U.S. patent application number 09/035636 was filed with the patent office on 2002-02-28 for particle binding to fibers.
Invention is credited to HANSEN, MICHAEL R., YOUNG, RICHARD H. SR..
Application Number | 20020025435 09/035636 |
Document ID | / |
Family ID | 46276216 |
Filed Date | 2002-02-28 |
United States Patent
Application |
20020025435 |
Kind Code |
A1 |
HANSEN, MICHAEL R. ; et
al. |
February 28, 2002 |
PARTICLE BINDING TO FIBERS
Abstract
A binder is applied to particles which are then combined with
fibers -to bind the particles to the fibers. The particles have
functional sites for forming a hydrogen bond or a coordinate
covalent bond. The fibers have hydrogen bonding functional sites.
The binder comprises binder molecules, the binder molecules having
at least one functional group that is capable of forming a hydrogen
bond or a coordinate covalent bond with the particles, and at least
one functional group that is capable of forming a hydrogen bond
with the fibers. A substantial portion of the particles that are
adhered to the fibers may be adhered in particulate form by
hydrogen bonds or coordinate covalent bonds to the binder, and the
binder in turn may be adhered to the fibers by hydrogen bonds.
Fibers containing particles bound by this method are easily
densified.
Inventors: |
HANSEN, MICHAEL R.;
(SEATTLE, WA) ; YOUNG, RICHARD H. SR.; (RENTON,
WA) |
Correspondence
Address: |
CHRISTENSEN, O'CONNOR, JOHNSON, KINDNESS, PLLC
1420 FIFTH AVENUE
SUITE 2800
SEATTLE
WA
98101-2347
US
|
Family ID: |
46276216 |
Appl. No.: |
09/035636 |
Filed: |
March 4, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09035636 |
Mar 4, 1998 |
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08791335 |
Jan 31, 1997 |
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09035636 |
Mar 4, 1998 |
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08791335 |
Jan 31, 1997 |
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08791335 |
Jan 31, 1997 |
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08486686 |
Jun 7, 1995 |
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08486686 |
Jun 7, 1995 |
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08108218 |
Aug 17, 1993 |
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5641561 |
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08108218 |
Aug 17, 1993 |
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07931059 |
Aug 17, 1992 |
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5543215 |
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08108218 |
Aug 17, 1993 |
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07931277 |
Aug 17, 1992 |
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5538783 |
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08108218 |
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07931213 |
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5300192 |
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08108218 |
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07931278 |
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5352480 |
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08108218 |
Aug 17, 1993 |
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07931284 |
Aug 17, 1992 |
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5308896 |
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08108218 |
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07931279 |
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5589256 |
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Current U.S.
Class: |
428/403 |
Current CPC
Class: |
D21H 11/16 20130101;
A61F 2013/0091 20130101; A61F 2013/530525 20130101; A61F
2013/530445 20130101; A61F 2013/530496 20130101; A61F 2013/530554
20130101; A61F 2013/530569 20130101; D06M 13/285 20130101; D06M
13/342 20130101; A61F 13/533 20130101; A61F 2013/530189 20130101;
D06M 13/288 20130101; A61F 13/0203 20130101; D06M 13/184 20130101;
A61F 2013/530007 20130101; Y10T 442/699 20150401; A61L 15/60
20130101; A61F 2013/00472 20130101; A61F 2013/15422 20130101; A61F
2013/00927 20130101; A61F 13/53 20130101; A61F 2013/15951 20130101;
A61F 13/511 20130101; D06M 23/00 20130101; A61F 2013/51078
20130101; D06M 23/08 20130101; D06M 2200/00 20130101; Y10T 428/2991
20150115; D04H 1/587 20130101; D04H 1/64 20130101; A61F 2013/00748
20130101; A61F 2013/5104 20130101; D06M 13/292 20130101; D06M
13/256 20130101; A61F 2013/530583 20130101; D06M 2400/01 20130101;
A61F 2013/530613 20130101 |
Class at
Publication: |
428/403 |
International
Class: |
B32B 005/16 |
Claims
We claim:
1. A method of binding particles to fibers with a binder,
comprising the steps of: providing fibrous material comprising a
fiber having a hydrogen bonding functionality; providing particles
having a hydrogen bonding or a coordinate covalent bond forming
functionality; selecting a binder from the group consisting of a
polymeric binder, a non-polymeric organic binder, and non-reactive
combinations thereof with each other or with other binders, the
binders comprising binder molecules, the binder molecules having at
least one functional group capable of forming a hydrogen bond or a
coordinate covalent bond with the particles, and at least one
functional group capable of forming a hydrogen bond with the
fibrous material, wherein the polymeric binder is selected from the
group consisting of a polyglycol, a polycarboxylic acid, a
polycarboxylate, a poly(lactone) polyol, a polyamide, a polyamine,
a polysulfonic acid, a polysulfonate, and combinations thereof, and
wherein the non-polymeric organic binder has a volatility less than
water; exposing the particles to sufficient amounts of the binder
to at least partially coat the particles with the binder; and
binding the particles to the fibrous material.
2. The method according to claim 1 wherein the functional groups
are each capable of forming hydrogen bonds.
3. A fibrous product made by the method of claim 1.
4. The method of claim 1 wherein the binder is the polymeric
binder.
5. The method of claim 4 wherein the binder is selected from the
group consisting of a polyamine, a polycarboxylic acid, and a
polyamide.
6. The method of claim 4 wherein the binder is a polypeptide.
7. The method of claim 1 wherein the binder is the non-polymeric
organic binder.
8. The method of claim 7 wherein the non-polymeric organic binder
has functional groups that are selected from the group consisting
of a carboxyl, a carboxylate, a carbonyl, a sulfonic acid, a
sulfonate, a hydroxyl, a phosphoric acid, a phosphate, an amide, an
amine, and combinations thereof.
9. The method of claim 8 wherein the non-polymeric organic binder
is selected from the group consisting of glycerin, a glycerin
monoester, a glycerin diester, glyoxal, ascorbic acid, urea,
glycine, pentaerythritol, a monosaccharide, a disaccharide, citric
acid, taurine, tartaric acid, dipropylene glycol, an urea
derivative, and combinations thereof.
10. The method of claim 9 wherein the non-polymeric organic binder
is selected from the group consisting of glycerin, a glycerin
monoester, a glycerin diester, urea, and combinations thereof.
11. The method of claim 1 wherein the binder is present in an
amount of from about 0.01 to 50 percent of the weight of the
particles, and the particles are present in an amount of 0.05 to 80
percent of the total weight of the fibrous material and
particles.
12. The method of claim 1 wherein the binder is present in an
amount of from 0.03 to 20 percent of the weight of the
particles.
13. The method of claim 1 wherein the binder is present in an
amount of from 0.03 to 5 percent of the weight of the
particles.
14. The method of claim 1 wherein the step of exposing the
particles to the binder comprises the step of exposing the
particles to the binder as the particles are being combined with
the fibrous material.
15. The method of claim 1 wherein the step of exposing the
particles to the binder comprises providing the binder on the
particles in the absence of the fibrous material, allowing the
binder to assume an inactive state, then later activating the
binder from an inactive state by providing heat, an activating
fluid, or by applying kinetic energy to the particles, or to the
fibers in the presence of the particles, or by adding the particles
to the fibers while activating fluid is on the fibers.
16. The method according to claim 15 wherein the non-polymeric
binder includes a functionality selected from the group consisting
of a carboxyl, a carboxylate, a carbonyl, a sulfonic acid, a
sulfonate, a phosphate, a phosphoric acid, a hydroxyl, an amine, an
amide, and combinations thereof.
17. The method according to claim 16 wherein there are at least two
functionalities on the molecule selected from this group, and the
two functionalities are the same or different.
18. The method of claim 15 wherein the binder is selected from the
group consisting of a polyglycol, a poly (lactone) polyol, a
polycarboxylic acid, a polyamide, a polyamine, and copolymers
thereof.
19. The method of claim 1 wherein the fibers are wood pulp fibers
in a wet laid fiber sheet or web manufacturing line, and the binder
coated particles are combined with the fibers.
20. The method of claim 1 wherein the step of exposing the
particles to the binder comprises providing the binder on the
particles in the absence of the fibrous material, allowing the
binder to assume an inactive state, then later activating the
binder from an inactive state by adding an activating fluid before,
simultaneously with, or after combining the binder coated particles
with the fibrous material.
21. The method of claim 20 wherein the activating fluid is water in
the form of a liquid, steam or humid gas.
22. The method of claim 1 wherein the binder is selected form the
group consisting of a poly (lactone) polyol, a polycarboxylic acid,
a polyamide, a polyamine, and copolymers thereof.
23. The method according to claim 1, further comprising the steps
of: providing individualized cellulose fibers that have hydrogen
bonding functional sites, wherein the individualized fibers are
cured in the presence of a crosslinking material to produce high
bulk fibers with intrafiber covalent crosslinks, and the fibers are
fiberized to reduce interfiber bonding between the cured fibers;
and wherein the step of binding the particles to the fibrous
material comprises the step of adding the particles to the fibers
before, during or after the fibers are cured wherein the particles
are bound to the fibers.
24. The method of claim 23 wherein the curing step comprises using
any crosslinking material and curing the crosslinking material
before combining the binder coated particles and the cured fibrous
material.
25. The method of claim 1 wherein the particles comprise
superabsorbent particles.
26. The method of claim 23 wherein the particles comprise
superabsorbent particles.
27. The method of claim 1 and including the step of densifying the
fibers and the bound particles by applying external pressure to the
fibers.
28. The method of claim 27 wherein the particles are superabsorbent
particles.
29. The method of claim 27 wherein the particles are superabsorbent
particles and the binder is in an active state.
30. The method of claim 27 including the step of forming the fibers
into a web or sheet before the densifying step such that the web or
sheet is densified by applying external pressure to the web or
sheet.
31. The method of claim 23 further including the step of densifying
the fibers and the bound particles by applying external pressure to
the fibers.
32. The method of claim 31 wherein the particles are superabsorbent
particles.
33. The method of claim 31 wherein the particles are superabsorbent
particles and the binder is in an active state.
34. The method of claim 29 or 33 wherein the densifying step
comprises densifying the fibers and adhered particles under
conditions of ambient temperature.
35. The method of claim 29 or 33 in which the densifying step
comprises applying pressure to the web or sheet to produce a
product having a density of from about 0.05 g/cc to about 0.7
g/cc.
36. The method of claim 1 wherein the particles are soluble in
water and are sparingly soluble in the binder.
37. The method of claim 1 wherein the particles have a solubility
in water of at least 10 g in 300 ml of water at 25.degree. C., and
a solubility in the binder of no more than about 5 g in 300 ml of
the binder at 25.degree. C.
38. The method of claim 1 wherein the particles are substantially
soluble in water and in the binder.
39. The method of claim 37 further comprising the step of
activating the binder on the particles from an inactive state by
providing heat, an activating fluid, or by applying kinetic energy
to the particles, or to the fibers in the presence of the
particles, or by adding the particles to the fibers while
activating fluid is on the fibers.
40. A fibrous product comprising: fibrous material comprising a
fiber having a hydrogen bonding functionality; particles having a
hydrogen bonding or a coordinate covalent bond forming
functionality; a binder selected from the group consisting of a
polymeric binder, a non-polymeric organic binder, and non-reactive
combinations thereof with each other or with other binders, the
binder comprising binder molecules, the binder molecules having a
functional group capable of forming a hydrogen bond or a coordinate
covalent bond with the particles, and a hydrogen bond with the
fibrous material, wherein the polymeric binder is selected from the
group consisting of a polyglycol, a polycarboxylic acid, a
polycarboxylate, a poly(lactone) polyol, a polyamide, a polyamine,
a polysulfonic acid, a polysulfonate, and combinations thereof, and
wherein the non-polymeric organic binder has a volatility less than
water; and wherein the binder is primarily present on the particles
and wherein the particles are bound to the fibrous material.
41. The product of claim 40 wherein the binder is selected from the
group consisting of a polyamine, a polycarboxylic acid, and a
polyamide.
42. The product of claim 40 wherein the non-polymeric organic
binder has functional groups that are selected from the group
consisting of a carboxyl, a carboxylate, a carbonyl, sulfonic acid,
a sulfonate, a hydroxyl, a phosphoric acid, a phosphate, an amide,
an amine, and combinations thereof.
43. The product of claim 40 wherein the non-polymeric organic
binder is selected from the group consisting of glycerin, a
glycerin monoester, a glycerin diester, glyoxal, ascorbic acid,
urea, glycine, pentaerythritol, a monosaccharide, a disaccharide,
citric acid, taurine, tartaric acid, dipropylene glycol, an urea
derivative, and combinations thereof.
44. The product of claim 40 wherein the non-polymeric organic
binder is selected from the group consisting of glycerin, a
glycerin monoester, a glycerin diester, urea, and combinations
thereof.
45. The product of claim 40 wherein the binder is selected from the
group consisting of a polyglycol, a poly (lactone) polyol, a
polycarboxylic acid, a polyamide, a polyamine, and copolymers
thereof.
46. The product of claim 40 wherein the particles are soluble in
water and are sparingly soluble in the binder.
47. The product of claim 40 wherein the particles comprise
superabsorbent particles.
48. The product of claim 40 in the form of a web having a density
of from 0.05 to 0.7 g/cc.
49. A fibrous product according to claim 40 comprising:
individualized, high bulk fibers having intrafiber covalent bonds
wherein the fibers have hydrogen bonding functionalities; bound
particles which are at least partially coated with a binder, the
binder being primarily present on the particles, and which are
bound to the fibers in the presence of the binder, wherein the
particles have a hydrogen bonding or coordinate covalent bonding
functionality, and the binder comprises binder molecules, the
binder molecules having at least one functional group that is
capable of forming a hydrogen bond or a coordinate covalent bond,
and at least one functional group that is capable of forming a
hydrogen bond, wherein the product comprises 0.05-80 percent of
said bound particles.
50. A product according to claim 49 having a density of from 0.05
g/cc to 0.7 g/cc.
51. A method of binding particles to fibers with a binder,
comprising the steps of: providing fibrous material comprising a
fiber having a hydrogen bonding functionality; providing particles
having a hydrogen bonding or a coordinate covalent bond forming
functionality; selecting a binder from the group consisting of a
polymeric binder, a non-polymeric organic binder, and non-reactive
combinations thereof with each other or with other binders, the
binder comprising binder molecules, the binder molecules having at
least one functional group capable of forming a hydrogen bond or a
coordinate covalent bond with the particles, and at least one
functional group capable of forming a hydrogen bond with the
fibrous material, wherein the polymeric binder is selected from the
group consisting of a polyglycol, a polycarboxylic acid, a
polycarboxylate, a poly(lactone) polyol, a polyamide, a polyamine,
a polysulfonic acid, a polysulfonate, and combinations thereof, the
polymeric binder having repeating units, wherein the non-polymeric
organic binder has a volatility less than water; and spraying the
binder on the particles as the particles are being combined with
the fibrous material, the binder being sprayed in sufficient
amounts to bind the particles to the fibrous material.
