CREPING ADHESIVES AND PROCESSES FOR MAKING AND USING SAME
20240150967 · 2024-05-09
Assignee
Inventors
- Ashish Dhawan (Aurora, IL, US)
- David J. Castro (DeKalb, IL, US)
- Gary S. Furman (St. Charles, IL, US)
- Christopher Kaley (Hoffman Estates, IL, US)
Cpc classification
C09J129/04
CHEMISTRY; METALLURGY
C09J129/04
CHEMISTRY; METALLURGY
D21H17/36
TEXTILES; PAPER
C08G73/0286
CHEMISTRY; METALLURGY
C08L29/04
CHEMISTRY; METALLURGY
C08L29/04
CHEMISTRY; METALLURGY
International classification
D21H21/14
TEXTILES; PAPER
Abstract
Creping adhesives and processes for making and using same. In some embodiments, the creping adhesive can include a solvent, a modified polyvinyl alcohol, and a crosslinked resin. The crosslinked resin can include polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, where the primary crosslinking moieties can be derived from a functionally symmetric crosslinker In other embodiments, the crosslinked resin can include polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, where the primary crosslinking moieties can be derived from a first functionally symmetric crosslinker and the secondary crosslinking moieties can be derived from a second functionally symmetric crosslinker In other embodiments, the crosslinked resin can include polyamidoamine backbones crosslinked by primary crosslinking moieties, where the primary crosslinking moieties can be derived from a functionally symmetric crosslinker The modified polyvinyl alcohol can include a carboxylated, a sulfonated, a sulfated, and/or a sulfonated-carboxylated polyvinyl alcohol.
Claims
1. A creping adhesive, comprising: a solvent; a modified polyvinyl alcohol comprising a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker
2. The creping adhesive of claim 1, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
3. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I): ##STR00151## and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
4. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II): ##STR00152## and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
5. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III): ##STR00153## and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
6. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV): ##STR00154## and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
7. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V): ##STR00155## and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
8. The creping adhesive of claim 1, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI): ##STR00156## and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
9. The creping adhesive of claim 1, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
10. The creping adhesive of claim 1, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII): ##STR00157## wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group; ##STR00158## wherein x is a number from 1 to about 100; ##STR00159## wherein y is a number from 1 to about 100; ##STR00160## wherein x+y is a number from 1 to about 100; ##STR00161## wherein z is a number from 1 to about 100; or ##STR00162## wherein a q/p ratio is a number from about 10 to about 1000.
11. The creping adhesive of claim 1, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from ##STR00163## and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
12. The creping adhesive of claim 1, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
13. The creping adhesive of claim 1, wherein the propanediyl moieties are derived from an epihalohydrin.
14. The creping adhesive of claim 13, wherein the crosslinked resin is made by reacting the epihalohydrin with a polyamidoamine crosslinked by the primary crosslinking moieties in the presence of the solvent, and wherein a mixture of the solvent and the crosslinked resin is blended with the modified polyvinyl alcohol to produce the creping adhesive.
15. The creping adhesive of claim 13, wherein the crosslinked resin is made by reacting the epihalohydrin with a polyamidoamine crosslinked by the primary crosslinking moieties in the presence of the solvent and the modified polyvinyl alcohol.
16. The creping adhesive of claim 1, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa, and wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
17. The creping adhesive of claim 1, wherein: the solvent comprises water, the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, wherein: the sulfonated polyvinyl alcohol has the following chemical formula (III): ##STR00164## and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20, the functionally symmetric crosslinker comprises a bis(acrylamide), the propanediyl moieties are derived from an epihalohydrin, the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin, and the crosslinked resin is made by reacting the epihalohydrin with a polyamidoamine crosslinked by the primary crosslinking moieties in the presence of the solvent, and wherein a mixture of the solvent and the crosslinked resin is blended with the modified polyvinyl alcohol to produce the creping adhesive.
18. The creping adhesive of claim 1, wherein the polyamidoamine backbones are derived from a polyamidoamine having the following chemical formula (XIV): ##STR00165## wherein R.sup.1 is (CH.sub.2).sub.u and u is 1, 2, 3, 4, or 5, each R.sup.2 is independently (CH.sub.2).sub.v and v is 2, 3, or 4, i is 1, 2, or 3, and j is a number from 1 to about 10,000.
19. A process for making a creping adhesive, comprising: blending a resin mixture with a modified polyvinyl alcohol to produce the creping adhesive, wherein: the resin mixture comprises: a solvent; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker, and the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
20. A process for creping a paper web, comprising: applying to a rotating creping cylinder a creping adhesive; pressing the paper web against the creping cylinder to adhere the paper web to the creping cylinder; and dislodging the paper web from the creping cylinder with a doctor blade, wherein the creping adhesive comprises a solvent, a modified polyvinyl alcohol, and a crosslinked resin, wherein the crosslinked resin comprises polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker, and wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
Description
EXAMPLES
[0126] 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. All parts, proportions, and percentages are by weight unless otherwise indicated.
Example 1
[0127] A first crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, where the primary crosslinking moieties were derived from a functionally symmetric crosslinker and the propanediyl moieties were derived from an epihalohydrin was produced according to the following process. A prepolymer (about 41.3 wt % solids, about 14.03 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an a resistance temperature detector (RTD) probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 34.23 g) and a sulfonated polyvinyl alcohol (Sekisui 52012, about 15 wt % solids, about 50 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Epichlorohydrin (about 0.47 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 5 hours to produce the creping adhesive. After 5 hours, the creping adhesive was cooled to a temperature of less than 35? C. The pH of the creping adhesive was adjusted to about 6.1 by adding concentrated sulfuric acid (about 1.36 g). A final creping adhesive (Ex. 1) that included about 15.11 wt % of solids was obtained.
Example 2
[0128] A second crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, where the primary crosslinking moieties were derived from a functionally symmetric crosslinker and the propanediyl moieties were derived from an epihalohydrin was produced according to the following process. A prepolymer (about 41.3 wt % solids, about 13.49 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 34.55 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 15 wt % solids, about 50 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Epichlorohydrin (about 0.64 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 5 hours to produce the creping adhesive. After 5 hours, the creping adhesive was cooled to a temperature of less than 35? C. and had a solids content of about 15.02 wt %. The pH of the creping adhesive was adjusted to about 6.6 by adding concentrated sulfuric acid (about 1.31 g). A final creping adhesive (Ex. 2) resulted in a stable single phase.
