a weight average molecular weight
of greater than 200,000.
[0124] 10. The creping adhesive, method, or product according to
any one of paragraphs 6 to 9, wherein the molar ratio of the third
epihalohydrin to the secondary amine groups in the third
polyamidoamine of the second thermosetting
polyamidoamine-epihalohydrin is greater than 0.5:1 to about 0.7:1,
and wherein the molar ratio of the fifth epihalohydrin to the
secondary amine groups in the fifth polyamidoamine of the third
thermosetting polyamidoamine-epihalohydrin resin is less than
0.5:1.
[0125] 11. The creping adhesive, method, or product according to
any one of paragraphs 6 to 10, wherein the second thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of less than 700,000, and wherein the third thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of greater than 700,000.
[0126] 12. The creping adhesive, method, or product according to
any one of paragraphs 6 to 11, wherein the first thermosetting
polyamidoamine-epihalohydrin resin comprises less than 500 moles of
reactive groups per mole of the first thermosetting
polyamidoamine-epihalohydrin resin, and wherein the third
thermosetting polyamidoamine-epihalohydrin resin comprises greater
than 500 moles of reactive groups per mole of the third
thermosetting polyamidoamine-epihalohydrin resin.
[0127] 13. The creping adhesive, method, or product according to
any one of paragraphs 1 to 12, wherein the first thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 1,000,000 to about 1,200,000, wherein the first
thermoplastic polyamidoamine-epihalohydrin resin has a weight
average molecular weight of about 60,000 to about 120,000.
[0128] 14. The creping adhesive, method, or product according to
any one of paragraphs 4 to 12, wherein the second thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 150,000 to about 500,000.
[0129] 15. The creping adhesive, method, or product according to
any one of paragraphs 5 to 14, wherein the second thermoplastic
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 650,000 to about 850,000.
[0130] 16. The creping adhesive, method, or product according to
any one of paragraphs 6 to 15, wherein the third thermosetting
polyamidoamine-epihalohydrin resin has a weight average molecular
weight of about 750,000 to about 950,000.
[0131] 17. The creping adhesive, method, or product according to
any one of paragraphs 1 to 16, wherein the one or more re-wetting
agents comprise a protonated amine, a protonated polyamine, a
quaternary ammonium salt, glycerin, a salt of a polycarboxylic
acids neutralized with triethanolamine, or any mixture thereof.
[0132] 18. The creping adhesive, method, or product according to
any one of paragraphs 1 to 16, wherein the one or more re-wetting
agents comprise a poly-quaternary ammonium salt.
[0133] 19. The creping adhesive, method, or product according to
any one of paragraphs 1 to 18, wherein the first thermosetting
polyamidoamine-epihalohydrin resin has a secondary amine
concentration of about 0.01 mmols per gram of the first
thermosetting polyamidoamine-epihalohydrin resin to about 5 mmols
per gram of the first thermosetting polyamidoamine-epihalohydrin
resin, and wherein the first thermoplastic
polyamidoamine-epihalohydrin resin has a secondary amine
concentration of about 4 mmols per gram of the first thermoplastic
polyamidoamine-epihalohydrin resin to about 8 mmols per gram of the
first thermoplastic polyamidoamine-epihalohydrin resin.
[0134] 20. The creping adhesive, method, or product according to
any one of paragraphs 4 to 19, wherein the second thermosetting
polyamidoamine-epihalohydrin resin has a secondary amine
concentration of about 4 mmols per gram of the second thermosetting
polyamidoamine-epihalohydrin resin to about 8 mmols per gram of the
second thermosetting polyamidoamine-epihalohydrin resin.
[0135] 21. The creping adhesive, method, or product according to
any one of paragraphs 5 to 19, wherein the second thermoplastic
polyamidoamine-epihalohydrin resin has a secondary amine
concentration of about 4 mmols per gram of the second thermoplastic
polyamidoamine-epihalohydrin resin to about 8 mmols per gram of the
second thermoplastic polyamidoamine-epihalohydrin resin.
[0136] 22. The creping adhesive, method, or product according to
any one of paragraphs 6 to 19, wherein the third thermosetting
polyamidoamine-epihalohydrin resin has a secondary amine
concentration of about 0.05 mmols per gram of the third
thermosetting polyamidoamine-epihalohydrin resin to about 0.3 mmols
per gram of the third thermosetting polyamidoamine-epihalohydrin
resin.
[0137] 23. The creping adhesive, method, or product according to
any one of paragraphs 1 to 22, wherein the creping adhesive has a
swelling index of about 5 g of water per gram of crosslinked
polymer to about 250 g of water per gram of crosslinked polymer, as
measured after extraction in a Soxhlet extractor with boiling water
for 75 minutes.
[0138] 24. The creping adhesive, method, or product according to
any one of paragraphs 1 to 22, wherein the swelling index of the
creping adhesive is about 10 g of water per gram of crosslinked
polymer to about 75 g of water per gram of crosslinked polymer, as
measured after extraction in a Soxhlet extractor with boiling water
for 75 minutes.