52. A method of binding particles to fibers with a binder,
comprising the steps of: providing fibrous material comprising a
fiber having a hydrogen bonding functionality; providing particles
having a hydrogen bonding or a coordinate covalent bond forming
functionality; selecting a binder from the group consisting of a
polymeric binder, a non-polymeric organic binder, and non-reactive
combinations thereof with each other or with other binders, the
binder comprising binder molecules, the binder molecules having at
least one functional group capable of forming a hydrogen bond or a
coordinate covalent bond with the particles, and at least one
functional group capable of forming a hydrogen bond with the
fibrous material, wherein the polymeric binder is selected from the
group consisting of a polyglycol, a polycarboxylic acid, a
polycarboxylate, a poly(lactone) polyol, a polyamide, a polyamine,
a polysulfonic acid, a polysulfonate, and combinations thereof, and
wherein the non-polymeric organic binder has a volatility less than
water; and combining the particles with sufficient amounts of the
binder and introducing the combined particles and binder to the
fibrous material, under conditions that favor formation of
non-covalent bonds, to bind the particles to the fibrous
material.
53. The method of claim 52 wherein the step of providing fibrous
material comprises the step of providing individualized cellulose
fibers that have hydrogen bonding functional sites, wherein the
individualized fibers are cured in the presence of a crosslinking
material to produce high bulk fibers with intrafiber covalent
crosslinks.
54. Binder coated particles that will adhere to fiber with hydrogen
bonding functional sites comprising: particles that have a
hydrogen-bonding functional site or a coordinate-covalent bonding
functional site; and a binder having a volatility less than water,
the binder also having at least one functional group that is
capable of forming a hydrogen bond with fibers, and at least one
functional group that is capable of forming a hydrogen bond or
coordinate-covalent bond with the particles, the binder being
present in a sufficient amount to bond the particles to the fibers
and in an amount of at least 0.03 percent by weight of the
particles, after the binder is activated.
55. Binder coated particles that will adhere to fibrous material
with hydrogen bonding functional sites comprising: particles that
have at least one functional site that is either a hydrogen-bonding
functional site or a coordinate-covalent bonding functional site;
and a binder selected from the group consisting of glycerin, a
glycerin monoester, a glycerin diester, urea, and combinations
thereof, the binder having a volatility less than water, and the
binder comprising binder molecules, the binder molecules having at
least one functional group that is capable of forming hydrogen
bonds or coordinate covalent bonds with the particles, and at least
one functional group that is capable of forming hydrogen bonds with
the fibrous material.
56. The method according to claim 1 wherein the polymeric binder
comprises repeating units, and each repeating unit has at least one
functional group capable of forming a hydrogen bond with the
fibrous material, and at least one functional group capable of
forming a hydrogen bond or a coordinate covalent bond with the
particles.
57. Binder coated particles, comprising: particles having at least
one hydrogen bonding functionality or a coordinate covalent bonding
functionality; and a binder selected from the group consisting of
glycerin, a glycerin monoester, a glycerin diester, urea, and
combinations thereof, the binder having a volatility less than
water, the binder comprising binder molecules, wherein the binder
molecules have at least one functional group that is capable of
forming hydrogen bonds or coordinate covalent bonds with the
particles, and at least one functional group that is capable of
forming hydrogen bonds with fibrous material, an effective amount
of the binder being on surfaces of the particles to bind the
particles to the fibrous material.
58. A fiber product produced by the method of claims 12, 15, 19,
20, 21, 23, 25, 26, 31, 32, 36, 39, 51, 52 or 53.
59. An absorbent article comprised of the fiber product of claims
40, 41, 43, 44, 46, 47, 48 or 49.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation-in-part application of the following
U.S. Patent Applications, each of which was filed on Aug. 17, 1992,
and each of which is hereby incorporated herein by reference: (1)
Ser. No. 07/931,059, entitled "POLYMERIC BINDERS FOR BINDING
PARTICLES TO FIBERS"; (2) Ser. No. 07/931,277, entitled
"NON-POLYMERIC ORGANIC BINDERS FOR BINDING PARTICLES TO FIBERS";
(3) Ser. No. 07/931,213, entitled "WET LAID FIBER SHEET
MANUFACTURING WITH REACTIVATABLE BINDERS FOR BINDING PARTICLES TO
BINDERS"; (4) Ser. No. 07/931,278, entitled "REACTIVATABLE BINDERS
FOR BINDING PARTICLES TO FIBERS"; (5) Ser. No. 07/931,284, entitled
"PARTICLE BINDERS FOR HIGH BULK FIBERS"; and (6) Ser. No.
07/931,279, entitled "PARTICLE BINDERS THAT ENHANCE FIBER
DENSIFICATION."
FIELD OF THE INVENTION
[0002] This invention concerns polymeric and non-polymeric binders
for particles and the use of such binders in binding particles to
fibers. The fibers and bound particles may be easily densified by
external application of pressure. The binders are reactivatable,
and may be applied to particles, which thereafter may be bound to
fibers on a wet-laid fiber sheet manufacturing line. In particular
embodiments, the invention concerns binding superabsorbent
particles to cellulosic fibers which may then be used, for example,
to make absorbent fibers that are densified and incorporated into
absorbent products. In other embodiments, the invention concerns
the reactivation and use of binder coated particles, preferably at
an article manufacturing plant, at a location remote from a
pulp-sheet manufacturing line to bind superabsorbent and/or other
particles to cellulosic fibers which may then be used, for example,
as absorbent fibers incorporated into absorbent products.
BACKGROUND OF THE INVENTION
[0003] Superabsorbent polymers have been developed in recent years
that are capable of absorbing many times their own weight of
liquid. These polymers, which are also known as water insoluble
hydrogels, have been used to increase the absorbency of sanitary
products such as diapers and sanitary napkins. Superabsorbent
polymers are often provided in the form of particulate powders,
granules, or fibers that are distributed throughout absorbent
cellulosic products to increase the absorbency of the product.
Superabsorbent particles are described, for example, in U.S. Pat.
No. 4,160,059; U.S. Pat. No. 4,676,784; U.S. Pat. No. 4,673,402;
U.S. Pat. No. 5,002,814; and U.S. Pat. No. 5,057,166. Products such
as diapers that incorporate absorbent hydrogels are shown in U.S.
Pat. No. 3,669,103 and U.S Pat. No. 3,670,731.
[0004] One problem with the use of superabsorbents is that the
superabsorbent material can be physically dislodged from the
cellulosic fibers of an absorbent product. Separation of the
superabsorbent from its substrate reduces the absorbency of the
product and diminishes the effectiveness of the superabsorbent
material. This problem was addressed in European Patent Application
442 185 A1, which discloses use of a polyaluminum chloride binder
to bind an absorbent polymer to a fibrous substrate. The
polyaluminum binder, however, suffers from the drawback of being an
inorganic product that is not readily biodegradable. Moreover, that
European patent does not offer any guidance for selecting binders
other than polyaluminum chloride that would be useful in binding
absorbent particles.
[0005] A method of immobilizing superabsorbents is disclosed in
U.S. Pat. No. 4,410,571 in which a water swellable absorbent
polymer is converted to a non-particulate immobilized confluent
layer. Polymer particles are converted to a coated film by
plasticizing them in a polyhydroxy organic compound such, as
glycerol, ethylene glycol, or propylene glycol. The superabsorbent
assumes a non-particulate immobilized form that can be foamed onto
a substrate. The individual particulate identity of the
superabsorbent polymer is lost in this process. The confluent
nature of the superabsorbent material can also result in gel
blocking, in which absorption is diminished as the water swollen
polymers block liquid passage through the film layer.
[0006] U.S. Pat. No. 4,412,036 and U.S. Pat. No. 4,467,012 disclose
absorbent laminates in which a hydrolyzed starch polyacrylonitrile
graft copolymer and glycerol mixture is laminated between two
tissue layers. The tissue layers are laminated to each other by
applying external heat and pressure. The reaction conditions form
covalent bonds between the tissue layers that firmly adhere the
tissue layers to one another.
[0007] Numerous other patents have described methods of applying
binders to fibrous webs. Examples include U.S. Pat. No. 2,757,150;
U.S. Pat. No. 4,584,357; and U.S. Pat. No. 4,600,462. Such binders
are not described as being useful in binding particulates, such as
superabsorbent particles, to fibers. Yet other patents disclose
crosslinking agents such as polycarboxylic acids that form covalent
intrafiber bonds with individualized cellulose fibers, as in
European Patent Application 440 472 A1; European Patent Application
427 317 A2; European Patent Application 427 316 A2; and European
Patent Application 429 112 A2. The covalent intrafiber bonds are
formed at elevated temperatures and increase the bulk of cellulose
fibers treated with the crosslinker by forming intrafiber ester
crosslinks. Crosslinking must occur under acidic conditions to
prevent reversion of the ester bonds. The covalent bonds within the
fibers produce a pulp sheet that is more difficult to compress to
conventional pulp sheet densities than in an untreated sheet.
Covalent crosslink bonds may also form between the fibers and
particles, and occupy functional groups that would otherwise be
available for absorption, hence absorption efficiency is
decreased.
[0008] A particular disadvantage of forming covalent ester
intrafiber crosslinks is that the resulting fiber product resists
densification. Energy requirements for making densified absorbent
products are increased because very high compression pressures must
be used to densify the absorbent product. It would be advantageous
to provide a method of enhancing densification of crosslinked
fibers by reducing energy requirements for densification.
[0009] Many different types of particles other than superabsorbents
may be added to fibers for different end uses. Antimicrobials,
zeolites and fire retardants are but a few examples of particles
that are added to fibers. It would be advantageous to provide a
method of attaching particles that could be accommodated to the
many different particle needs of end users. Moreover, it would be
advantageous to reduce particulate waste in the attachment process,
and simplify shipment of fiber products that require particulate
addition. It would be further advantageous to bind particulates to
fibers without requiring the shipment of bulk fibers with adhered
particulates because shipping and excessive handling of these
fibers subject them to mechanical impact which can dislodge some
particles from the fibers. It would also be advantageous under some
circumstances to incorporate binder coated particles onto fibers
during the initial pulp sheet manufacturing process so that the
fibers with particles are ready for use at a remote product
manufacturing location. However, the particles are then subject to
dislodgement during the subsequent manufacturing processes.
[0010] It has previously been important that particles added to
cellulose products be insoluble in liquids such as water or liquid
binders. It has been thought that liquid insolubility (particularly
water insolubility) was an essential characteristic for particles
bound to cellulose fibers because soluble particles would be
dissolved by a water containing binder. Although the particle could
eventually resolidify as the binder evaporated, dissolution of the
particle in the binder would cause the particle to diffuse to areas
of the product where it was not needed or desired. Water soluble
particles have therefore not been used for particles that were to
be bound to fibers using a binder.
SUMMARY OF THE INVENTION
[0011] The foregoing and other problems have been overcome by
providing fibers with hydrogen bonding functional sites, and
binders that have a volatility less than water. The binder has a
functional group that forms a hydrogen bond with the fibers, and a
functional group that is also capable of forming a hydrogen bond or
a coordinate covalent bond with particles that have a hydrogen
bonding or coordinate covalent bonding functionality. The binder is
applied to the particles to at least partially coat the particles.
The binder containing particles, when combined with the fibers, are
bonded to the fibers by a bond that has been found to be resistant
to mechanical disruption. A significant advantage of these binders
is that the binder and particle together on the fiber have been
found to reduce the pressure required to densify the fibers. This
is particularly true for superabsorbent particles, and preferably
comprises using superabsorbent particles and a binder in an active
state. The binders can also be present on particles in an inactive
state for more than a week, a month, or a even a year, then later
activated or reactivated to bind particles to the fibers. Liquid
binders (which includes neat liquids or aqueous solutions of solid
binders) can be placed on the particles, dried, and later
reactivated by moistening the particles. Alternatively, a dry solid
binder may be blended with the particles and later activated by
addition of a liquid. An inactive binder can also be activated by
applying kinetic energy to the binder containing particles in the
presence of the fibers. Typically, an inactive state is one where
the binder and particles reach an equilibrium moisture content with
the atmosphere (hereinafter referred to as "air dry"). Kinetic
energy can be applied to the binder and fibers, for example and
without limitation, by applying mechanical agitation, pressure from
an external source, or using ultrasonics. In yet other embodiments,
the binder may be activated or reactivated by heating the binder
containing particles after applying the binder to the
particles.
[0012] The capacity for activation or reactivation allows the
binder to be applied to the particles, which are then shipped to
distribution points with the binder in an inactive form. The binder
is then activated at the distribution point (for example, a
customer's facility) where binder containing particles are added to
the fibers and bound thereto. As used herein, binder "activation"
includes both activation of previously inactive binders (such as
solid binders in the absence of liquid) or reactivation of
previously active binders (such as a liquid binder that has been
air dried). More typically, the particles are exposed to the
binder, e.g. by spraying binder onto a stream of particles, as the
particles are being deposited on a web of fibers or are otherwise
being combined with the fibers. The binder binds the particles to
the fibers. By applying binder primarily to the particles instead
of directing the binder to the fibers, lesser quantities of binder
are required to bind the particles to the fibers.
[0013] Another advantage of the present invention is that the
binder containing particles can be applied to a fiber product in a
pattern that corresponds to a desired distribution of particles in
fibrous material. The binder may then be reactivated to bind the
particles in place. A reactivation fluid, such as a reactivation
liquid, for example, can be applied to binder containing particles
deposited in the areas of a diaper that will be initially moistened
by urine during use. Examples, without limitation, of suitable
reactivation liquids include water, glycerin, lower alkyl alcohols,
polyols, such as glycols, glycerin and monoglycerates, acetone, and
combinations thereof, such as water and glycerin. When the
reactivating fluid is a liquid, for example water, the liquid may
be sprayed or otherwise applied and may be provided in the form of
a gas. When water is the reactivating liquid, then it may be
provided as steam or moisture-laden gas, such as humid air. Other
liquid reactivation fluids may be applied in the same manner.