TABLE-US-00001 TABLE 1 Film PAE/PVOH Crosslinker, Test Solubility, Example Prepolymer Mass Ratio Crosslinker % pH % Ex. 1 PAA 1:1 Epichlorohydrin 0.47 6.1 50.8 crosslinked with MBA Ex. 2 PAA 1:1 Epichlorohydrin 0.64 6.6 36.3 crosslinked with MBA
[0129] As can be seen in Table 1, the film solubility decreased as the epichlorohydrin content increased.
Example 3
[0130] A first crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, where the primary crosslinking moieties were derived from a first functionally symmetric crosslinker and the secondary crosslinking moieties were derived from a second functionally symmetric crosslinker was produced according to the following process. A prepolymer (about 39.6 wt % solids, about 12.10 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 44.02 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 10.4 wt % solids, about 57.78 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 0.62 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. The creping adhesive (Ex. 3) had a pH of about 9.36 and contained about 9.97 wt % of solids.
Example 4
[0131] A second crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, where the primary crosslinking moieties were derived from a first functionally symmetric crosslinker and the secondary crosslinking moieties were derived from a second functionally symmetric crosslinker was produced according to the following process. A prepolymer (about 39.6 wt % solids, about 23.55 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 80.16 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 11 wt % solids, about 104.99 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 2.21 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. The creping adhesive (Ex. 4) had a pH of about 9.09 and contained about 10.95 wt % of solids.
Example 5
[0132] A third crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, where the primary crosslinking moieties were derived from a first functionally symmetric crosslinker and the secondary crosslinking moieties were derived from a second functionally symmetric crosslinker was produced according to the following process. A prepolymer (about 39.6 wt % solids, about 21.98 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 79.93 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 10.4 wt % solids, about 104.99 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 2.63 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. The creping adhesive (Ex. 5) had a pH of about 9.16 and contained about 10.62 wt % of solids.
Example 6
[0133] A fourth crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, where the primary crosslinking moieties were derived from a first functionally symmetric crosslinker and the secondary crosslinking moieties were derived from a second functionally symmetric crosslinker was produced according to the following process. A prepolymer (about 39.6 wt % solids, about 22.00 g) produced by reacting a polyamidoamine (diethylenetriamine-dimethyl glutarate) and about 1 wt % of a first crosslinker (N,N-methylenebisacrylamide (MBA)), based on the weight of the prepolymer, was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 79.95 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 11 wt % solids, about 105.02 g) and the mixture was stirred at about 500 revolutions per minute (rpm). The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 3.01 g) was added to the reactor over a period of about 90 minutes. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. and had a solids content of about 11.08 wt %. The creping adhesive (Ex. 6) had a pH of about 9.03 and was adjusted to about 6.7 by adding concentrated sulfuric acid resulting in a stable single-phase product.
TABLE-US-00002 TABLE 2 Viscosity Viscosity before after Film PAE/PVOH Crosslinker, crosslinked crosslinked Test Solubility, Example Mass Ratio Crosslinker % (cP) (cP) pH % Ex. 3 1:1 EGDGE 0.54 31 40 7.0 62.7 Ex. 4 1:1 EGDGE 1.05 45 96 6.4 43.6 Ex. 5 1:1 EGDGE 1.26 32 79 6.5 40.9 Ex. 6 1:1 EGDGE 1.43 45 292 6.9 28.5
[0134] As can be seen in Table 2, the film solubility decreased as the ethylene glycol diglycidyl ether content increased.
Example 7
[0135] A crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties, where the primary crosslinking moieties were derived from a functionally symmetric crosslinker was produced according to the following process. A polyamidoamine (un-crosslinked diethylenetriamine-dimethyl glutarate, about 45 wt % solids, about 19.97 g) was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 79.93 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 11% solids, about 48.04 g,) and the mixture was stirred at 500 rpm. The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 2.13 g) was added to the reactor over a period of about 90 min. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. The creping adhesive (Ex. 7) had a pH of about 9.3 and contained about 10.93 wt % of solids.
Example 8
[0136] A crosslinked resin that included polyamidoamine backbones crosslinked by primary crosslinking moieties, where the primary crosslinking moieties were derived from a functionally symmetric crosslinker was produced according to the following process. A polyamidoamine (un-crosslinked diethylenetriamine-dimethyl glutarate, about 45 wt % solids, about 19.95 g) was added to a 3-neck, 250-mL reactor equipped with an RTD probe, oil bath, overhead motor, and magnetic stir bar. The reactor was charged with deionized water (about 79.98 g) and a sulfonated polyvinyl alcohol (Sekisui S2012, about 11% solids, about 49.60 g,) and the mixture was stirred at 500 rpm. The mixture was heated to a temperature of about 70? C. Ethylene glycol diglycidyl ether (about 1.51 g) was added to the reactor over a period of about 90 min. The mixture was maintained at a temperature of about 70? C. for an additional 6 hours to produce the creping adhesive. After 6 hours, the creping adhesive was cooled to a temperature of less than 35? C. and had a solids content of about 10.56 wt %. The creping adhesive (Ex. 8) had a pH of about 9.1 and was adjusted to about 6.6 by adding concentrated sulfuric acid resulting a stable single phase product.
TABLE-US-00003 TABLE 3 Viscosity Viscosity before after Film PAE/PVOH Crosslinker crosslinked crosslinked Test Solubility Example Mass Ratio Crosslinker % (cP) (cP) pH % Ex. 7 1.9 EGDGE 1.00 34 67 7.0 74.6 Ex. 8 2.1 EGDGE 1.42 27 434 6.4 47.9
[0137] As can be seen in Table 3, the film solubility decreased as the ethylene glycol diglycidyl ether content increased.
[0138] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:
[0139] 1. A creping adhesive, comprising: a solvent; a modified polyvinyl alcohol comprising a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker
[0140] 2. The creping adhesive of paragraph 1, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0141] 3. The creping adhesive of paragraph 1 or 2, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0142] 4. The creping adhesive of any of paragraphs 1 to 3, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00021## [0143] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0144] 5. The creping adhesive of any of paragraphs 1 to 4, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00022## [0145] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and 1 is a number from 0-10.
[0146] 6. The creping adhesive of any of paragraphs 1 to 5, wherein the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00023## [0147] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0148] 7. The creping adhesive of any of paragraphs 1 to 6, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00024## [0149] and wherein k is a number from 1 to 98,1 is a number from 1 to 20, and m is a number from 0 to 30.
[0150] 8. The creping adhesive of any of paragraphs 1 to 7, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00025## [0151] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0152] 9. The creping adhesive of any of paragraphs 1 to 8, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00026## [0153] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0154] 0. The creping adhesive of any of paragraphs 1 to 9, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0155] 1. The creping adhesive of any of paragraphs 1 to 10, wherein the solvent comprises water.