[0139] 25. The creping adhesive, method, or product according to
any one of paragraphs 1 to 22, wherein the swelling index of the
creping adhesive is about 60 g of water per gram of crosslinked
polymer to about 160 g of water per gram of crosslinked polymer, as
measured after extraction in a Soxhlet extractor with boiling water
for 75 minutes.
[0140] 26. The creping adhesive, method, or product according to
any one of paragraphs 1 to 22, wherein the swelling index of the
creping adhesive is about 110 g of water per gram of crosslinked
polymer to about 175 g of water per gram of crosslinked polymer, as
measured after extraction in a Soxhlet extractor with boiling water
for 75 minutes.
[0141] 27. The creping adhesive, method, or product according to
any one of paragraphs 1 to 22, wherein the swelling index of the
creping adhesive is about 160 g of water per gram of crosslinked
polymer to about 240 g of water per gram of crosslinked polymer, as
measured after extraction in a Soxhlet extractor with boiling water
for 75 minutes.
[0142] 28. The creping adhesive, method, or product according to
any one of paragraphs 1 to 27, wherein the creping adhesive has a
pH of about 2 to about 8.5.
[0143] 29. The creping adhesive, method, or product according to
any one of paragraphs 1 to 28, wherein the creping adhesive has a
pH of about 4 to about 8.
[0144] 30. The creping adhesive, method, or product according to
any one of paragraphs 1 to 29, wherein the creping adhesive has a
pH of about 5 to about 7.
[0145] 31. The creping adhesive, method, or product according to
any one of paragraphs 1 to 30, wherein the creping adhesive further
comprises one or more mineral acids, one or more organic acids, or
any mixture thereof.
[0146] 32. The creping adhesive, method, or product according to
any one of paragraphs 1 to 30, wherein the creping adhesive further
comprises a mineral acid, and wherein the mineral acid comprises
hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or
any mixture thereof.
[0147] 33. The creping adhesive, method, or product according to
any one of paragraphs 1 to 30, wherein the creping adhesive further
comprises an organic acid, and wherein the organic acid comprises
methanesulfonic acid, formic acid, acetic acid, citric acid, lactic
acid, lactobionic acid, or any mixture thereof.
[0148] 34. The creping adhesive, method, or product according to
any one of paragraphs 1 to 33, wherein the creping adhesive further
comprises polyvinyl alcohol, hemicellulose, polyvinyl amine,
polyacrylamide, or any mixture thereof.
[0149] 35. The method according to any one of paragraphs 2 or 4 to
34, further comprising heating the cellulosic fiber web to a
temperature of about 20.degree. C. to about 80.degree. C. when
adhered to the drying surface.
[0150] 36. The method according to any one of paragraphs 2 or 4 to
34, wherein the drying surface is heated to a temperature of about
100.degree. C. to about 210.degree. C.
[0151] 37. The method according to any one of paragraphs 2 or 4 to
34, wherein the drying surface is heated to a temperature of at
least 180.degree. C. to about 210.degree. C.
[0152] 38. The method according to any one of paragraphs 6 to 38,
wherein third thermosetting polyamidoamine-epihalohydrin resin is
applied to the to the drying surface separately, with respect to
the first thermosetting polyamidoamine-epihalohydrin resin, the
first thermoplastic polyamidoamine-epihalohydrin resin, the second
thermosetting polyamidoamine-epihalohydrin resin, and the second
thermoplastic polyamidoamine-epihalohydrin resin.
[0153] 39. The method according to any one of paragraphs 6 to 38,
wherein applying the creping adhesive to the drying surface
comprises applying a mixture comprising the first thermosetting
polyamidoamine-epihalohydrin resin, the first thermoplastic
polyamidoamine-epihalohydrin resin, the second thermosetting
polyamidoamine-epihalohydrin resin, the second thermoplastic
polyamidoamine-epihalohydrin resin, and the one or more re-wetting
agents; and applying the third thermosetting
polyamidoamine-epihalohydrin resin to the drying surface separately
from the mixture such that the mixture and the third thermosetting
polyamidoamine-epihalohydrin resin contact one another after being
applied to the drying surface.
[0154] Certain embodiments and features have been described using a
set of numerical upper limits and a set of numerical lower limits.
It should be appreciated that ranges including the combination of
any two values, e.g., the combination of any lower value with any
upper value, the combination of any two lower values, and/or the
combination of any two upper values are contemplated unless
otherwise indicated. Certain lower limits, upper limits and ranges
appear in one or more claims below. All numerical values are
"about" or "approximately" the indicated value, and take into
account experimental error and variations that would be expected by
a person having ordinary skill in the art.
[0155] Various terms have been defined above. To the extent a term
used in a claim is not defined above, it should be given the
broadest definition persons in the pertinent art have given that
term as reflected in at least one printed publication or issued
patent. Furthermore, all patents, test procedures, and other
documents cited in this application are fully incorporated by
reference to the extent such disclosure is not inconsistent with
this application and for all jurisdictions in which such
incorporation is permitted.
[0156] While the foregoing is directed to embodiments of the
present invention, other and further embodiments of the invention
can be devised without departing from the basic scope thereof, and
the scope thereof is determined by the claims that follow.
* * * * *