Binder containing particles, such as superabsorbent particles can
be added to areas of the diaper to which an activation fluid is or
will be applied and will be adhered almost exclusively in those
areas where initial urine absorption is required. Targeted
activation of binder containing particles allows the particles to
be efficiently and economically attached to the fibers, with
reduced particle wastage. Moreover, targeted binder activation and
particle adherence increases the absorptive efficiency of the
product by diminishing excessive wicking of liquid within the plane
of an absorptive product.
[0014] The particles of the present invention may be bound to the
fibers with a polymeric or non-polymeric binder. The binder
comprises binder molecules wherein the binder molecules have at
least one functional group capable of forming a hydrogen bond or
coordinate covalent bond with the particles, and at least one
functional group capable of forming a hydrogen bond with fibrous
material. The polymeric binder may be selected from the group
consisting of polyglycols [especially polyethylene glycol or
poly(propyleneglycol)], a polycarboxylic acid, a polycarboxylate, a
poly(lactone) polyol, such as diols, a polyamide, a polyamine, a
polysulfonic acid, a polysulfonate and combinations thereof.
Specific examples of some of these binders, without limitation, are
as follows: polyglycols include polypropylene glycol (PPG) and
polyethylene glycol (PEG); poly(lactone) polyols include
poly(caprolactone) diol;, polycarboxylic acids include polyacrylic
acid (PAA); polyamides include polyacrylamide or polypeptides;
polyamines include polyethylenimine and polyvinylpyridine;
polysulfonic acids or polysulfonates include
poly(sodium-4-styrenesulfonate) or
poly(2-acrylamido-methyl-1-propanesulf- onic acid); and copolymers
thereof (for example a polypropylene glycol/polyethylene glycol
copolymer). The polymeric binder typically has repeating units. The
repeating unit may be the backbone of a compound, such as with a
polypeptide, wherein the repeating polyamides occur in the peptide
chain. The repeating unit may also refer to units other than
backbones, for instance a repeating acrylic acid unit. In such a
case, the repeating units may be the same or different. The binder
has a functional group capable of forming a hydrogen bond or a
coordinate covalent bond with particles, and a functional group
capable of forming a hydrogen bond with the fibers. At this time,
the most preferred polymeric binder is polyethylene glycol although
another especially preferred polymeric binder is an amide binder
such as a polypeptide binder with polyglycine being a specifically
preferred example.
[0015] The non-polymeric binder has a volatility less than water, a
functional group that is capable of forming a hydrogen bond or
coordinate covalent bond with the particles, and a functional group
that is capable of forming a hydrogen bond with the cellulose or
other fibers. The non-polymeric binder is an organic binder, and
preferably includes a functional group selected from the group
consisting of a carboxyl (for example, carboxylic acids), a
carboxylate, a carbonyl (for example, aldehydes), a sulfonic acid,
a sulfonate, a phosphoric acid, a phosphate, an amide, an amine, a
hydroxyl (such as an alcohol) and combinations thereof (for
example, an amino acid or an hydroxy acid), wherein there are at
least two functionalities on the molecule selected from this group,
and the two functionalities are the same or different. Examples of
such binders include polyols, polyamines (a non-polymeric organic
binder with more than one amine group), polyamides (a non-polymeric
organic binder with more than one amide group), polycarboxylic
acids (a non-polymeric organic binder with more than one carboxylic
acid functionality), polyaldehydes (a non-polymeric organic binder
with more than one aldehyde), amino alcohols, hydroxy acids and
other binders. These binders have functional groups that are
capable of forming the specified bonds with the particles and
fibers.
[0016] More preferably, the organic non-polymeric binder is
selected from the group consisting of glycerin, a glyceride
monoester, including monoglycerides, a glycerin diester, including
diglycerides, glyoxal, ascorbic acid, urea, glycine,
pentaerythritol, a monosaccharide or a disaccharide, citric acid,
tartaric acid, taurine (2-aminoethanesulfonic acid),
p-aminosalicylic acid, dipropylene glycol, urea derivatives such as
DMDHEU, and combinations thereof. Suitable saccharides include
glucose, sucrose, lactose, ribose, fructose, mannose, arabinose,
and erythrose. The preferred binders are non-polymeric molecules
with a plurality of hydrogen bonding functionalities that permit
the binder to form hydrogen bonds to both the fibers and particles.
Particularly preferred binders include those that can form five or
six membered rings, most preferably six membered rings, with a
functional group on the particle surface. At present, glycerin, a
glycerin monoester, a glycerin diester, and blends of these with
urea are the preferred binders. At this time, a specifically
preferred non-polymeric binder is glycerin.
[0017] The fibrous material may be cellulosic or synthetic fibers
that are capable of forming hydrogen bonds with the binder, while
the particles are selected to be of the type that are capable of
forming hydrogen bonds or coordinate covalent bonds with the
binder. It has unexpectedly been found that this binder system
secures particles to fibers exceptionally well. A superior fibrous
product is therefore produced that has improved absorbent
properties as compared to unbound or covalently bound particles.
Formation of the noncovalent bond allows production of a fiber
product that is easily manufactured and a web that is easily
densified, and that is readily biodegradable and disposable.
[0018] In one preferred embodiment, an absorbent product comprises
a fibrous cellulosic mat that contains superabsorbent hydrogel
particles in particulate form. The superabsorbent particles are
capable of forming hydrogen bonds or coordinate covalent bonds with
the binder, depending upon the binder, while the binder in turn is
capable of forming hydrogen bonds with the hydroxyl groups of the
cellulose fibers. These noncovalent, relatively flexible bonds
between the binder and particles maintain the particles in contact
with the fibers, and resist dislodgement of the particles by
mechanical forces applied to the mat during manufacture, storage or
use. The amount of binder present typically depends on a number of
factors, including the nature of the binder and particles, and
whether the particles are immediately added to the fibers or after
a period of time. Hence, one skilled in the art will realize that
the amount of binder suitable and particularly useful for a
particular application will vary. However, the binder may suitably
be present in an amount of from about 0.01 to 50 percent of the
total weight of the particles, preferably from 0.03 to 20 percent,
more preferably 0.03 to 5 percent and most preferably 0.03 to 1
percent. This lower percentage range produces very strong bonds
that would require a much higher quantity of binder if the binder
were applied to the fibers instead of the particles. The particles
bound by the binder of the present invention (via
hydrogen/coordinate covalent bonds) may suitably be present in an
amount of 0.05 to 80 percent of the total weight of the fibrous
material and the particles, preferably 1 to 80 percent or 5 to 80
percent, or more than 5 percent by weight. A particularly suitable
range of particles is 5 to 70 percent by weight of the fibrous
material and particles. A preferred weight ratio of particle to
binder is 90:1 to 500:1. An example of a suitable particle is a
superabsorbent polymer such as a starch graft polyacrylate hydrogel
fine or larger size particle such as a granule, which is capable of
forming hydrogen bonds with the binder. The binder also is capable
of forming hydrogen bonds with the hydroxyl groups of the
cellulose, thereby securely attaching the superabsorbent particles
to the fibers.
[0019] The present invention also includes a method of binding
particles to fibers wherein the particles are insoluble in the
binder (and soluble in water) and therefore retain their solid
particulate form following binding. The particles, whether water
soluble or not, preferably have functional groups that can form
hydrogen bonds or coordinate covalent bonds with the binder, and
the binder in turn is capable of forming hydrogen bonds to the
fibers. Other particles without the desired functionality may also
be included in the fiber product, but such particles will not be
bound as strongly in the same manner.
[0020] In especially preferred embodiments, the fibers are
cellulosic and the particles are superabsorbent particles that are
bound to the binder by hydrogen bonds. The fibers also may be
continuous or discontinuous synthetic or natural fibers having a
hydrogen bonding functional group that hydrogen bonds with the
binder. The binder is suitably applied to the particles in an
amount of at least 0.03 percent, and preferably no more than 80
percent, more preferably no more than 20 percent and most
preferably 0.1 to 3 percent, by total weight of the particles. The
particles may be bound to the fibers at less than 150.degree. C. or
without any external application of heat at ambient temperature
(e.g., about 25.degree. C.). Particles may also be bound in the
absence of any external application of pressure, or in the absence
of external heat and pressure.
[0021] In some embodiments the binder is associated with the
particles as a solid (for example, a dry powder or a dried liquid),
and the fibers contain at least 7 percent water by weight when the
binding step is performed. This level of moisture in the fibers
provides sufficient mobility of reactants to allow the particles
and fibers to bind well to each other. When a liquid binder is used
(for example, glycerin or a solution of glycine powder), the fibers
suitably contain at least about 0.5 percent water by weight. A
solid binder is suitably used with fibers having less than 0.5
percent water by weight if the binder is heated above its melting
point to liquefy it. A solid binder may be thermoplastic or
meltable, such that it can be heated above its melting point and
then cooled to fuse fibers to each other. The thermoplastic
properties of the binder can also provide additional mechanical
adherence between the particles and fibers. In some embodiments, a
meltable binder such as urea may be employed which can adhere
particles both physically and with hydrogen bonding.
[0022] In other embodiments, the particles are soluble in water but
have reduced solubility in the binder such that the particles can
be bound in solid particulate form to the fibers. Addition of the
binder does not dissolve the particle and cause it to diffuse away
from its desired site of attachment to the fibers.
[0023] The invention also is directed to fibrous products produced
by any of the methods described herein and to absorbent products or
articles comprised of such fibrous products.
[0024] The present invention relates to the above objects, features
and advantages individually as well as collectively. The foregoing
and other features and advantages of the invention will become more
apparent from the following detailed descriptions and accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is a schematic illustration of a wet laid sheet
manufacturing line illustrating the application of binder coated
particles in accordance with the present invention during the
manufacture of a fiber sheet.
[0026] FIG. 2 is a schematic illustration of a web manufacturing
line illustrating binder reactivation and particulate attachment
process in accordance with the present invention.
[0027] FIG. 3 is a schematic depiction of the components of an
apparatus of the present invention that produce high bulk
fibers.
[0028] FIG. 4 is a top plan view of a structure into which
particles with binders are combined with fibers, the fibers being
in the form of an illustrated absorbent pad.
[0029] FIG. 5 represents a partial sectional view of the pad of
FIG. 4.
[0030] FIG. 6 illustrates a plan view of a bandage incorporating
particles with binder adhered to fibers in accordance with the
present invention.
[0031] FIG. 7 is a sectional view of the bandage of FIG. 6, taken
along line 7-7 of FIG. 6.
[0032] FIG. 8 is a plan view of a disposable diaper including a
core of particles with binder adhered to fibers in accordance with
the present invention.
[0033] FIG. 9 is a vertical sectional view along line 9-9 of the
diaper of FIG. 8.
[0034] FIG. 10 is a view of an enlarged fiber with particles bonded
to the fiber with the binders of the present invention.
[0035] FIG. 11 is a schematic view of a cellulose mat with
particles bound to all its surfaces and throughout its depth.
[0036] FIG. 12A, 12B are photomicrographs of particles adhered to
fibers with a para-aminosalicylic acid binder.
[0037] FIGS. 13A, 13B are photomicrographs of particles bound to
fibers with a taurine binder.
DETAILED DESCRIPTION OF SEVERAL PREFERRED EMBODIMENTS OF THE
INVENTION
I. Processing of Fibers
[0038] FIG. 1 illustrates a wet laid sheet manufacturing line such
as a pulp sheet manufacturing line 10. In this manufacturing line,
a pulp slurry 12 is delivered from a headbox 14 through a slice 16
and onto a Fourdrinier wire 18. The pulp slurry 12 typically
includes cellulose fibers such as wood pulp fibers and may also
include synthetic or other non-cellulose fibers as part of the
slurry. Water is drawn from the pulp deposited on wire 18 by a
conventional vacuum system, not shown, leaving a deposited pulp
sheet 20 which is carried through a dewatering station 22,
illustrated in this case as two sets of calendar rolls 24, 26 each
defining a respective nip through which the pulp sheet or mat 20
passes. From the dewatering station, the pulp sheet 20 enters a
drying section 30 of the pulp manufacturing line. In a conventional
pulp sheet manufacturing line, drying section 30 may include
multiple canister dryers with the pulp mat 20 following a
serpentine path around the respective canister dryers and emerging
as a dried sheet or mat 32 from the outlet of the drying section
30. Other alternate drying mechanisms, alone or in addition to
canister dryers, may be included in the drying stage 30. The dried
pulp sheet 32 has a maximum moisture content pursuant to the
manufacturer's specifications. Typically, the maximum moisture
content is no more than 10% by weight of the fibers and most
preferably no more than about 6% to 8% by weight. Otherwise, the
fibers tend to be too damp. Unless overly damp fibers are
immediately used, these fibers are subject to degradation by, for
example, mold or the like. The dried sheet 32 is taken up on a roll
40 for transportation to a remote location, that is, one separate
from the pulp sheet manufacturing line, such as at a user's plant
for use in manufacturing products. Alternatively, the dried sheet
32 is collected in a baling apparatus 42 from which bales of the
pulp 44 are obtained for transport to a remote location.
[0039] A binder of the type explained in detail below is applied to
particles and then the binder containing particles are applied to
the pulp sheet from one or more particle applying devices, one of
which is indicated at 50 in FIG. 1. Any binder applying device may
be used for applying binder to particles, such as sprayers, or
immersion applicators or the like. Sprayers are typically easier to
utilize and incorporate into a pulp sheet manufacturing line. The
binder is applied to the particles and then the particles are
deposited onto the pulp sheet where the binder adheres the
particles to the fibers of the sheet. The binder also may be
sprayed or otherwise applied to the particles as they fall or are
otherwise deposited onto the sheet. Also, the binder may be
combined with the particles at another location, allowed to dry or
become inactive, and then applied to the sheet. The binder may then
be activated as explained below. Also, the moisture in the sheet
may be enough to activate the binder for binding particles to the
fibers. As indicated by the arrows 52, 54 and 56, the binder
containing particles may be applied at various locations or at
multiple locations on the pulp sheet manufacturing line, such as
ahead of the drying stage 30 (indicated by line 52), intermediate
the drying stage 30 (as indicated by line 54), or downstream from
the drying stage 30 (as indicated by the line 56). Particles with
water-soluble binders, such as non-polymeric urea, are typically
applied at a location where sufficient drying can still take place
in the drying stage to produce a dried binder particle containing
fiber sheet with no more than the maximum desired moisture content.
Consequently, to take advantage of the drying stage 30, particles
with wet water-based binders may be applied at locations 52 or 54.
If wet water-based binder containing particles are applied at
location 56 in an amount which would cause the moisture content of
the sheet to exceed the desired maximum level, an additional drying
stage (not shown) may be included in the pulp manufacturing line to
bring the moisture content down to the desired level.