[0156] 2. The creping adhesive of any of paragraphs 1 to 11, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00027## [0157] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00028## [0158] wherein x is a number from 1 to about 100;
##STR00029## [0159] wherein y is a number from 1 to about 100;
##STR00030## [0160] wherein x+y is a number from 1 to about 100;
##STR00031## [0161] wherein z is a number from 1 to about 100; or
##STR00032## [0162] wherein a q/p ratio is a number from about 10 to about 1000.
[0163] 3. The creping adhesive of any of paragraphs 1 to 12, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00033## [0164] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0165] 4. The creping adhesive of any of paragraphs 1 to 13, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0166] 5. The creping adhesive of any of paragraphs 1 to 14, wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0167] 6. The creping adhesive of any of paragraphs 1 to 15, wherein the propanediyl moieties are derived from an epihalohydrin.
[0168] 7. The creping adhesive of paragraph 16, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or a mixture thereof.
[0169] 8. The creping adhesive of any of paragraphs 1 to 17, wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the propanediyl moieties are derived from epichlorohydrin.
[0170] 9. The creping adhesive of any of paragraphs 16 to 18, wherein the crosslinked resin is made by reacting the epihalohydrin with a polyamidoamine crosslinked by the primary crosslinking moieties in the presence of the solvent and the modified polyvinyl alcohol.
[0171] 20. The creping adhesive of paragraph 19, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0172] 21. The creping adhesive of paragraph 19 or 20, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0173] 22. The creping adhesive of any of paragraphs 19 to 21, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0174] 23. The creping adhesive of any of paragraphs 19 to 22, wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0175] 24. The creping adhesive of any of paragraphs 19 to 23, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0176] 25. The creping adhesive of any of paragraphs 16 to 18, wherein the crosslinked resin is made by reacting the epihalohydrin with a polyamidoamine crosslinked by the primary crosslinking moieties in the presence of the solvent, and wherein a mixture of the solvent and the crosslinked resin is blended with the modified polyvinyl alcohol to produce the creping adhesive.
[0177] 26. The creping adhesive of paragraph 25, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0178] 27. The creping adhesive of paragraph 25 or 26, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0179] 28. The creping adhesive of any of paragraphs 25 to 27, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0180] 29. The creping adhesive of any of paragraphs 25 to 28, wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0181] 30. The creping adhesive of any of paragraphs 25 to 29, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0182] 31. A creping adhesive, comprising: a solvent; a modified polyvinyl alcohol comprising a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, wherein the primary crosslinking moieties are derived from a first functionally symmetric crosslinker, and wherein the secondary crosslinking moieties are derived from a second functionally symmetric crosslinker
[0183] 32. The creping adhesive of paragraph 31, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0184] 33. The creping adhesive of paragraph 31 or 32, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0185] 34. The creping adhesive of any of paragraphs 31 to 33, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00034## [0186] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0187] 35. The creping adhesive of any of paragraphs 31 to 34, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00035## [0188] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0189] 36. The creping adhesive of any of paragraphs 31 to 35, wherein the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00036## [0190] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0191] 37. The creping adhesive of any of paragraphs 31 to 36, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00037## [0192] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0193] 38. The creping adhesive of any of paragraphs 31 to 37, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00038## [0194] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0195] 39. The creping adhesive of any of paragraphs 31 to 38, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00039## [0196] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0197] 40. The creping adhesive of any of paragraphs 31 to 39, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0198] 41. The creping adhesive of any of paragraphs 31 to 40, wherein the solvent comprises water.
[0199] 42. The creping adhesive of any of paragraphs 31 to 41, wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently have the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00040## [0200] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00041## [0201] wherein x is a number from 1 to about 100;
##STR00042## [0202] wherein y is a number from 1 to about 100;
##STR00043## [0203] wherein x+y is a number from 1 to about 100;
##STR00044## [0204] wherein z is a number from 1 to about 100; or
##STR00045## [0205] wherein a q/p ratio is a number from about 10 to about 1000.
[0206] 43. The creping adhesive of any of paragraphs 31 to 42, wherein at least one of the first functionally symmetric crosslinker and the second functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00046## [0207] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0208] 44. The creping adhesive of any of paragraphs 31 to 43, wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0209] 45. The creping adhesive of any of paragraphs 31 to 44, wherein first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0210] 46. The creping adhesive of any of paragraphs 31 to 45, wherein the first functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the second functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether.
[0211] 47. The creping adhesive of any of paragraphs 31 to 46, wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker are different from one another.
[0212] 48. The creping adhesive of any of paragraphs 31 to 47, wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker are the same functionally symmetric crosslinker, wherein the primary crosslinking moieties are formed by reacting a polyamidoamine and a first portion of the functionally symmetric crosslinker in the presence of the solvent to produce a prepolymer, and wherein the secondary crosslinking moieties are formed by reacting the prepolymer and a second portion of the functionally symmetric crosslinker in the presence of the solvent and the modified polyvinyl alcohol.
[0213] 49. The creping adhesive of any of paragraphs 31 to 48, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0214] 50. The creping adhesive of any of paragraphs 31 to 49, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0215] 51. The creping adhesive of any of paragraphs 31 to 50, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0216] 52. The creping adhesive of any of paragraphs 31 to 51, wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0217] 53. The creping adhesive of any of paragraphs 31 to 52, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0218] 54. A creping adhesive, comprising: a solvent; a polyvinyl alcohol, a modified polyvinyl alcohol, or a mixture thereof; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker
[0219] 55. The creping adhesive of paragraph 54, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the crosslinked resin, any polyvinyl alcohol and any modified polyvinyl alcohol.
[0220] 56. The creping adhesive of paragraph 54 or 55, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, up to about 70 wt % of the polyvinyl alcohol, up to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, any polyvinyl alcohol, any modified polyvinyl alcohol, and the crosslinked resin, and wherein the creping adhesive comprises about 1 wt % to about 70 wt % of a total amount of any polyvinyl alcohol and any modified polyvinyl alcohol, based on the combined weight of the solvent, any polyvinyl alcohol, any modified polyvinyl alcohol, and the crosslinked resin.
[0221] 57. The creping adhesive of any of paragraphs 54 to 56, wherein the creping adhesive comprises the modified polyvinyl alcohol, and wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0222] 58. The creping adhesive of paragraph 57, wherein the creping adhesive comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00047## [0223] wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0224] 59. The creping adhesive of paragraph 57 or 58, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00048## [0225] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and 1 is a number from 0-10.
[0226] 60. The creping adhesive of any of paragraphs 57 to 59, wherein the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00049## [0227] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0228] 61. The creping adhesive of any of paragraphs 57 to 60, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00050## [0229] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0230] 62. The creping adhesive of any of paragraphs 57 to 61, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00051## [0231] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0232] 63. The creping adhesive of any of paragraphs 57 to 62, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00052## [0233] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0234] 64. The creping adhesive of any of paragraphs 57 to 63, wherein the creping adhesive comprises the polyvinyl alcohol, and wherein the polyvinyl alcohol has the following chemical formula (XIII):
##STR00053## [0235] and wherein k is a number from 1 to 99 and 1 is a number from 0 to 30.
[0236] 65. The creping adhesive of any of paragraphs 57 to 64, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0237] 66. The creping adhesive of any of paragraphs 57 to 65, wherein the solvent comprises water.
[0238] 67. The creping adhesive of any of paragraphs 57 to 66, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00054## [0239] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00055## [0240] wherein x
##STR00056## [0241] wherein y is a number from 1 to about 100;
##STR00057## [0242] wherein x+y is a number from 1 to about 100;
##STR00058## [0243] wherein z is a number from 1 to about 100; or
##STR00059## [0244] wherein a q/p ratio is a number from about 10 to about 1000.
[0245] 68. The creping adhesive of any of paragraphs 57 to 67, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00060## [0246] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0247] 69. The creping adhesive of any of paragraphs 57 to 68, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0248] 70. The creping adhesive of any of paragraphs 57 to 69, wherein functionally symmetric crosslinker comprises methylene-bis-acrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0249] 71. The creping adhesive of any of paragraphs 57 to 70, wherein the functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether.
[0250] 72. The creping adhesive of any of paragraphs 57 to 71, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0251] 73. The creping adhesive of any of paragraphs 57 to 72, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0252] 74. The creping adhesive of any of paragraphs 57 to 73, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0253] 75. The creping adhesive of any of paragraphs 57 to 74, wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0254] 76. The creping adhesive of any of paragraphs 57 to 75, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0255] 77. The creping adhesive of any of paragraphs 1 to 76, wherein the polyamidoamine backbones are derived from a polyamidoamine having chemical formula (XIV)
##STR00061## [0256] wherein R.sup.1 is (CH.sub.2).sub.u and u is 1, 2, 3, 4, or 5, each R.sup.2 is independently (CH.sub.2).sub.v and v is 2, 3, or 4, i is 1, 2, or 3, and j is a number from 1 to about 10,000.
[0257] 78. The creping adhesive of paragraph 77, wherein the polyamidoamine has a weight average molecular weight of about 3 kDa to about 20 kDa.
[0258] 79. A process for making a creping adhesive, comprising: reacting a polyamidoamine and a first crosslinker in the presence of a solvent to produce a prepolymer comprising polyamidoamine backbones crosslinked by primary crosslinking moieties, wherein the first crosslinker comprises a first functionally symmetric crosslinker; and reacting the prepolymer and a second crosslinker in the presence of the solvent and a modified polyvinyl alcohol to produce a crosslinked resin comprising polyamidoamine backbones crosslinked by the primary crosslinking moieties and secondary crosslinking moieties, wherein the second crosslinker comprises an epihalohydrin, a second functionally symmetric crosslinker, or a mixture thereof.
[0259] 80. A process for making a creping adhesive, comprising: reacting a polyamidoamine and a first crosslinker in the presence of a solvent and a modified polyvinyl alcohol to produce a prepolymer comprising polyamidoamine backbones crosslinked by primary crosslinking moieties, wherein the first crosslinker comprises a first functionally symmetric crosslinker; and reacting the prepolymer and a second crosslinker in the presence of the solvent and the modified polyvinyl alcohol to produce a crosslinked resin comprising polyamidoamine backbones crosslinked by the primary crosslinking moieties and secondary crosslinking moieties, wherein the second crosslinker comprises an epihalohydrin, a second functionally symmetric crosslinker, or a mixture thereof.
[0260] 81. The process of paragraph 79 or 80, wherein the polyamidoamine and the first crosslinker are reacted at a temperature of about 30? C. to about 100? C. for about 30 minutes to about 12 hours to produce the prepolymer.
[0261] 82. The process of any of paragraphs 79 to 81, wherein the prepolymer and the second crosslinker are reacted at a temperature of about 40? C. to about 90? C. for about 30 minutes to about 10 hours to produce the crosslinked resin.
[0262] 83. The process of any of paragraphs 79 to 82, wherein the prepolymer and the second crosslinker are reacted at a temperature of about 50? C. to about 80? C. for about 1 hour to about 8 hours to produce the crosslinked resin.
[0263] 84. A process for making a creping adhesive, comprising: reacting a polyamidoamine, a first crosslinker, and a second crosslinker in the presence of a solvent and a modified polyvinyl alcohol to produce a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, wherein: the first crosslinker comprises a first functionally symmetric crosslinker, and the second crosslinker comprises an epihalohydrin, a second functionally symmetric crosslinker, or a mixture thereof.
[0264] 85. The process of paragraph 84, wherein the polyamidoamine, the first crosslinker, and the second crosslinker are reacted at a temperature of about 30? C. to about 100? C. for about 30 minutes to about 12 hours to produce the crosslinked resin.
[0265] 86. The process of paragraph 84, wherein the polyamidoamine, the first crosslinker, and the second crosslinker are reacted at a temperature of about 40? C. to about 90? C. for about 30 minutes to about 10 hours to produce the crosslinked resin.
[0266] 87. The process of any of paragraphs 79 to 86, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0267] 88. The process of any of paragraphs 79 to 87, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0268] 89. The process of any of paragraphs 79 to 88, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0269] 90. The process of any of paragraphs 79 to 89, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0270] 91. The process of any of paragraphs 79 to 90 wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0271] 92. The process of any of paragraphs 79 to 91, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0272] 93. The process of any of paragraphs 79 to 92, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0273] 94. The process of any of paragraphs 79 to 93, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0274] 95. The process of any of paragraphs 79 to 94, wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0275] 96. The process of paragraph 95, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00062## [0276] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0277] 97. The process of paragraph 95 or 96, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00063## [0278] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0279] 98. The process of any of paragraphs 95 to 96, wherein modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00064## [0280] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0281] 99. The process of any of paragraphs 95 to 98, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00065## [0282] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0283] 100. The process of any of paragraphs 95 to 99, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V)
##STR00066## [0284] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0285] 01. The process of any of paragraphs 95 to 100, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00067## [0286] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0287] 102. The process of any of paragraphs 79 to 101, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0288] 103. The process of any of paragraphs 79 to 102, wherein the solvent comprises water.