[0040] Particles with a non-aqueous based binder, such as glycerin,
would most preferably be added downstream from the drying stage at
location 56 or during the drying stage as indicated by location 54.
However, particles with liquid non-aqueous binders may also be
added at a location, such as location 52, upstream of the drying
stage. At this latter location, the water in the wet web at this
point may tend to attract these binders into the mat or sheet as
many of the binders tend to be hydroscopic. Since non-aqueous
binders typically do not enhance the degradation of the product due
to the addition of moisture to the sheet, particles with such
binders can be applied downstream from the drying stage without
bringing the moisture content of the sheet above the desired
maximum level.
[0041] Again, the binder containing particulate materials, selected
as explained below, may be added to the sheet and adhered thereto
by the binders on the pulp manufacturing line. Another suitable
particulate applicator is indicated at 60 and may comprise a bulk
or volumetric metering device. These particles may be sprinkled,
poured or otherwise added to the sheet. To facilitate the adherence
of these particulates to the sheet at this location, enough
moisture must remain in the sheet or on the particles, in the case
of aqueous binders on the particles, to enable the bonding between
the particles and fibers as explained below. For non-aqueous
binders, the particles in this case are preferably added while the
binder is still wet or heated to facilitate the binding.
[0042] Although the above approach is advantageous because the
particles are strongly bound to the fibers, during transportation
of rolls or bales of these fibers it is possible for particles to
become dislodged by mechanical impact during transport. In
addition, this approach interferes with the customization of the
fiber application at a user's location. For example, a user may
want the capability of selecting particular types or brands of
particles for adherence to the fibers in the user's products,
without having this selection made by a pulp-sheet manufacturer who
incorporates the particles into the pulp sheet during its
manufacture. Also, certain particles may degrade over time, making
it advantageous to add such particles immediately prior to
incorporation into products. For example, superabsorbent particles
are susceptible to absorbing moisture from the atmosphere during
shipment. Particles with a relatively short shelf life, such as
certain zeolites (e.g. Abscents with odor absorbing materials which
can become saturated with odors over time) being one example, may
also degrade over time. Another example is zeolites with silver
salts as antimicrobial agents which can photodegrade. Therefore, it
is also advantageous to provide a fibrous product in which the end
user of the product may incorporate the desired particles with
binders at the time the fibers are converted into products.
[0043] Therefore, in keeping with this latter preferred approach,
as illustrated in FIG. 2, the respective rolls 40 or bales 44 of
fibers, without particles, are transported to a remote location for
use by a user. These rolls or bales (or otherwise transported
fibers, e.g., bagged, containerized or otherwise in bulk form) are
then refiberized by a fiberizing apparatus 70. Although any
fiberizer may be used, a typical fiberizing apparatus 70 is a
hammermill which may be used alone or in conjunction with other
devices such as picker rolls or the like for breaking up the sheet
32 or bales 42 into individual fibers.
[0044] A particulate material adding mechanism 72 (e.g. like
mechanism 60) delivers the desired binder coated particulate
materials to the fibers at the desired location in the user's
process. Again, the device 72 typically comprises a metering
mechanism, although any suitable device for adding particulates to
fibrous materials may be used. For example, the particulates may be
delivered as indicated by line 74 to the fiberizing apparatus 70.
In the case of some binders, agitation of fibers within the
fiberizer 70, as explained in greater detail below, reactivates the
binders and causes the particulates to be adhered to the fibers by
the binder. Alternatively, a reactivating fluid, which may be a
liquid such as, for example water, glycerin, lower-alkyl alcohols,
polyols, acetone, and combinations thereof, such as water and
glycerin, may be sprayed or otherwise applied to the fibers, such
as from a reactivation fluid tank or source 78 by way of a sprayer
(not shown) at location 80. The particles may then be applied, as
indicated by line 84 to the fibers downstream from the application
of the reactivation liquid 80. The binder on the fibers may be
reactivated by the activating fluid to adhere to the fibers.
Alternatively, the binder containing particles may be added prior
to or at location 80 where they are adhered to the fibers by the
binder upon reactivation of the binder at location 80. Binder may
also be combined with the particles as the particles are added to
the fiber sheet. As yet another alternative, the fiberized fibers
are delivered to an air-laying device 90 and reformed into a
desired product such as a web indicated at 92. In the case of
air-laid fibers, the reactivation fluid or liquid may be applied to
the web at location 96 with the binder containing particles then
being added at location 98 as shown with the reactivated binder
then adhering the particles to the fibers. The particles with
binder may be applied at a location in the process upstream from
the application of the reactivating liquid at location 96.
Alternatively, the activating fluid may be added simultaneously
with the addition of binder coated particles, so that the
reactivation occurs simultaneously with the addition of particles.
The reactivating fluid also may be added after the binder coated
particles are added to the fibers. In addition, the binder coated
particles may be applied to specifically defined locations on the
web 92, such as in target zones of an absorbent core of a product,
thereby minimizing the wasting of the particulate material. A
specific example of a target zone is the crotch region of a diaper
where most diaper wetting would occur. The application of
superabsorbent particles to such a zone places these particles at a
location where they are most useful in absorbing liquid. The web
92, with or without other components of the end user's product, is
then processed into the user's product, such as being included
within a disposable diaper 100.
[0045] Again, with this approach, the end user of the fibers may
readily select particles to be applied to its product and may, if
required, activate the binder as required to enhance the efficient
production of the user's product. In addition, the user has
flexibility in air laying fibers with binder-coated particles or
otherwise combining the binder coated particles into a finished
product with the desired particulates. Not only is handling and
shipping of the particulate-containing products avoided by the
manufacturer of the pulp sheet, enhanced adhesion of particulates
to the fibers results because the particles are not subjected to
mechanical forces between the location of manufacture of the fibers
and the location at which the particulate materials and binder are
added.
II. Fiber Characteristics
[0046] The present invention includes a method of binding particles
to fibers, and the product, including absorbent end-products, that
are produced by such method. In particularly preferred embodiments,
the product is a cellulosic or synthetic fiber to which
superabsorbent hydrogel polymer particles are adhered by a binder,
and absorbent products made therefrom. The invention also includes
a combination of wood pulp and certain binders, which for the
purpose of this combination are bulk fibers in roll form having a
basis weight of at least 350 grams per square meter (g/m.sup.2) or
bale form. The bulk fibers can have a density of at least about 400
kg/m.sup.3. Preferred bulk fibers are wood pulp fibers or softwood
pulp fibers. The pulp fibers may be chemical or thermomechanical or
chemithermomechanical or combinations thereof. The preferred pulp
fiber is chemical. Suitable fibers include wood-pulp fibers, which
can be obtained from well known chemical processes such as the
kraft and sulfite processes. In these processes, the best starting
material is prepared from long fiber coniferous wood species, such
as pine, douglas fir, spruce and hemlock. Wood pulp fibers can also
be obtained from mechanical processes, such as ground wood,
mechanical, thermomechanical, chemimechanical, and
chemithermomechanical pulp processes. The fibers are preferably
elongated, for example having a length to width ratio of about 10:1
to 5:1.
[0047] The fibers of the present invention also include fibers that
are pretreated prior to the application of a binder to the fibers.
This pretreatment may include physical treatment, such as
subjecting the fibers to steam or chemical treatment, such as
cross-linking the fibers. Although not to be construed as a
limitation, examples of pretreating fibers include the application
of fire retardants to the fibers, such as by spraying the fibers
with fire retardant chemicals. Specific fire-retardant chemicals
include, by way of example, sodium borate/boric acid, urea,
urea/phosphates, etc. In addition, the fibers may be pretreated
with surfactants or other liquids, such as water or solvents, which
modify the surface of the fibers. Other pretreatments include
exposure to antimicrobials or pigments.
[0048] The fibers also may be pretreated in a way which increases
their wettability. The fibers also may be a pretreated with
conventional cross-linking materials and may be twisted or crimped,
as desired. Pretreating cellulose fibers with chemicals which
result in lignin or cellulose rich fiber surfaces also may be
performed in a conventional manner.
[0049] Bleaching processes, such as chlorine or ozone/oxygen
bleaching may also be used in pretreating the fibers. In addition,
the fibers may be pretreated, as by slurrying the fibers in baths
containing various solutions. For example, antimicrobial solutions
(such as solutions of antimicrobial particles as set forth below),
as well as solutions of fertilizers and pesticides, and/or
fragrances and flavors, for release over time during the life of
the fibers. Fibers pretreated with other chemicals, such as
thermoplastic and thermoset resins also may be used. Combinations
of pretreatments also may be employed with the resulting pretreated
fibers then being subjected to the application of the binder
coating as explained below.
[0050] Ground wood fibers, recycled or secondary wood-pulp fibers,
and bleached and unbleached wood-pulp fibers can be used. Details
of the production of wood pulp fibers are well known to those
skilled in the art. These fibers are commercially available from a
number of companies, including Weyerhaeuser Company, the assignee
of the present invention.
[0051] The fibers also can be any of a variety of other natural or
synthetic fibers; however, all of the fibers to which particles are
attached in accordance with the present invention include a
hydrogen-bonding functionality. This does not preclude the blending
of such fibers with fibers lacking this characteristic. However,
the fibers lacking a hydrogen bonding functionality will not have
particles bonded thereto with the strength and manner of the bonds
that would be present if the fibers had a hydrogen-bonding
functionality.
[0052] A hydrogen bond is an intermolecular force that occurs
between hydrogen atoms that are covalently bonded to small,
strongly electronegative elements (such as nitrogen and oxygen) and
nonbonding electron pairs on other such electronegative elements. A
hydrogen bonding functionality is a functional group that contains
an oxygen or nitrogen atom, for example hydroxyls, carboxyls,
sulfonic acids, sulfonamides, ethers, esters, epoxides, carbonyls,
amines, urethanes and others, that is capable of forming a hydrogen
bond. The orbitals of the nonbonding electron pairs on the oxygen
or nitrogen overlap with the relatively empty is orbital of the
hydrogen covalently bonded to another nitrogen or oxygen atom. The
1s orbital of the hydrogen is relatively empty due to the unequal
sharing of the electrons in the covalent bond between it and the
small electronegative atom (oxygen or nitrogen) to which it is
bound.
[0053] Specific examples of natural fibers that contain a hydrogen
bonding functionality include chopped silk fibers, wood pulp
fibers, bagasse, hemp, jute, rice, wheat, bamboo, corn, sisal,
cotton, flax, kenaf, peat moss, and mixtures thereof. Suitable
synthetic fibers with hydrogen bonding functionalities include
acrylic, polyester, carboxylated polyolefins, rayon and nylon. The
hydrogen-bonding functionality is an ester in acrylic fibers and a
carboxylic acid in carboxylated polyolefin fibers, an ester in
polyester, an amide in nylon, and a hydroxyl in rayon. Polyethylene
and polypropylene would be unsuitable fibers for use in particle to
fiber bonding in the manner of the present invention because they
include only carbons and hydrogens without any other atoms, such as
oxygens or nitrogens, that can participate in hydrogen bonds.
[0054] For purposes of convenience, and not to be construed as a
limitation, the following description proceeds with reference to
the treatment of individual chemical wood-pulp fibers. The fibers
are individualized, for example by defiberization in a hammermill.
Such individualized fibers are conventionally formed into a mat,
and are commercially available, for example as NB 416 fibers from
the Weyerhaeuser Company. Another suitable cellulosic mat would
include Rayfloc JLD from ITT Rayonier. The cellulose fibers may be
in the form of a cellulosic web or loose cellulose fibers.
III. Particle Characteristics
[0055] In accordance with the present invention, particles are
added to the fibers to give the fibers desired properties, such as,
by way of example only, increased absorbency, abrasiveness, or
antimicrobial activity. The particle can be any particulate
material that has the desired property and which is capable of
forming hydrogen bonds or coordinate covalent bonds with the
binder. It should be understood that some portion of the particles
may dissolve in the binder form. In certain cases, the particles
may be substantially soluble in both water and binder.
[0056] Hydrogen bonds can be formed, as discussed above, by
particles that contain certain functional groups, particularly
those having an oxygen or nitrogen. Coordinate covalent bonds, in
contrast, are formed by donation of a lone pair of electrons on one
atom to an empty orbital of another atom. Coordinate covalent bonds
differ from covalent bonds in that covalent bonds are formed by a
pair of electrons wherein one of the electrons is donated from each
of the atoms that participate in the bond. Particles can form
coordinate covalent bonds if they have an empty p or d or f orbital
that is capable of accepting a pair of electrons from the
binder.
[0057] A coordinate covalent bond occurs between a donor atom that
has a lone pair of electrons to donate to the bond, and an acceptor
atom that has an empty orbital to accept the lone pair of electrons
from the donor. According to the Aufbau and Pauli principles,
electrons occupy the lobes of atomic orbitals one at a time with a
maximum of two electrons (with opposite spins) per lobe. The most
basic orbital is the s orbital, which is available for bonding the
elements in the first row of the periodic table. In the second row
of the periodic table, electrons fill first the 2s orbital of Li
and Be. However, metals in periods less than three do not have
sufficient affinity for electrons to participate in coordinate
covalent bonding. Beginning with Group IIIB (boron), the three p
orbitals participate in coordinate covalent bonding and the lobes
of the p orbitals begin to fill. Boron has one electron in one of
the 2p orbitals, thus leaving the other 2 p orbitals empty and
available for coordinate covalent bonding. An example of a
coordinate covalently bonded boron containing particle is boric
acid, which is used as an astringent, antiseptic and fire
retardant. As shown below, the boron atom of boric acid acts as an
acceptor for a lone pair of electrons donated by an oxygen atom of
polypropylene glycol (PPG), thereby forming a coordinate covalent
bond between a boric acid particle and a PPG binder. The depiction
of boric acid shown below may not be typical of the aqueous
chemistry of boron, but rather is provided to illustrate the type
of bonding that is believed to occur in a coordinate covalent bond.
1
[0058] The next element, carbon, usually hybridizes to have one
electron in the 2s orbital and the three remaining electrons are
singly placed in the three p orbitals. This leaves no lobes empty
for coordinate covalent bonding and electron additions proceeding
further across that row of the periodic table also leave no lobes
empty. Hence, boron is the only element in the second row of the
periodic table that is capable of forming coordinate covalent
bonds.
[0059] Next the third row begins to fill, and the two 3s electrons
fill first in sodium and magnesium, but these metals in groups Ia
and IIa do not form coordinate covalent bonds as discussed above.
Then aluminum, like boron, places one electron in one of the 3p
lobes, and the two other 3p lobes are empty and available for
coordinate covalent bonding. The same trends continue across the
third row, but the third row elements also have available five 3d
lobes so the potential for coordination bonding exists even though
3p orbitals are occupied in the third row. Hence, Al, P, S, and Cl
are capable of accepting a pair of electrons from an electron-pair
donor to form a coordinate covalent bond. An example of this is
found in the bonding in PCl.sub.5, aluminum trihydrate, or
phosphorous pentasulfide. A phosphorous pentasulfide particle can
be used to increase flammability of a product, while aluminum
trihydrate is a fire retardant. An example of a coordinate
covalently bonded aluminum compound is 2
[0060] aluminum trihydrate, which may participate in a coordinate
covalent bond with a polypropylene glycol (PPG) polymer. In this
example, the aluminum atom of aluminum trihydrate acts as an
electron acceptor for an electron pair donated by an oxygen atom of
the polypropylene glycol (PPG) binder. The depiction of aluminum
trihydrate shown above may not be typical of the aqueous chemistry
of aluminum, but rather is provided to illustrate the type of
bonding that may occur in a coordinate covalent bond.
[0061] In the next row, the 4s orbital is filled first, then the 3d
lobes begin to fill one electron per lobe until all have added a
single then a second electron to each lobe until all lobes are
filled. However, 4p and 4f orbitals also are available, hence many
of the transition elements are capable of forming coordinate
covalent bonds.
[0062] The elements that have empty orbitals that participate in
coordinate covalent bonding include all those except the metals
(which excludes hydrogen) in periods one and two, and C, N, O, F,
Ne and He. The metals do not have sufficient affinity for electrons
to participate in coordinate covalent bonding. Especially preferred
particles contain boron, aluminum, iron, rhodium, osmium, platinum,
and palladium, and most particularly boron. Examples of particles
that are capable of coordinate covalent bonding are aluminum
trihydrate, antimony oxide, arsenic disulfide, bismuth aluminate,
bismuth iodide oxide, bismuth phosphate, bismuth subcarbonate,
bismuth subgallate, cadmium salycilate, chromic carbonate, chromic
hydroxide, chromic oxide, and chromic phosphate. All of the
polymeric binders of the present invention [polyglycols (such as
PPG), polycarboxylic acids (such as PAA), poly(lactone) polyols
(such as poly(caprolactone) diol), polyamides, polyamines, etc.]
are capable of donating a lone pair of electrons from an
electronegative atom, such as oxygen or nitrogen, to form a
coordinate covalent bond with a suitable particle that includes an
atom having an empty orbital for accepting electrons to form a
coordinate covalent bond.
IV. Superabsorbent Particles
[0063] In one disclosed embodiment the added particles are
superabsorbent particles, which comprise polymers that swell on
exposure to water and form a hydrated gel (hydrogel) by absorbing
large amounts of water. Superabsorbents are defined herein as
materials that exhibit the ability to absorb large quantities of
liquid, i.e., in excess of 10 to 15 parts of liquid per part
thereof. These superabsorbent materials generally fall into three
classes, namely starch graft copolymers, crosslinked
carboxymethylcellulose derivatives and modified hydrophilic
polyacrylates. Examples of such absorbent polymers are hydrolyzed
starch-acrylonitrile graft copolymer, a neutralized starch-acrylic
acid graft copolymer, a saponified acrylic acid ester-vinyl acetate
copolymer, a hydrolyzed acrylonitrile copolymer or acrylamide
copolymer, a modified cross-linked polyvinyl alcohol, a neutralized
self-crosslinking polyacrylic acid, a crosslinked polyacrylate
salt, carboxylated cellulose, and a neutralized crosslinked
isobutylene-maleic anhydride copolymer.
[0064] Superabsorbent particles are available commercially, for
example starch graft polyacrylate hydrogel fines (IM 1000F) from
Hoechst-Celanese of Portsmouth, Va., or larger particles such as
granules. Other superabsorbent particles are marketed under the
trademarks SANWET (supplied by Sanyo Kasei Kogyo Kabushiki Kaisha),
SUMIKA GEL (supplied by Sumitomo Kagaku Kabushiki Kaisha and which
is emulsion polymerized and spherical as opposed to solution
polymerized ground particles), FAVOR (supplied by Stockhausen of
Greensboro, N.C.), and NORSOCRYL (supplied by Atochem). The
superabsorbent particles come in a variety of sizes and
morphologies, for example IM 1000 and IM 1000F. The 1000F is finer
and will pass through a 200 mesh screen whereas IM 1000 has some
particles that will not pass through a 60 mesh screen. Another type
of superabsorbent particle is IM 5600 (agglomerated fines).
Superabsorbent particulate hydrophilic polymers also are described
in detail in U.S. Pat. No. 4,102,340. That patent discloses
hydrocolloid absorbent materials such as cross-linked
polyacrylamides.
V. Other Particles
[0065] Many particles that form hydrogen bonds or coordinate
covalent bonds are suitable for use with the present invention.
Some such particles are listed in Table I with an indication of the
function of the listed particles. The particles listed in Table I
are water-insoluble particles.
1TABLE I Water-Insoluble Particulates For Binding Name Function
Aluminum Trihydrate Fire retardant, astringent Acediasulfone
Antibacterial Agaricic acid Antiperspirant Alclometastone Topical
anti-inflammatory Calcium alginate Topical hemostatic Anidomycin
Fungicide Antimony oxide Fire retardant Apigenin Yellow dye,
mordant Arsenic disulfide Red Pigment Aspirin Anti-inflammatory;
antipyretic Azanidazole Antiprotozoal (Trichomonas) Azelaic acid
Antiacne Baicalein Astringent Bendazac Anti-inflammatory Benomyl
Fungicide; ascaricide Benzestrol Estrogen Benzylpenicillinic acid
Antibacterial Benzylsulfamide Antibacterial Bergaptene
Antipsoriatic Betasine Iodine source Bezitramide Narcotic analgesic
Bibrocathol Topical antiseptic Bietanautine Antihistaminic Bifenox
Herbicide Bifonazole Antifungal Binapacryl Fungicide, miticide Bis
(p-chlorophenoxy) Miticide methane Bismuth aluminate Antacid
Bismuth iodide oxide Anti-infective Bismuth phosphate Antacid;
protectant Bismuth subcarbonate Topical protectant Bismuth
subgallate Astringent, antacid; protectant Bisphenol A Fungicide
Bitertanol Agricultural fungicide Bithionol Topical anti-infective
Bromacil Herbicide Bromadiolone Rodenticide Bromcresol green
Indicator Bromcresol purple Indicator Bromethalinlin Rodenticide
p-Bromoacetanilide Analgesic; antipyretic 3-Bromo-d-camphor Topical
counterirritant Bromophos Insecticide Bromopropylate Acaricide
5-Bromosalicyl- antibacterial hydroxamic acid (tuberculostatic)
5-Bromosalycilic acid Analgesic acetate Bromosoligenin
Anti-inflammatory Bromthymol blue Indicator Broxyquinoline
Antiseptic; disinfectant Bucetin Analgesic Bumadizon Analgesic;
anti- inflammatory; antipyretic Bupirimate Fungicide Busulfan
Carcinogen, insect sterilant, antineoplastic Butamben Topical
anesthetic Butrylin Insecticide Butylated hydroxy- Antioxidant
(BHA) anisole Butyl paraben Pharmaceutic aid; food preservative
4-tert-Butylphenyl Light absorber salicylate Cacotheline Indicator
Cactinomycin Antineoplastic Cadmium salycilate Antiseptic Calamine
Skin protectant Calcium carbonate Antacid Calcium saccharate
Pharmaceutic aid Calcium tartrate Preservative; deodorant; antacid
Cambendazole Anthelminthic Candicidin Topical antifungal Candidin
Topical antifungal Capsaicin Topical analgesic Captan Fungicide;
bacteriostat Carbadox Antimicrobial Carbamazepine Anticonvulsant;
analgesic Carbarsone Antiamebic Carbaryl Contact insecticide
Carbazochrome Antihemorrhagic salycilate Carbendazim Fungicide
Carbochloral Hypnotic Carbophenothion Miticide; insecticide
Carboquone Antineoplastic Carisoprodol Skeletal muscle relaxant
Carthamin Dye Carvacrol Disinfectant Cephalin Local hemostatic
Chalcomycin Antibiotic Chartreusin Antibiotic Chitin Vulnerary
Chloramben Herbicide Chloramphenacol Antimicrobial palmitate
Chloranil Fungicide Chlorbetamide Antiamebic Chlordimeform
Insecticide Chlorfenac Herbicide Chlorfenethol Acaricide
Chlorhexidine Topical antibacterial Chloroazodin Antibacterial;
topical anesthetic Chlorophacinone Anticoagulant rodenticide
p-Chlorophenol Antiseptic Chlorothricin Antibiotic Chlorotrianisene
Estrogen Chloroxylenol Antiseptic; germicide Chlorphenesin Topical
antifungal chlorphenesin carbamate Relaxant (skeletal muscle)
Chlorphenoxamide Antiamebic Chlorpropamide Antidiabetic
Chlorpyrifos Insecticide Chlorquinaldol Topical antibaterial
Chlorsulfuron Herbicide Chlorothion Insecticide Chlozoxazone
Relaxant Cholesterol Pharmaceutic aid Chromic carbonate Pigment
Chromic hydroxide Pigment Chromic oxide Abrasive Chromic phosphate
Green pigment Chrysamminic acid Explosive Chrysarobin Antipsoriatic
Cilastazol Antithrombotic Cinoxate Sunscreen agent
[0066] Other suitable water-insoluble particles include proteins,
vitamins, zeolites and silica, each of which contains
electronegative atoms, such as oxygen or nitrogen groups, or both.
An example of a suitable zeolite is Abscents odor absorber
available from UOP of Tarrytown, N.Y. An example of a suitable
antimicrobial particle is chlorhexidine (N,N"-Bis(4-chlorophenyl)
-3,12-diimino-2,4,11,13-tetraazat- etradecanediimidamide). The list
in Table I is by no means exhaustive as it can be readily
determined for each type of particle whether it is capable of
forming a hydrogen bond or a coordinate covalent bond. Many of the
particles are non-absorbent, or not superabsorbent polymers.
[0067] The particles listed in Table I have chemical properties
that make them suitable for binding to fibers with the binders of
the present invention. The listed particles are organic or
inorganic compounds that have little or no water solubility, yet
have the capacity to hydrogen bond. Water solubility is preferably
low, for example, less than 10 g dissolves completely in 300 ml of
water at 25.degree. C., more preferably less than about 1 g in 300
ml at 25.degree. C. This low solubility allows the particles to
remain solid, and the hydrogen-bonding capacity allows them to
adhere to the fibers even in cases when an aqueous binder is used.
Once bound, the particles substantially retain a discrete
particulate form instead of dissolving or fusing. Hence, once bound
more of the particles are discrete than fused.
[0068] Many water-soluble particles that are capable of forming
hydrogen bonds or coordinate covalent bonds are suitable for use
with the binders of the present invention. Some such water-soluble
particles are listed in Table II with an indication of the function
of the listed particles.
2TABLE II Particulates For Binding Name Function
Ethylenediaminetetraacetic Odor absorbent acid (EDTA) disodium salt
of EDTA Chelator Sodium bicarbonate Odor absorbent/pH modifier
Acarbose Antidiabetic Acefylline Piperazine Bronchodilator
Acenocoumarol, sodium salt Anticoagulant Acephate Insecticide
Acetaminophen Analgesic Acetylleucine Antivertigo agent
Monoethanolamine Acid Violet 7B Dye/Stain Acitretin Antipsoriatic
Acranil Antiprotozoal (Giardia) Acriflavine Anti-infective
Actaplanins Growth stimulant Algestone Acetophenide Antiacne Algin
Hemostatic Almagate Antacid (-)-Ambroxide Fragrance Ambucaine
hydrochloride Local anesthetic Amodiaquin Antimalarial Anabasine
hydrochloride Insecticide o-Anisaldehyde Fragrance Anisomycin
hydrochloride Topical antitrichomonal Aralkonium chloride
Antiseptic, germicide Asiaticoside Dermatide, wounds, burns
Aspartame Non-nutritive sweetener Azidoamphenicol Antimicrobial in
eye infections Bebeerine Antimalarial Potassium benzoate
Preservative, antifungal Benzoyl peroxide Dermatide, antiacne
Benzylidene acetone Fragrance Bidrin Insecticide Biphenamine
hydrochloride Antiseborrheic Bishydroxycoumarin Anticoagulant
Bismuth tribromophenate Topical antiseptic Blasticidin S
hydrochloride Antimicrobial Bromocresyl green Indicator Bromophenol
blue Indicator Butathamine hydrochloride Anesthetic Caffeine
hydrochloride CNS Stimulant Calcium ascorbate Vitamin C/Calcium
source Calcium bisulfite Germicide Calcium thioglycollate
Depilatory Carbachol Ophthalmic parasympathomimetic Carbowax
Ointment base Cetalkonium chloride Antibacterial Cethoxonium
bromide Antiseptic Chartreusin Antimycobacterial Chloramine-T
Topical antiseptic Cinnamic acid Fragrance Cotarnine chloride
Hemostatic Demercarium bromide Topical antiglaucoma D-2-deoxyribose
DNA synthesis Dequalinium chloride Antiseptic Dermostatin Anti
fungal Dexamethasone Glucocorticoid Diacetone acrylamide Mfr
coatings, adhesives 2,4-Diamino-6- Indicator of hydroxypyrimidine
nitrates/nitrites 2,4-Diaminophenol Photographic developer
dihydrochioride Diamthazole dihydrochloride Antifungal Diatrizoate
sodium Diagnostic aid Dibekacin sulfate Antibacterial Disodium
4',5'- FDA approved dye dibromofluorescein 3,5-Dibromo-4- Topical
disinfectant hydroxybenzenesulfonic acid, sodium salt
Dibromopropamidine Cosmetic preservative Diflorasone Topical
anti-inflammatory Dihydroxyacetone Artificial tanning agent
Diisobutyl sodium Wetting agent/detergent sulfosuccinate Dikegulac
Plant growth regulator Dimethisoquin Topical anesthetic
Diphenicillin sodium Antibacterial Diphetarsone Antiamebic Dipyrone
Analgesic, antipyretic Diquat dibromide Herbicide, defoliant Dodine
Fungicide Domiphen bromide Topical anti-infective Dulcin
Non-nutritive sweetener Dymixal .RTM. Topical burn treatment
Ecognidine Topical anesthetic Edetic acid Antioxidant Edoxudine
Antiviral Ellagic acid Hemostatic Endothal Herbicide, defoliant
Eosine I bluish Dye Eosine yellowish Cosmetic dye Erythrosine Food
dye Esculin Skin protectant Ethacridine Antiseptic Ethambutol
hydrochloride Antibacterial (tuberculostatic) Ethamsylate
Hemostatic Ethylidene dicoumarol Anticoagulant Ethylstibamine
Antiprotozoal Euprocin dihydrochloride Topical anesthetic Fast
green FCF Food coloring Fenticonazole nitrate Topical antifungal
Ferric albuminate Hematinic Ferric chloride hexahydrate Astringent,
styptic Ferric formate Silage preservative Ferrulic acid, sodium
salt Food preservative Fluorescein, disodium salt Diagnostic aid
Fluoridamid Plant growth retardant Forminitrazol Antiprotozoal
(Trichomonas) Fortimicin(s) Antibacterial Foscarnet sodium
Antiviral (HIV-1) Fosetyl Al Systemic fungicide Fungichromin
Topical antifungal Gallic acid Astringent, styptic Gentian violet
Topical anti-infective Gluconolactone Cleaner Gossypol Rubber
antioxidant Heparin Anticoagulant Hexainethylolmelamine
Fireproofing agent Mexamidine Antiseptic, anti-acne Homatropine
Anticholinergic (opthtalmic) Hydrastinine hydrochloride Uterine
hemostatic Hydrocortisone phosphate, Glucocorticoid disodium salt
Hydroquinine hydrochloride Depigmentor hemihydrate
Hydroxyamphetamine Andregenic (opthtalmic) hydrobromide
Hydroxybutyranilide Antioxidant 3-Hydroxycamphor Topical
antipruritic 1-(Hydroxymethyl)-5,5- Cosmetic preservative
dimethylhydantion 8-Hydroxyquinoline sulfate Antiperspirant,
deodorant Iodic acid Astringent Itraconazole Antifungal
Kanamycin(s) Antibacterial Kermesic acid Dye Kojic acid Flavor
enhancer Laccaic acid Crimson dye Lactic acid Acidulant Litmus
Indicator L-Lysine L-glutamate Flavor additive Lyxoflavine
Feedstuff, growth- promoter Maclurin Dye Malachite green Dye Maltol
Flavor enhancer Maneb Agricultural fungicide ~Manganese acetate
Mordant Meralein sodium Topical anti-infective
[0069] Plus a host of others, including a wide range of inorganic
salts.