[0289] 104. The process of any of paragraphs 79 to 103, wherein the first functionally symmetric crosslinker comprises or the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00068## [0290] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00069## [0291] wherein x is a number from 1 to about 100;
##STR00070## [0292] wherein y is a number from 1 to about 100;
##STR00071## [0293] wherein x+y is a number from 1 to about 100;
##STR00072## [0294] wherein z is a number from 1 to about 100; or
##STR00073## [0295] wherein a q/p ratio is a number from about 10 to about 1000.
[0296] 105. The process of any of paragraphs 79 to 104, wherein the first functionally symmetric crosslinker or at least one of the first functionally symmetric crosslinker and the second functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00074## [0297] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0298] 106. The process of any of paragraphs 79 to 105, wherein the first functionally symmetric crosslinker comprises or the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or any mixture thereof.
[0299] 107. The process of any of paragraphs 79 to 106, wherein the first functionally symmetric crosslinker comprises or the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0300] 108. The process of any of paragraphs 79 to 107, wherein the second crosslinker comprises the epihalohydrin, and wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or a mixture thereof.
[0301] 109. The process of any of paragraphs 79 to 108, wherein the first crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the second crosslinker comprises epichlorohydrin.
[0302] 110. The process of any of paragraphs 79 to 109, wherein the first crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the second crosslinker comprises ethylene glycol diglycidyl ether.
[0303] 111. A process for making a creping adhesive, comprising: reacting a polyamidoamine and a functionally symmetric crosslinker in the presence of a solvent to produce a prepolymer comprising polyamidoamine backbones crosslinked by primary crosslinking moieties derived from the functionally symmetric crosslinker; reacting the prepolymer and an epihalohydrin in the presence of the solvent to produce a crosslinked resin comprising polyamidoamine backbones crosslinked by the primary crosslinking moieties and propanediyl moieties; and blending the crosslinked resin with a modified polyvinyl alcohol to produce the creping adhesive.
[0304] 112. The process of paragraph 111, wherein the polyamidoamine and the functionally symmetric crosslinker are reacted at a temperature of about 30? C. to about 100? C. for about 30 minutes to about 12 hours to produce the prepolymer.
[0305] 113. The process of paragraph 111 or 112, wherein the prepolymer and the epihalohydrin are reacted at a temperature of about 40? C. to about 90? C. for about 30 minutes to about 10 hours to produce the crosslinked resin.
[0306] 114. The process of any of paragraphs 111 to 113, wherein the prepolymer and the epihalohydrin are reacted at a temperature of about 50? C. to about 80? C. for about 1 hour to about 8 hours to produce the crosslinked resin.
[0307] 115. The process of any of paragraphs 111 to 114, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0308] 116. The process of any of paragraphs 111 to 115 wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0309] 117. The process of any of paragraphs 111 to 116, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0310] 118. The process of any of paragraphs 111 to 117, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0311] 119. The process of any of paragraphs 111 to 118 wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0312] 120. The process of any of paragraphs 111 to 119, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0313] 121. The process of any of paragraphs 111 to 120, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0314] 122. The process of any of paragraphs 111 to 121, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0315] 123. The process of any of paragraphs 111 to 122, wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0316] 124. The process of paragraph 123, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00075## [0317] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0318] 125. The process of paragraph 123 or 124, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00076## [0319] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0320] 126. The process of any of paragraphs 123 to 125, wherein modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00077## [0321] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0322] 127. The process of any of paragraphs 123 to 126, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00078## [0323] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0324] 128. The process of any of paragraphs 123 to 127, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00079## [0325] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0326] 129. The process of any of paragraphs 123 to 128, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00080## [0327] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0328] 130. The process of any of paragraphs 111 to 129, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0329] 131. The process of any of paragraphs 111 to 130, wherein the solvent comprises water.
[0330] 132. The process of any of paragraphs 111 to 131, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00081## [0331] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00082## [0332] wherein x is a number from 1 to about 100;
##STR00083## [0333] wherein y is a number from 1 to about 100;
##STR00084## [0334] wherein x+y is a number from 1 to about 100;
##STR00085## [0335] wherein z is a number from 1 to about 100; or
##STR00086## [0336] wherein a q/p ratio is a number from about 10 to about 1000.
[0337] 133. The process of any of paragraphs 111 to 132, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00087## [0338] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0339] 134. The process of any of paragraphs 111 to 133, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0340] 135. The process of any of paragraphs 111 to 134, wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0341] 136. The process of any of paragraphs 111 to 135, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or a mixture thereof.
[0342] 137. A process for making a creping adhesive, comprising: reacting a polyamidoamine with a functionally symmetric crosslinker in the presence of a solvent and a polyvinyl alcohol, a modified polyvinyl alcohol, or a mixture thereof to produce a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties derived from the functionally symmetric crosslinker
[0343] 138. The process of paragraph 137, wherein the polyamidoamine and the functionally symmetric crosslinker are reacted at a temperature of about 40? C. to about 100? C. for about 30 minutes to about 10 hours to produce the prepolymer.
[0344] 139. The process of paragraph 137 or 138, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0345] 140. The process of any of paragraphs 137 to 139, wherein the creping adhesive has a pH of about 7 to about 9.
[0346] 141. The process of any of paragraphs 137 to 140, wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0347] 142. The process of any of paragraphs 137 to 141, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0348] 143. The process of any of paragraphs 137 to 142, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0349] 144. The process of any of paragraphs 137 to 143, wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0350] 145. The process of any of paragraphs 137 to 144, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0351] 146. The process of any of paragraphs 137 to 145, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the crosslinked resin, any polyvinyl alcohol, and any modified polyvinyl alcohol.
[0352] 147. The process of any of paragraphs 137 to 146, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the crosslinked resin, up to about 70 wt % of the polyvinyl alcohol, and up to about 70 wt % of the modified alcohol, based on a combined weight of the solvent, the crosslinked resin, any polyvinyl alcohol, and any modified polyvinyl alcohol, and wherein the creping adhesive comprises about 1 wt % to about 70 wt % of a total amount of any polyvinyl alcohol and any modified polyvinyl alcohol, based on the combined weight of the solvent, any polyvinyl alcohol, any modified polyvinyl alcohol, and the crosslinked resin.
[0353] 148. The process of any of paragraphs 137 to 147, wherein the creping adhesive comprises the modified polyvinyl alcohol, and wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0354] 149. The process of paragraph 148, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00088## [0355] wherein a is a number from 1 to 98, b is a number from 0 to 30, and c is a number from 1 to 20.