[0070] The list in Table II is by no means exhaustive as it can be
readily determined for each type of particle whether it is capable
of forming a hydrogen bond or a coordinate covalent bond. All or
most of the particles are non-absorbent, or not superabsorbent
polymers. Solubility of the particle in water and the binder can be
easily ascertained, for example in standard chemical reference
materials.
[0071] The particles listed in Table II have chemical properties
that make them suitable for binding to fibers with the binders of
the present invention. The listed particles are organic or
inorganic compounds that are water soluble, yet have the capacity
to hydrogen bond. Water solubility is preferably high. By water
soluble it is meant that the particles dissolve at a rate higher
than 10 g in 300 ml of water at 25.degree. C. The range of
solubilities can extend, for example, from a lower limit of 10 g in
300 ml of water at 25.degree. C., to an upper limit in which the
particle is miscible in all proportions with water at 25.degree. C.
This high solubility allows the particles to dissolve when exposed
to aqueous liquids such as urine, but the hydrogen bonding capacity
allows them to adhere to the fibers in the presence of binder but
in the absence of aqueous liquid during use by an end user after
the manufacturing process is completed. While bound, many of the
particles substantially retain a discrete particulate form instead
of dissolving or fusing, at least until they are exposed to an
aqueous liquid. More of the particles are discrete rather than
agglomerated while bound in the absence of an aqueous liquid. If
the particles are exposed to fibers with binder in liquid form, for
the particles to retain their particulate form a binder is
preferably selected so that the particles are sparingly soluble in
the binder. By sparingly soluble it is meant that no more than
about 5 g of particles dissolve in 300 ml of the binder at
25.degree. C.
[0072] The amount of particles added to the fibers can vary widely,
for example from 0.05 to 80 percent of the total weight of the
fibrous material and particles. Antimicrobials such as
chlorhexidine are effective in very low amounts, such as 0.05
percent. Superabsorbent particles are preferably added in an amount
of 3-80 percent, especially 20-60 percent by weight of the fibrous
materials and particles.
VI. Polymeric Binder Characteristics
[0073] The particles may be bound to the fibers by combining the
particles with a polymeric binder, which may be water soluble. The
polymeric binder is selected from a predetermined group of
polymeric binders. The polymeric binders comprise polymeric binder
molecules wherein the polymeric binder molecules have at least one
hydrogen bonding functionality or coordinate covalent bond forming
functionality. Preferred binders may further comprise repeating
units, wherein the repeating units have such functionalities on
each repeating unit of the polymer, although this is not necessary
for adequate binder functions. In accordance with the present
invention, the predetermined groups of polymeric binders include
the group of binders consisting of polyglycols [especially
poly(propyleneglycol)], a polycarboxylic acid, a polycarboxylate, a
poly(lactone) polyol, such as diols, a polyamide, a polyamine, a
polysulfonic acid, a polysulfonate, and combinations thereof.
Specific examples of some of these compounds, without limitation,
are as follows: polyglycols may include polypropylene glycol (PPG)
and polyethylene glycol (PEG); poly(lactone) polyols include
poly(caprolactone) diol and poly(caprolactone) triol;
polycarboxylic acids include polyacrylic acid (PAA) and polymaleic
anhydride; polyamides include polyacrylamide or polypeptides;
polyamines include polyethylenimine and polyvinylpyridine;
polysulfonic acids or polysulfonates include
poly(sodium-4-styrenesulfonate) or
poly(2-acrylamido-methyl-1-propanesulfonic acid; and copolymers
thereof (for example a polypropylene glycol/polyethylene glycol
copolymer). The polymeric binder typically has repeating units. The
repeating unit may be the backbone of a compound, such as with a
polypeptide, wherein the repeating polyamides occur in the peptide
chain. The repeating unit may also refer to units other than
backbones, for instance repeating acrylic acid units. In such a
case, the repeating units may be the same or different. The binder
has a functional group capable of forming a hydrogen bond or a
coordinate covalent bond with particles, and a functional group
capable of forming a hydrogen bond with the fibers.
[0074] As used herein, a polymer is a macromolecule formed by
chemical union of 5 or more identical or different combining units
(monomers). A polyamine is a polymer that contains amine functional
groups and a polyamide is a polymer that contains amide functional
groups. Each of the binders has a hydrogen bonding or a coordinate
covalent bonding functionality, and each of the binders may have
such functionalities on each repeating unit (monomer) of the
polymer. This repeating functionality may be a hydroxyl, a
carboxyl, a carboxylate, a sulfonic acid, a sulfonate, an amide, an
ether, an amine or combinations thereof. These binders are capable
of forming hydrogen bonds because they have a functional group that
contains an electronegative element, such as oxygen or a
nitrogen.
[0075] The polyglycol has repeating ether units with hydroxyl
groups at the terminal ends of the molecule. The polycarboxylic
acid, such as polyacrylic acid, has a repeating carboxyl group in
which a hydrogen is bound to an electronegative oxygen, creating a
dipole that leaves the hydrogen partially positively charged. The
polyamide (such as a polypeptide) or polyamine has a repeating NR
group in which a hydrogen may be bound to an electronegative
nitrogen that also leaves the hydrogen partially positively
charged. The hydrogen in both cases can then interact with an
electronegative atom, particularly oxygen or nitrogen, on the
particle or fiber to form a hydrogen bond that adheres the binder
to the particle and fiber. The electronegative oxygen or nitrogen
of the binder also can form a hydrogen bond with hydrogenatoms in
the particle or fiber that have positive dipoles induced by
electronegative atoms, such as oxygens or nitrogens, to which the
hydrogen is attached. The polyamide also has a carbonyl group with
an electronegative oxygen that can interact with hydrogen atoms in
the particles or fibers. Thus, the polymeric binders can enhance
the hydrogen bonding (a) between the fibers and binder; and (b) in
the case of particles with hydrogen bonding functionalities,
between the binder and the particles.
[0076] Alternatively, the polymeric binder may form a coordinate
covalent bond with the particles and a hydrogen bond to the fibers.
For example, the oxygen or nitrogen on the binder has an unbound
pair of electrons that can be donated to an empty orbital in the
particle to form a coordinate covalent bond. For example, one free
pair of electrons on the oxygen or nitrogen can be donated to the
empty p orbital of a boron-containing particle to form a coordinate
covalent bond that adheres the particle to the binder. The fibers
themselves contain functional groups that can form hydrogen bonds
with the binder, and allow the binder to adhere to the fiber.
Cellulosic and synthetic fibers, for example, may contain hydroxyl,
carboxyl, carbonyl, amine, amide, ether and ester groups that will
hydrogen bond with the hydroxyl, carboxylic acid, carboxylate,
amide or amine groups of the binder. Hence, the polymeric binder
will adhere the particle with a coordinate covalent bond and the
fiber will adhere with a hydrogen bond.
[0077] In some preferred embodiments, the polymeric binder is bound
to both the fibers and the particle by hydrogen bonds. A
polypropylene glycol binder, for example, can be used to bind
water-insoluble polyacrylate hydrogel particles to cellulosic
fibers. The hydroxyl and ether groups on the glycol binder
participate in hydrogen-bonding interactions with the hydroxyl
groups on the cellulose fibers and the carboxyl groups on the
polyacrylate hydrogel, as shown below: 3
[0078] Alternatively, a polypropylene glycol (PPG) binder, for
example, can be used to bind a water-soluble particle to cellulosic
fibers. The hydroxyl and ether groups on the glycol binder
participate in hydrogen bonding interactions with the hydroxyl
groups on the cellulose fibers and appropriate functionalities on
the water-soluble particle, as shown on page 41.
[0079] Hence, the binder will adhere both the particle and fiber
with hydrogen bonds. The presence of a hydrogen-bonding
functionality on each repeating unit of the polymeric binder has
been found to increase the number of hydrogen bonding interactions
per-unit-mass of polymer, which provides superior binding
efficiency and diminishes separation of particles from the fibers.
The repeating ether functionality on the glycol binder provides
this efficiency in the examples diagrammed above. A repeating
carboxyl group is the repeating functionality on polyacrylic acid,
while repeating carbonyls and NR groups (wherein R is either an H
or 4
[0080] alkyl, preferably lower alkyl i.e., less than five carbon
atoms, in a normal or iso configuration) of the amide linkages are
the repeating functionalities on polyamides such as polypeptides. A
repeating amine group is present on polyamines.
[0081] The polymeric organic binders of the present invention are
expected to increase in binding efficiency as the length of the
polymer increases, at least within the ranges of molecular weights
that are reported in the examples below. This increase in binding
efficiency would be attributable to the increased number of
hydrogen bonding or coordinate covalent bonding groups on the
polymer with increasing molecular length. Each of the polymeric
binders has a hydrogen bonding or coordinate covalent bonding
functionality, and each such binder may have such functionalities
on each repeating unit of the polymer. Hence, longer polymers
provide more hydrogen bonding groups or coordinate covalent bonding
groups that can participate in hydrogen-bonding interactions or in
coordinate covalent bonds.
[0082] Although the invention is not limited to polymeric binders
of particular molecular weights, polymeric binders having a
molecular weight greater than 500 grams/mole are preferred because
they provide attractive physical properties, and the solid is less
volatile as compared to low-molecular-weight polymeric binders.
Polymeric binders with molecular weights greater than 4000
grams/mole are especially preferred because they have minimal
volatility and are less likely to evaporate from the particles.
Low-molecular weight materials typically are more mobile than are
the higher-molecular weight materials. Low-molecular weight
materials can more easily move to the fiber-particle interface, and
are more easily absorbed by the fiber, thus making them less
available to bond the particles to the fibers. The higher molecular
weight materials are less apt to be absorbed by the fibers, and are
less volatile than the low-molecular weight materials. As a result,
higher molecular weight polymeric binders, to a greater extent,
remain on the surface of the particles where they are more
available to bond particles to fibers. In some particular
embodiments, polymers with molecular weights between 4000 and 8000
grams/mole have been used. Polymers with molecular weights above
8000 may be used, but such exceedingly high molecular weight
polymers may decrease binding efficiency because of processing
difficulties.
[0083] Certain polymeric binders have greater binding efficiency
because their repeating functionality is a more efficient hydrogen
bonding group. It has been found that repeating amide groups are
more efficient than repeating carboxyl functionalities, which are
more efficient than repeating hydroxyl functionalities, which in
turn are more efficient than amine or ether functionalities. Hence,
polymeric binders may be preferred that have repeating amine or
ether functionalities, more preferably repeating hydroxyl
functionalities, and even more preferably repeating carbonyl or
carboxyl functionalities, and most preferably repeating amide
functionalities. Binding may occur at any pH, but is suitably
performed at a neutral pH of 5-8, preferably 6-8, to diminish acid
hydrolysis of the resulting fibrous product. Suitable binders may
be selected from the group consisting of polyglycols such as
polyethylene glycol or polypropylene glycol, polycarboxylic acids
such as polyacrylic acid, polyamides, polyamines, poly(lactone)
polyols, such as poly(caprolactone) diol, and combinations or
copolymers thereof.
[0084] The group consisting of polycarboxylic acids (such as
acrylic acid), polyamides and polyamines has been found to have a
especially good binding efficiency. Among polyamides, polypeptides
are especially preferred.
VII. Non-Polymeric Binder Characteristics
[0085] The particles may be bound to the fibers by a non-polymeric
organic binder selected from a predetermined group of binders that
each have a volatility less than water. The vapor pressure of the
binder may, for example, be less than 10 mm Hg, at 25.degree. C.,
and more preferably less than 1 mm Hg at 25.degree. C. The
non-polymeric binders comprise non-polymeric binder molecules
wherein the non-polymeric binder molecules have at least one
functional group that forms hydrogen bonds or coordinate covalent
bonds with the particles. In accordance with the present invention,
the predetermined group of non-polymeric binders may include a
functional group selected from the group consisting of a carboxyl a
carboxylate, a carbonyl, a sulfonic acid, a sulfonate, a phosphate,
a phosphoric acid, a hydroxyl, an amide, an amine, and combinations
thereof (such as an amino acid or a hydroxy acid) wherein each
binder includes at least two such functionalities, and the two
functionalities are the same or different. A requirement for the
non-polymeric binder is that it have a plurality of functional
groups that are capable of hydrogen bonding, or at least one group
that can hydrogen bond and at least one group that can form
coordinate covalent bonds. As used herein, the term "non-polymeric"
refers to a monomer, dimer, trimer, tetramer, and oligomers,
although some particular non-polymeric binders are monomeric and
dimeric, preferably monomeric.