[0356] 150. The process of paragraph 148 or 149, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00089## [0357] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0358] 151. The process of any of paragraphs 148 to 150, wherein the modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, and wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00090## [0359] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0360] 152. The process of any of paragraphs 148 to 151, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00091## [0361] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0362] 153. The process of any of paragraphs 148 to 152, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00092## [0363] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0364] 154. The process of any of paragraphs 148 to 152, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00093## [0365] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0366] 155. The process of any of paragraphs 137 to 154, wherein the creping adhesive comprises the polyvinyl alcohol, wherein the polyvinyl alcohol has the following chemical formula (XIII)
##STR00094## [0367] and wherein k is a number from 1 to 99 and 1 is a number from 0 to 30.
[0368] 156. The process of any of paragraphs 137 to 155, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0369] 157. The process of any of paragraphs 137 to 156, wherein the solvent comprises water.
[0370] 158. The process of any of paragraphs 137 to 157, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00095## [0371] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00096## [0372] wherein x is a number from 1 to about 100;
##STR00097## [0373] wherein y is a number from 1 to about 100;
##STR00098## [0374] wherein x+y is a number from 1 to about 100;
##STR00099## [0375] wherein z is a number from 1 to about 100; or
##STR00100## [0376] wherein a q/p ratio is a number from about 10 to about 1000.
[0377] 159. The process of any of paragraphs 137 to 158, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00101## [0378] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0379] 160. The process of any of paragraphs 137 to 159, wherein the functionally symmetric crosslinker a comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0380] 161. The process of any of paragraphs 137 to 160, wherein functionally symmetric crosslinker comprises poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, polyethylene glycol diacrylate, or a mixture thereof.
[0381] 162. The process of any of paragraphs 137 to 161, wherein the functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether.
[0382] 163. The process of any of paragraphs 79 to 162, wherein the polyamidoamine backbones are derived from a polyamidoamine having chemical formula (XIV):
##STR00102## [0383] wherein R.sup.1 is (CH.sub.2).sub.u and u is 1, 2, 3, 4, or 5, each R.sup.2 is independently (CH.sub.2).sub.v and v is 2, 3, or 4, i is 1, 2, or 3, and j is a number from 1 to about 10,000.
[0384] 164. The process of paragraph 163, wherein the polyamidoamine has a weight average molecular weight of about 3 kDa to about 20 kDA.
[0385] 165. A process for making a creping adhesive, comprising: blending a resin mixture with a modified polyvinyl alcohol to produce the creping adhesive, wherein: the resin mixture comprises: a solvent; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker, and the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0386] 166. The process of paragraph 165, wherein the crosslinked resin and the modified polyvinyl alcohol are blended at a temperature of about 20? C. to about 60? C. for about 15 minutes to about 2 hours to produce the creping adhesive.
[0387] 167. The process of paragraph 165 or 166, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0388] 168. The process of any of paragraphs 165 to 167 wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0389] 169. The process of any of paragraphs 165 to 168, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0390] 170. The process of any of paragraphs 165 to 169, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0391] 171. The process of any of paragraphs 165 to 170 wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0392] 172. The process of any of paragraphs 165 to 171, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0393] 173. The process of any of paragraphs 165 to 172, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0394] 174. The process of any of paragraphs 165 to 173, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0395] 175. The process of any of paragraphs 165 to 174, wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0396] 176. The process of paragraph 175, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00103## [0397] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0398] 177. The process of paragraph 175 or 176, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00104## [0399] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0400] 178. The process of any of paragraphs 175 to 177, wherein modified polyvinyl alcohol comprises the sulfonated polyvinyl alcohol, wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00105## [0401] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0402] 179. The process of any of paragraphs 175 to 178, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00106## [0403] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0404] 180. The process of any of paragraphs 175 to 179, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00107## [0405] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0406] 181. The process of any of paragraphs 175 to 180, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00108## [0407] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0408] 182. The process of any of paragraphs 165 to 181, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0409] 183. The process of any of paragraphs 165 to 182, wherein the solvent comprises water.
[0410] 184. The process of any of paragraphs 165 to 183, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII)
##STR00109## [0411] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00110## [0412] wherein x is a number from 1 to about 100;
##STR00111## [0413] wherein y is a number from 1 to about 100;
##STR00112## [0414] wherein x+y is a number from 1 to about 100;
##STR00113## [0415] wherein z is a number from 1 to about 100; or
##STR00114## [0416] wherein a q/p ratio is a number from about 10 to about 1000.
[0417] 185. The process of any of paragraphs 165 to 184, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00115## [0418] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0419] 186. The process of any of paragraphs 165 to 185, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0420] 187. The process of any of paragraphs 165 to 186, wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0421] 188. The process of any of paragraphs 165 to 187, wherein the propanediyl moieties are derived from an epihalohydrin.
[0422] 189. The process of paragraph 188, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or a mixture thereof.
[0423] 190. A process for creping a paper web, comprising: applying to a rotating creping cylinder a creping adhesive; pressing the paper web against the creping cylinder to adhere the paper web to the creping cylinder; and dislodging the paper web from the creping cylinder with a doctor blade, wherein the creping adhesive comprises a solvent, a modified polyvinyl alcohol, and a crosslinked resin, and wherein: the crosslinked resin comprises polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker, or the crosslinked resin comprises polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, wherein the primary crosslinking moieties are derived from a first functionally symmetric crosslinker, and wherein the secondary crosslinking moieties are derived from a second functionally symmetric crosslinker
[0424] 191. The process of paragraph 190, wherein the rotating creping cylinder is at a temperature of about 100? C. to about 120? C., and wherein the creping adhesive is at a temperature of about 20? C. to about 70? C. when applied to the rotating cylinder.
[0425] 192. The process of paragraph 190 or 191, wherein the creping adhesive is applied to the surface of the rotating creping cylinder at a rate of about 10 mg/m 2 to about 70 mg/m 2 .
[0426] 193. The process of any of paragraphs 190 to 192, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0427] 194. The process of paragraph 190 to 193, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0428] 195. The process of any of paragraphs 190 to 194 wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0429] 196. The process of any of paragraphs 190 to 195, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the modified polyvinyl alcohol and the crosslinked resin.
[0430] 197. The process of any of paragraphs 190 to 196, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, about 1 wt % to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, the modified polyvinyl alcohol, and the crosslinked resin.
[0431] 198. The process of any of paragraphs 190 to 197, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch.
[0432] 199. The process of any of paragraphs 190 to 198, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0433] 200. The process of any of paragraphs 190 to 199 wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0434] 201. The process of any of paragraphs 190 to 200, wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00116## [0435] and wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0436] 202. The process of any of paragraphs 190 to 201, wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00117## [0437] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0438] 203. The process of any of paragraphs 190 to 202, wherein the modified polyvinyl alcohol comprises a sulfonated polyvinyl alcohol, wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00118## [0439] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0440] 204. The process of any of paragraphs 190 to 203, wherein the modified polyvinyl alcohol comprises a sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00119## [0441] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0442] 205. The process of any of paragraphs 190 to 204, wherein the modified polyvinyl alcohol comprises a sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00120## [0443] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0444] 206. The process of any of paragraphs 190 to 205, wherein the modified polyvinyl alcohol comprises a sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00121## [0445] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0446] 207. The process of any of paragraphs 190 to 206, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof. 208. The process of any of paragraphs 190 to 207, wherein the solvent comprises water.
[0447] 209. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00122## [0448] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00123## [0449] wherein x is a number from 1 to about 100;
##STR00124## [0450] wherein y is a number from 1 to about 100;
##STR00125## [0451] wherein x+y is a number from 1 to about 100;
##STR00126## [0452] wherein z is a number from 1 to about 100; or
##STR00127## [0453] wherein a q/p ratio is a number from about 10 to about 1000.
[0454] 210. The process of any of paragraphs 190 to 209, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00128## [0455] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0456] 211. The process of any of paragraphs 190 to 210, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0457] 212. The process of any of paragraphs 190 to 211, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0458] 213. The process of any of paragraphs 190 to 212, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the propanediyl moieties are derived from an epihalohydrin.
[0459] 214. The process of paragraph 213, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or a mixture thereof.
[0460] 215. The process of any of paragraphs 190 to 214, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the propanediyl moieties, and wherein the functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the propanediyl moieties are derived from epichlorohydrin.
[0461] 216. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently have the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00129## [0462] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00130## [0463] wherein x is a number from 1 to about 100;
##STR00131## [0464] wherein y is a number from 1 to about 100;
##STR00132## [0465] wherein x+y is a number from 1 to about 100;
##STR00133## [0466] wherein z is a number from 1 to about 100; or
##STR00134## [0467] wherein a q/p ratio is a number from about 10 to about 1000.
[0468] 217. The process of any of paragraphs 190 to 208 or 216, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein at least one of the first functionally symmetric crosslinker and the second functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00135## [0469] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0470] 218. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0471] 219. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein first functionally symmetric crosslinker and the second functionally symmetric crosslinker independently comprise N,N-methylene-bis-acrylamide, N,N-methylene-bis-methacrylamide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0472] 220. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein the first functionally symmetric crosslinker comprises N,N-methylene-bis-acrylamide, and wherein the second functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether.
[0473] 221. The process of any of paragraphs 190 to 208, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, and wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker are different from one another.
[0474] 222. The process of any of paragraphs 190 to 208 or 216 to 221, wherein the crosslinked resin comprises the polyamidoamine backbones crosslinked by the primary crosslinking moieties and the secondary crosslinking moieties, wherein the first functionally symmetric crosslinker and the second functionally symmetric crosslinker are the same functionally symmetric crosslinker, wherein the primary crosslinking moieties are formed by reacting a polyamidoamine and a first portion of the functionally symmetric crosslinker in the presence of the solvent to produce a prepolymer, and wherein the secondary crosslinking moieties are formed by reacting the prepolymer and a second portion of the functionally symmetric crosslinker in the presence of the solvent and the modified polyvinyl alcohol.
[0475] 223. A process for creping a paper web, comprising: applying to a surface of a rotating creping cylinder a creping adhesive; pressing the paper web against the creping cylinder to adhere the paper web to the creping cylinder; and dislodging the paper web from the creping cylinder with a doctor blade, wherein the creping adhesive comprises a solvent, a crosslinked resin, and a polyvinyl alcohol, a modified polyvinyl alcohol, or a mixture thereof, and wherein the crosslinked resin comprises polyamidoamine backbones crosslinked by primary crosslinking moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker
[0476] 224. The process of paragraph 223, wherein the rotating creping cylinder is at a temperature of about 100? C. to about 120? C., and wherein the creping adhesive is at a temperature of about 20? C. to about 70? C. when applied to the rotating cylinder.
[0477] 225. The process of paragraph 223 or 224, wherein the creping adhesive is applied to the surface of the rotating creping cylinder at a rate of about 10 mg/m 2 to about 70 mg/m 2 .
[0478] 226. The process of any of paragraphs 223 to 225, wherein the crosslinked resin has a weight average molecular weight of about 25 kDa to about 1,500 kDa.
[0479] 227. The process of any of paragraphs 223 to 226, wherein the creping adhesive has a pH of about 6.5 to about 10.
[0480] 228. The process of any of paragraphs 223 to 227 wherein the creping adhesive has a viscosity of about 20 cP to about 1,000 cP at a temperature of about 25? C.
[0481] 229. The process of any of paragraphs 223 to 228, wherein the creping adhesive comprises about 1 wt % to about 99 wt % of the crosslinked resin based on a combined weight of the crosslinked resin, any polyvinyl alcohol and any modified polyvinyl alcohol.
[0482] 230. The process of any of paragraphs 223 to 229, wherein the creping adhesive comprises about 1 wt % to about 98 wt % of the solvent, up to about 25 wt % of the polyvinyl alcohol, up to about 70 wt % of the modified polyvinyl alcohol, and about 1 wt % to about 70 wt % of the crosslinked resin, based on a combined weight of the solvent, any polyvinyl alcohol, any modified polyvinyl alcohol, and the crosslinked resin, and wherein the creping adhesive comprises about 1 wt % to about 70 wt % of a total amount of any polyvinyl alcohol and any modified polyvinyl alcohol, based on the combined weight of the solvent, any polyvinyl alcohol, any modified polyvinyl alcohol, and the crosslinked resin.
[0483] 231. The process of any of paragraphs 223 to 230, wherein the creping adhesive has an adhesion of about 25 gram-force per inch to about 800 gram-force per inch when applied to the surface of the rotating creping cylinder.
[0484] 232. The process of any of paragraphs 223 to 231, wherein the creping adhesive has a film solubility of about 10% to about 99%.
[0485] 233. The process of any of paragraphs 223 to 232 wherein the creping adhesive has a film solubility of about 20% to about 80%.
[0486] 234. The process of any of paragraphs 223 to 233, wherein the creping adhesive comprises the modified polyvinyl alcohol, and wherein the modified polyvinyl alcohol comprises a carboxylated polyvinyl alcohol, a sulfonated polyvinyl alcohol, a sulfated polyvinyl alcohol, a sulfonated-carboxylated polyvinyl alcohol, or a mixture thereof.