[0086] Particularly preferred non-polymeric organic binders are
capable of forming five or six membered rings with a functional
group on the surface of the particle. An example of such a binder
is an amine or amino acid (for example, a primary amine or an amino
acid such as glycine) which forms six-membered rings by forming
hydrogen bonds: 5
[0087] A six-membered ring also is formed by the hydroxyl groups of
carboxylic acids, alcohols, and amino acids, for example: 6
[0088] A five membered ring can be formed by the binder and the
functionality on the surface of the particle, for example: 7
[0089] wherein the particle is a water-insoluble particle such as
SAP and the binder is an alcohol, such as a polyol with hydroxyl
groups on adjacent carbons, for example 2,3-butanediol. A binder
that forms a five-membered ring can also be used with a
water-soluble particle, for example wherein the particle is EDTA
and the binder is an alcohol, such as a polyol with hydroxyl groups
on adjacent carbons, for example 2,3-butanediol.
[0090] Other alcohols that do not form a five-membered ring also
can be used, for example alcohols that do not have hydroxyl groups
on adjacent carbons. Examples of suitable alcohols include primary,
secondary or tertiary alcohols.
[0091] Amino alcohol binders are alcohols that contain an amine
group (--NR.sub.2), and include binders such as ethanolamine
(2-aminoethanol), and diglycolamine (2-(2-aminoethoxy)ethanol)).
Non-polymeric polycarboxylic acids contain more than one carboxylic
acid functional group, and include such binders as citric acid,
propane tricarboxylic acid, maleic acid, butanetetracarboxylic
acid, cyclopentanetetracarboxyli- c acid, benzene tetracarboxylic
acid and tartaric acid. A polyol is an alcohol that contains a
plurality of hydroxyl groups, and includes diols such as the
glycols (dihydric alcohols) ethylene glycol, propylene glycol and
trimethylene glycol; triols such as glycerin (1,2,3-propanetriol);
esters of hydroxyl containing binders may also be used, with mono-
and di-esters of glycerin, such as monoglycerides and diglycerides,
being especially preferred; and polyhydroxy or polyearboxylic acid
compounds such as tartaric acid or ascorbic acid (vitamin C): 8
[0092] Hydroxy acid binders are acids that contain a hydroxyl
group, and include hydroxyacetic acid (CH.sub.2OHCOOH) and lactic,
tartaric, ascorbic, citric, and salicylic acid. Amino acid binders
include any amino acid, such as glycine, alanine, valine, serine,
threonine, cysteine, glutamic acid, lysine, or .beta. alanine.
[0093] Sulfonic acid binders and sulfonates are compounds that
contain a sulfonic acid group (--SO.sub.3H) or a sulfonate
(--SO.sub.3.sup.-). Amino-sulfonic acids also can be used. One
example of an amino-sulfonic acid binder suitable for the present
invention is taurine, which is 2-aminoethanesulfonic acid.
[0094] Non-polymeric polyamide binders are small molecules (for
example, monomers or dimers) that have more than one amide group,
such as oxamide, urea and biuret. Similarly, a non-polymeric
polyamine binder is a non-polymeric molecule that has more than one
amine group, such as ethylene diamine, EDTA or the amino acids
asparagine and glutamine.
[0095] Although other non-polymeric organic binders are suitable in
accordance with the discussion above, the non-polymeric organic
binder is preferably selected from the group consisting of
glycerin, a glycerin monoester, a glycerin diester, glyoxal,
ascorbic acid, urea, glycine, pentaerythritol, a monosaccharide, a
disaccharide, citric acid, taurine, tartaric acid,
dipropyleneglycol, an urea derivative, phosphate, phosphoric acid,
and combinations thereof (such as hydroxy acids). The non-polymeric
binder also is most preferably selected from the group consisting
of glycerin, a glycerin monoester, a glycerin diester, a
polyglycerin oligomer, a propylene glycol oligomer, urea and
combinations thereof (such as glycerin and urea). As used herein,
an oligomer refers to a condensation product of polyols, wherein
the condensation product contains less than ten monomer units. A
polyglycerin oligomer as referred to herein means a condensation
product of two or more glycerin molecules. A propylene glycol
oligomer as referred to herein means a condensation product of two
or more propylene glycol molecules. The non-polymeric binders also
preferably include functionalities selected from the group
consisting of a carboxyl, a carboxylate, a carbonyl, a sulfonic
acid, a sulfonate, a phosphate, a phosphoric acid, a hydroxyl, an
amine, an amide, and combinations thereof (such as amino acids and
hydroxy acids). The non-polymeric binders may have at least two
functionalities from such group, and the groups may be the same or
different.
[0096] Each of the non-polymeric binders disclosed above is capable
of forming hydrogen bonds because it has a functional group that
contains electronegative atoms, particularly oxygens or nitrogens,
or has electronegative groups, particularly groups containing
oxygens or nitrogens, and that also may include a hydrogen. An
amino alcohol, amino acid, carboxylic acid, alcohol and hydroxy
acid all have a hydroxyl group in which a hydrogen is bound to an
electronegative oxygen, creating a dipole that leaves the hydrogen
partially positively charged. The amino alcohol, amino acid, amide
and amine all have an NR group in which a hydrogen may be bound to
an electronegative nitrogen that also leaves the hydrogen partially
positively charged. The partially positively charged hydrogen in
both cases then can interact with an electronegative element, such
as oxygen or nitrogen, on the particle or fiber to help adhere the
binder to the particle and fiber. The polycarboxylic acid, hydroxy
acid, amino acid and amide also have a carboxyl group with an
electronegative oxygen that can interact with hydrogen atoms in the
particles and fibers, or in intermediate molecules between the
binder and particles or fibers. Similarly, electronegative atoms
(such as oxygen or nitrogen) on the fiber or particle can interact
with hydrogen atoms on the binder that have positive dipoles, and
partially positive hydrogen atoms on the fiber or particle can
interact with electronegative atoms on the binder.
[0097] Several proposed hydrogen bonding interactions of two of the
binders (glycine and 1,3-propanediol) with cellulose are shown
below: 9
[0098] The hydrogen bonding interactions are shown as dotted lines.
One such interaction is shown between the nitrogen of glycine and a
hydrogen of an --OH on cellulose. A hydrogen bond with glycine is
also shown between an oxygen of the --OH on glycine and the hydroxy
hydrogen of an alcohol sidechain on cellulose. Hydrogen bonding
interactions of the 1,3-propanediol are shown in dotted lines
between an oxygen on an --OH group of the binder and a hydrogen of
an --OH group on the cellulose molecule. Another hydrogen bond is
also shown between a hydrogen on an --OH group of the glycol binder
and an oxygen in an alcohol sidechain of the cellulose.
[0099] It also is possible for water or other hydrogen bonding
molecules to be interposed between the fiber and binder, such that
the fiber and binder are both hydrogen bonded to the water
molecule.
[0100] Alternatively, an atom on the binder may have an unbound
pair of electrons, such as a lone pair of electrons from an oxygen
or nitrogen atom, that can be donated to an empty orbital of an
acceptor atom in the particle to form a coordinate covalent bond.
The free pair of electrons on the oxygen or nitrogen can be donated
to the empty p, d or f orbital of a particle (for example a
boron-containing particle) to form a coordinate covalent bond that
adheres the particle to the binder. The fibers themselves do not
normally contain functional groups that can act as electron
acceptors in the formation of coordinate covalent bonds with the
binders, but hydrogen bonding interactions allow the binder to
adhere to the fiber. Cellulosic and synthetic fibers, for example,
contain hydroxyl, carboxyl and ester groups that will hydrogen bond
with the hydroxyl, carboxylic acid, amide, amine, or other groups
of the binder. Non-cellulosic or non-synthetic fibers that have
these functionalities also can be used, for example silk, which has
an amide linkage. Hence the binder will adhere the particle with a
coordinate covalent bond and the fiber with a hydrogen bond.
[0101] In some preferred embodiments, the binder is bound to both
the fibers and the particle by hydrogen bonds. A polyol binder,
such as a diol, for example, can be used to bind polyacrylate
hydrogel particles to cellulosic fibers. The hydroxyl groups on the
polyol binder participate in hydrogen-bonding interactions with the
hydroxyl groups on the cellulose fibers and the carboxyl groups on
the polyacrylate hydrogel. Hence, the binder will adhere to both
the particle and fiber with hydrogen bonds. These hydrogen bonds
provide excellent binding efficiency and diminish separation of
bound particles from the fibers.
[0102] A structural drawing is shown below in which citric acid,
vitamin C and urea adhere water-insoluble SAP particles to
cellulose with hydrogen bonds, or water-soluble EDTA particles.
Some of the possible hydrogen bonding interactions are shown as
dashed lines. It is possible that other molecules (such as water
molecules) also may participate in some of these bonds, for
example, as an intermediary between the binder and particle or
fiber. 10
[0103] Particularly efficient hydrogen bonding binders include
those with carboxyl groups, such as ascorbic acid, or amide groups,
such as urea. Hydroxyl groups are also very efficient binders.
Amine and ether functionalities are less efficient binders.
[0104] Binders have functional groups that may be selected
independently or in combination from the group consisting of a
carboxyl, a carboxylate, a carbonyl, a hydroxyl, a sulfonic acid, a
sulfonate, a phosphoric acid, a phosphate, an amide, an amine, and
combinations thereof. These functional groups might be provided by
the following exemplary chemical compounds: a carboxyl group could
be provided by carboxylic acids, such as ascorbic acid; a
carboxylate, which is an ionized carboxylic acid, could be provided
by a material such as potassium citrate; a carbonyl group can be
provided by an aldehyde or ketone; a hydroxyl can be provided by an
alcohol or polyol, such as glycerol, or a mono- or diglyceride,
which are esters of glycerol; an amide, such as a urea; and an
amine, which may be provided by an alkyl amine, such as
ethanolamine, wherein the binder has at least two of these
functional groups, and each of the functional groups can be the
same (for example, a polyol, polyaldehyde, polycarboxylic acid,
polyamine or polyamide) or different (for example, an amino
alcohol, hydroxy acid, hydroxyamide, carboxyamide, or amino acid).
Functional groups also may be selected independently or in
combination from the group consisting of carboxyl, an alcohol, an
amide and an amine. An aldehyde may optionally be a member of each
of these groups, particularly if it is oxidized to a carboxylic
acid.
[0105] Combinations of polymeric and non-polymeric binders may also
be used, with or without other binders, providing that they are
non-reactive. That is, providing that the binders do not react in a
manner which prevents the binders from possessing the functional
groups required to be present for binding in accordance with the
present invention.
VIII. Process Advantages
[0106] The binders of the present invention also provide numerous
process advantages. Binding of particles to the fibers can occur,
for example, without external application of heat. Hence, if
desired, particle binding may occur at ambient temperature. The
present invention therefore is distinct from prior-art crosslinking
processes in which elevated temperatures are required to covalently
crosslink cellulose groups to one another. Moreover, the binders of
the present invention have the advantage of being reactivatable by
addition of a fluid, such as a liquid solvent (sometimes referred
to herein as a reactivation liquid, one example of which is water).
Hence, a liquid binder (which would include a solution of a solid
or liquid binder, or a binder that has a melting point below room
temperature) can be applied to particles and the binder allowed to
air dry, for example until the particles reach an equilibrium
moisture content with the moisture in the ambient air. The binder,
which at least partially coats the particle, may then be
reactivated in the presence of fibers to bind the particles in
place. Some of the binders-(especially the liquid binders) may,
after the particles are bound to fibers, diffuse throughout the
fibers to reach an equilibrium distribution of the binder.
Alternatively, the binder can be combined with the particles as a
solid, for example as particles or a powder. At a later stage of
processing, water or another activating fluid or liquid may be
added to the combined binder and particles. The particles with
activated binder then may be added to the mat and adhered, for
example to target areas of a fiber mat. Alternatively, the
particles and partially coating binder may be added to the mat
prior to or simultaneously with activation of the binder.
[0107] The binders may be liquids at room temperature (such as
glycerin), or liquid solutions of binders that are solids at room
temperature (for example, an aqueous solution of glycine), or
liquid hot melts of solid binders. Solid binders may be blended
with particles in particulate form, provided they are fixed or
adhered to the fibers at a later time, for example by the
subsequent application of heat, pressure, or liquid.
[0108] The binding reaction of the present invention can occur
across a broad range of pH without requiring a catalyst. A suitable
pH range without a catalyst is 1-14, but preferred ranges are 5-8
or 6-8 because such neutral pH ranges will produce fibrous products
(such as cellulose products) that are less prone to damage by acid
hydrolysis. A non-acidic pH (7 or greater) will provide an
environment that inhibits formation of ester bonds, and promotes
formation of the hydrogen bonds or coordinate covalent bonds that
adhere the particles of the present invention to the fibers with
the binder.
[0109] When water-insoluble particles are used, the moisture
content of the fibers during the binding reaction is 0.5-50%,
suitably 5-40%, or preferably 5-20% water by weight of the fibers,
binder and particle. A moisture content greater than 20%,
preferably 30%, or in the range 20-50%, or 30-50%, can be used even
though such high moisture contents interfere with intermediate
anhydride formation and inhibits formation of covalent bonds in the
production of high-bulk crosslinked fibers. When water-soluble
particles are used, the moisture content of the fibers during the
binding reaction is 0.5-30%, suitably 5-25%, preferably 12-20%.
Particles may be added to the fibers with the particles distributed
throughout a fibrous product without being confined to a surface of
the product. The particles can be distributed throughout the depth
of a fiber product such as a mat or web.
[0110] The binder suitably is present in an amount of at least 0.01
percent, and no more than 80 percent, by weight of the particles
("percent by weight"). In especially preferred embodiments, the
binder is present in an amount of 0.03 to 50 percent, preferably
0.03 to 20 percent, more preferably 0.03 to 5 percent, and even
more preferably 0.03 to 1 percent by weight of the particles. Below
about 0.01 percent when combined with the particles, an
insufficient amount of binder is present to achieve adequate
binding. Using excessive amounts of binder can introduce
unnecessary expense into the binding process. High percentages of
binder can also cause processing problems because the binder
material transfers to equipment surfaces. Therefore, it is often
preferred to use no more binder than is required to bind the
particles and fibers.