[0487] 235. The process of paragraph 234, wherein the carboxylated polyvinyl alcohol has the following chemical formula (I):
##STR00136## [0488] wherein a is a number from 1 to 99, b is a number from 0 to 30, and c is a number from 1 to 20.
[0489] 236. The process of paragraph 234 or 235, wherein the modified polyvinyl alcohol comprises the carboxylated polyvinyl alcohol, and wherein the carboxylated polyvinyl alcohol has the following chemical formula (II):
##STR00137## [0490] and wherein d is a number from 1 to 98, e is a number from 1 to 20, f is a number from 0 to 30, and g is a number from 0-10.
[0491] 237. The process of any of paragraphs 234 to 236, wherein the sulfonated polyvinyl alcohol has the following chemical formula (III):
##STR00138## [0492] and wherein h is a number from 1 to 98, i is a number from 0 to 30, and j is a number from 1 to 20.
[0493] 238. The process of any of paragraphs 234 to 237, wherein the modified polyvinyl alcohol comprises the sulfated polyvinyl alcohol, and wherein the sulfated polyvinyl alcohol has the following chemical formula (IV):
##STR00139## [0494] and wherein k is a number from 1 to 98, 1 is a number from 1 to 20, and m is a number from 0 to 30.
[0495] 239. The process of any of paragraphs 234 to 238, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (V):
##STR00140## [0496] and wherein a is a number from 1 to 97, b is a number from 1 to 30, c is a number from 1 to 20, and d is a number from 1 to 10.
[0497] 240. The process of any of paragraphs 234 to 239, wherein the modified polyvinyl alcohol comprises the sulfonated-carboxylated polyvinyl alcohol, and wherein the sulfonated-carboxylated polyvinyl alcohol has the following chemical formula (VI):
##STR00141## [0498] and wherein e is a number from 1 to 97, f is a number from 1 to 30, g is a number from 1 to 20, and h is a number from 1 to 20.
[0499] 241. The process of any of paragraphs 223 to 240, wherein the creping adhesive comprises the polyvinyl alcohol, and wherein the polyvinyl alcohol has the following chemical formula (XIII):
##STR00142## [0500] and wherein k is a number from 1 to 99 and 1 is a number from 0 to 30.
[0501] 242. The process of any of paragraphs 223 to 241, wherein the solvent comprises water, an alkylene glycol, a polyalkylene glycol, or a mixture thereof.
[0502] 243. The process of any of paragraphs 223 to 242, wherein the solvent comprises water.
[0503] 244. The process of any of paragraphs 223 to 243, wherein the functionally symmetric crosslinker has the following chemical formula (VII), (VIII), (IX), (X), (XI), or (XII):
##STR00143## [0504] wherein R.sup.4 is (CH.sub.2).sub.t, t is 1, 2, or 3, and R.sup.5 and R.sup.6 are both a hydrogen atom or a methyl group;
##STR00144## [0505] wherein x is a number from 1 to about 100;
##STR00145## [0506] wherein y is a number from 1 to about 100;
##STR00146## [0507] wherein x+y is a number from 1 to about 100;
##STR00147## [0508] wherein z is a number from 1 to about 100; or
##STR00148## [0509] wherein a q/p ratio is a number from about 10 to about 1000.
[0510] 245. The process of any of paragraphs 223 to 244, wherein the functionally symmetric crosslinker comprises a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer, with an azetidinium-functionalized monomer selected from
##STR00149## [0511] and a mixture thereof, wherein a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%.
[0512] 246. The process of any of paragraphs 223 to 245, wherein the functionally symmetric crosslinker comprises a di-acrylate, a bis(acrylamide), a di-epoxide, a polyazetidinium compound, an alkylene glycol diglycidyl ether, a poly(alkylene glycol) diglycidyl ether, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or a mixture thereof.
[0513] 247. The process of any of paragraphs 223 to 246, wherein functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly (ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, or a mixture thereof.
[0514] 248. The process of any of paragraphs 223 to 247, wherein the functionally symmetric crosslinker comprises ethylene glycol diglycidyl ether.
[0515] 249. The process of any of paragraphs 165 to 248, wherein the polyamidoamine backbones are derived from a polyamidoamine having chemical formula (XIV):
##STR00150## [0516] wherein R.sup.1 is (CH.sub.2).sub.u and u is 1, 2, 3, 4, or 5, each R.sup.2 is independently (CH.sub.2).sub.v and v is 2, 3, or 4, i is 1, 2, or 3, and j is a number from 1 to about 10,000.
[0517] 250. The process of paragraph 249, wherein the polyamidoamine has a weight average molecular weight of about 3 kDa to about 20 kDA.
[0518] 251. The creping adhesive or process according to any one of paragraph 1 to 250, wherein a pH of the creping adhesive is adjusted by combining one or more multi-functional acids with the creping adhesive.
[0519] 252. The creping adhesive or process according to any one of paragraphs 1 to 250, wherein a pH of the creping adhesive is adjusted by combining one or more multi-functional acids with the creping adhesive, and wherein the multi-functional acid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, isocitric acid, aconitic acid, carballylic acid, glycolic acid, lactic acid, malic acid, tartaric acid, gluconic acid, maleic acid, fumaric acid, ascorbic acid, aspartic acid, glutamic acid, 4-hydroxy-benzoic acid, 2,4-dihydroxy benzoic acid, sulfamic acid, methanesulfonic acid, 4-toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, or any mixture thereof.
[0520] 253. The creping adhesive or process according to any one of paragraphs 1 to 250, wherein a pH of the creping adhesive is adjusted by combining one or more acids with the creping adhesive, and wherein the acid comprises one or more mineral acids.
[0521] 254. The creping adhesive or process according to paragraph 253, wherein the mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, hydrofluoric acid, or a mixture thereof.
[0522] 255. A creping adhesive, comprising: a solvent; a modified polyvinyl alcohol; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and propanediyl moieties, wherein the primary crosslinking moieties are derived from a functionally symmetric crosslinker
[0523] 256. A creping adhesive, comprising: a solvent; a modified polyvinyl alcohol; and a crosslinked resin comprising polyamidoamine backbones crosslinked by primary crosslinking moieties and secondary crosslinking moieties, wherein the primary crosslinking moieties are derived from a first functionally symmetric crosslinker, and wherein the secondary crosslinking moieties are derived from a second functionally symmetric crosslinker
[0524] 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.
[0525] 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.
[0526] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.