[0111] Thermoplastic binders also may be used to help bind fibers
to each other and particles to fibers. The binder that has the
hydrogen bonding or coordinate covalent bonding functionalities
itself may be thermoplastic. The polymeric binders and some
non-polymeric binders of the present invention have the advantage
of being thermoplastic or meltable solids. Hence, particles treated
with such binders in accordance with the present invention may be
thermobonded by elevating the fiber temperature above the melting
temperature of the binder to melt or soften the thermoplastic
binder and physically bind the particles to the fibers and to a
limited extent (unless high percentage of binders are used) the
fibers to each other. Alternatively, an auxiliary or second binder
can be applied to the fibers as a solid at room temperature, and
the temperature of the second binder elevated above its melting
point to thermobond the fibers and particles. The auxiliary binder
may be applied to the fibers either before or after the primary
binder containing particles are combined with the fibers, but
before thermobonding.
[0112] The particles with binders of the present invention may be
used with fibers that have substantial intrafiber covalent
crosslinks (such as HBA available from Weyerhaeuser) or fibers
which are substantially free of intrafiber covalent crosslinking.
Examples of individualized intrafiber crosslinked fibers are seen
in European Patent Applications 440 472 A1 and 427 317 A2, which
produce products that those publications describe as being
substantially free of interfiber bonds. The fibers of the present
invention do not need to be processed as in those European
applications to eliminate interfiber bonds. Particles at least
partially coated with binders of the present invention can
therefore be used with natural fibers that have substantial
interfiber bonding, which are defined as fibers that have not been
processed as in European Applications 440 472 A1 and 427 317 A2 to
substantially eliminate interfiber bonds. Cellulose fibers that
have not been so processed are substantially free of intrafiber
bonds. The fibrous product of the present method (with or without
intrafiber crosslinking) may further be densified by external
application of pressure. The densified product is compact and
easily transported. And, when the particles are superabsorbent
particles, the resulting fibrous product has superior absorbent
properties as compared to nondensified products. The inventors have
found that the binders of the present invention produce a product
that can be easily densified. Easy densification is associated with
the hydrogen bonds and coordinate covalent bonds formed between the
binder and the particles and fibers. The fibers are particularly
easily densified when at least 5% by weight of the fibers,
particles and binder, more preferably 10%, are particles adhered to
the fibers. Moreover, densification appears to be facilitated by
using superabsorbent particles, and even more suitably densifying
using superabsorbent particles at least partially coated with an
active binder as the time densification occurs.
[0113] In accordance with this invention, the binders may be
applied to particles before, or simultaneously with, addition of
the particles to the fibers. A preferred approach is to simply
spray, as by a mist or fog, the binder onto the particles as the
particles are delivered to the fibers. Simultaneous addition can be
accomplished by two separate streams of particles and binder that
are simultaneously directed at a fibrous substrate, or
alternatively merged immediately or some time prior to impacting
against the substrate. Some of the binder may reach the fibers
without impacting a particle, but the bulk of the particles will be
at least partially coated with the binder. Without limiting the
invention, it appears that the addition of small amounts of
moisture to the particles may help bind superabsorbent particles
and perhaps other types of particles to the fibers. For example,
exposing the particles to air at 65 percent humidity as they are
delivered to binder coated particles may enhance the particle
bonding to the fibers.
[0114] Binding may be performed under conditions that favor
formation of hydrogen bonds or coordinate covalent bonds, and
discourage formation of covalent bonds. Conditions that favor
covalent bonds are those disclosed in U.S. Pat. No. 4,412,036 and
U.S. Pat. No. 4,467,012 wherein particle and binder would be
laminated between tissue layers under high temperature and pressure
to form laminated adherent tissue layers. That patent teaches that
minimal adhesion occurs at 200 pli (pounds per linear inch, as in a
calendar press) if no external heat is supplied, but adhesion
improves as the reaction temperature increases. Improved adhesion
of the tissue layers occurs because of enhanced covalent bonding as
the temperature increases.
[0115] Conditions that favor covalent bond formation are also shown
in European Patent Applications 440 472 A1; 427 317 A2; 427 316 A2;
and 429 112 A2. These European publications use polycarboxylic acid
crosslinkers, and require elevated temperatures (for example above
145.degree. C.) and acidic conditions (pH less than 7) to promote
formation of intrafiber covalent ester bonds and inhibit reversion
of the ester bonds. The present invention, in contrast, can form
hydrogen or coordinate covalent bonds below 145.degree. C., below
100.degree. C., and even at room temperature. The binders of the
present invention also can bind particles to fibers under neutral
or alkaline conditions, i.e., at a pH above 7, but preferably at a
pH of 5-8 or 7-8. Fibers that have high bulk as a result of
intrafiber covalent crosslinks are prepared by individualizing the
fibers (for example, in a fiberizer) and curing them at an elevated
temperature (above 150.degree. C.). Initial application of the
binder-coated particles on such high-bulk fibers preferably occurs
after the curing step, particularly if the binder is capable of
functioning as a crosslinking material. The specific types of
binders disclosed wherein that also can crosslink are polyols,
polyaldehydes, polycarboxylic acids, and polyamines (polymeric or
nonpolymeric binders with more than one amine group). If such
binders are present during curing, the binder that is in contact
with the fiber will tend to be consumed during the curing step to
form covalently crosslinked bonds. By consumed it is meant that the
hydrogen bonding sites on the binder tend to be used up so that
they are no longer available for bonding the particles via the
binder to the fibers. Thus, when this occurs, the binder is no
longer available for hydrogen bonding or coordinate covalent
bonding, and particle binding to fibers is ineffective.
[0116] The intrafiber covalent bond forming processes described in
the above European publications require formation of an anhydride
that then reacts with a hydroxy group on cellulose to form a
covalent ester bond. The presence of more than about 20% water by
weight in the fibers is believed to retard the formation of the
anhydride and inhibits covalent bond formation. Hence, in processes
that use polycarboxylic acids, polyols and polyamines (which
includes both polymeric and nonpolymeric amines having more than
one amine group) as binders on the particles in the present
invention, the fibers should contain at least 20% water (or 20-50%
water) by weight if the particles and binder are present in the
fibers when curing occurs. The water retards covalent bond
formation, and is expected to prevent all of the binder on the
particles from being used to form covalent intrafiber crosslinks.
Hence, some of the binder remains available to form the bonds with
the fibers and produce ease of densification in fiber products made
by the process of the present invention.
[0117] The present invention, in contrast, produces a product under
conditions that favor formation of hydrogen or coordinate covalent
bonds. Hence, the particles can be bound to the fibers in the
absence of the external application of heat or pressure. Particles
also may be bound and the resulting fiber product densified, for
example at less than 200 pli (about 8000 psi) with SAP, or less
than 100 pli (about 4000 psi) with SAP, in the absence of external
application of heat to produce a product in which a substantial
portion of the particles are bound by non-covalent bonds (hydrogen
or coordinate covalent bonds). A substantial portion of particles
bound by non-covalent bonds means at least half of the bonds
binding particles to fibers are other than covalent bonds, for
example, hydrogen or coordinate covalent bonds.
[0118] In yet other examples, particles may be bound in the absence
of external application of pressure, but at elevated
temperatures.
[0119] In particularly preferred embodiments, the particles are
substantially entirely bound to the fibers non-covalently.
IX. Binding Examples for Polymeric
[0120] Binders and Water-Insoluble Particles
[0121] Several examples are provided below to illustrate using the
polymeric binders within the present invention to attach
superabsorbent particles to southern bleached kraft pulp.
EXAMPLE 1
[0122] A 321 gram amount of NB-416 southern bleached kraft fluff
obtained from Weyerhaeuser Company may be air-entrained in a
blender-like mixing device. 5 grams of poly(caprolactone) diol
(average molecular weight 2000, supplied by Aldrich Chemical
Company of Milwaukee, Wis.) dissolved in 5 ml of deionized water
may be sprayed as a binder onto 435 grams of starch graft
polyacrylate hydrogel fines (IM 1000F; supplied by Hoechst-Celanese
of Portsmouth, Va.) as the fines are added to the blender and mixed
therein. The product may then be removed from the blender, and
spread out in a fume hood to air dry overnight. The resulting
product may then be airlaid on a small airlay line, from M & J
Machines (of Horsens, Denmark) and thermobonded at 140.degree. C.
for one minute to produce a web containing superabsorbent particles
(SAP) attached to the individualized fibers. This binder has a low
melting point, hence raising the temperature to 140.degree. C.
melted the binder and allows it to flow to some extent over the
fibers and particles to enhance hydrogen bonding interactions-and
provide mechanical encapsulation that further binds the fibers and
particles. This is also an example of activating a solid binder by
heating it, without liquid addition. A polypropylene
glycol/polyethylene glycol copolymer binder would also behave in
this manner.
EXAMPLE 2
[0123] A 321 gram amount of southern kraft fluff can be
air-entrained in a blender-like mixing device. 15 grams of a 65%
solution of polyacrylic acid (average molecular weight=2,000;
supplied by Aldrich Chemical Company of Milwaukee, Wis.) diluted
with 10 ml of deionized water may be sprayed onto 435 grams of
polyacrylate hydrogel (FAVOR 800 supplied by Stockhausen of
Greensboro, N.C.) as the hydrogel is added into the mixing device
and mixed with the fluff and polyacrylic acid binder. The product
can be removed and spread out to dry and then fed to a hammermill
with a three-eighths inch round hole screen and shunted to a small
airlay line to produce a web containing SAP attached to the
individualized fibers.
EXAMPLE 3
[0124] A 321 gram amount of southern bleached kraft fluff may be
air-entrained in a blender-like mixing device and 10 grams of
polyglycine (molecular weight=5,000-15,000; supplied as a dry
powder by Sigma Chemical Company of St. Louis, Mo.) diluted with 10
ml of deionized water may be sprayed onto 435 grams of starch graft
polyacrylate hydrogel fines (IN 1000F; supplied by Hoechst-Celanese
of Portsmouth, Va.) as the particles are delivered to the blender
for mixing. The product may then be removed and spread out in a
fume hood to dry overnight. The resulting product may be fed into a
Fitz hammermill with a three-eighths inch round hole screen and
shunted to a small M & J airlay line to produce a web
containing SAP attached to the fibers.
EXAMPLE 4
[0125] A 321 gram amount of southern bleached kraft fluff may be
air-entrained in a blender-like mixing device and 200 grams of a
50% solution of polyethyleneimine (molecular weight=50,000-100,000;
supplied by ICN Biomedicals, Inc. of Costa Mesa, Calif.), or
polyvinyl pyridine may be sprayed onto 435 grams of starch graft
polyacrylate hydrogel fines (IN 1000F; supplied by Hoechst-Celanese
of Portsmouth, Va.) and added to the blender for mixing. The
product may be removed and spread out in a fume-hood to dry
overnight. The resulting product may be fed into a Fitz hammermill
with a three-eighths inch round hole screen and shunted to a small
M & J airlay line to produce a web containing SAP attached to
the fibers.
[0126] The classes of polymeric binders that encompass those
described in Examples 1-4 are especially preferred over other
multiple hydrogen bonding functionality polymers for a number of
reasons. One important reason is that their functionalities produce
very strong, effective hydrogen bonding. Other important reasons
include their relative lack of reactivity (as compared with
polyaldehydes or polyisocyanates) and their low toxicity (again, as
compared with polyaldehydes or polyisocyanates).
EXAMPLE 5
[0127] 0.03 grams of polyethylene glycol (MW 200, supplied by
Aldrich, Milwaukee, Wis.) were dropped onto 30 grams of a starch
graft polyacrylate hydrogel (IM 3900; supplied by Hoeschst
Celanese, Portsmouth, Va.) and the resulting mixture was air
entrained in a blender-like mixing device for 30 seconds to ensure
complete mixing. 1.2 grams of a southern bleached kraft pulp sheet
(NB 416; supplied by Weyerhaeuser, Tacoma, Wash.) were fiberized in
a Waring blender. While the blender was running, 0.80 grams of the
PEG-treated hydrogel were added to the fluff. The blender was then
stopped and the mixture was removed. The resulting product was
examined by a light microscope and revealed fibers with attached
hydrogel particles.
X. Non-Polymeric Binding Examples
[0128] Several examples are provided below to illustrate the use of
several non-polymeric organic binders of the present invention to
attach superabsorbent particles to southern bleached kraft pulp.
Several examples of binder activation and reactivation also are
provided.
EXAMPLE 6
[0129] 30 grams of a starch graft polyacrylate hydrogel (IM 3900;
supplied by Hoechst Celanese, Portsmouth, Va.) were treated with
polyethylene glycol (MW 400, supplied by Aldrich, Milwaukee, Wis.)
as described above in Example 5. Similar results were obtained.
EXAMPLE 7
[0130] A 3171 gram amount of southern bleached kraft fluff and 4348
grams of starch graft polyacrylate hydrogel fines (IM 1000;
supplied by Hoechst-Celanese of Portsmouth, Va.) were air-entrained
in a blender-like mixing device and 100 grams of glycerin (96%,
USP; supplied by Dow Chemical Co. of Midland, Mich.) diluted with
50 grams of deionized water, were sprayed onto mixture. The blender
was stopped, the product was vacuumed out, and spread out in a fume
hood to dry overnight. The resulting product was examined by
scanning electron microscope and revealed superabsorbent particles
attached to fibers. This example demonstrates that the fibers and
particles may be simultaneously exposed to the binder to produce
fibers with attached particles.
[0131] Glycerin is advantageous because it tends to penetrate the
fibers and soften them in addition to binding the particles to the
fibers. However, over time less glycerin is available at the
surface of the particles for use in binding particles in the event
the glycerin/particle material is stored for long periods prior to
use in adhering to fibers (e.g. if reactivation is delayed for
several weeks or more). This can be compensated for in part by
using higher percentages of glycerin on the particles. Also,
monoglyceride and diglyceride binders do not penetrate as readily
and therefore can be stored longer before reactivation to adhere
particles.
EXAMPLE 8
[0132] 30 grams of a starch graft polyacrylate hydrogel (IM 3900;
supplied by Hoechst Celanese, Portsmouth, Va.) were stirred into 50
grams of glycerin (Supplied by Dow chemical of Midland, Mich.) and
the excess glycerin was removed by suction filtration. 1.2 grams of
a southern bleached kraft pulp sheet (NB 416; supplied by
Weyerhaeuser, Tacoma, Wash.) were fiberized in a Waring blender.
While the blender was running, 0.80 grams of the glycerin-treated
hydrogel were added to the fluff. The blender was then stopped and
the mixture was removed. The resulting product was examined by
light microscopy and revealed fibers with attached hydrogel
particles. The glycerin level in the hydrogel particles produced in
the manner described above was determined to be 61% by NMR
spectroscopy.
EXAMPLE 9
[0133] 0.03 grams of glycerin (96%, USP, supplied by Dow, Midland,
Mich.) were dropped onto 30 grams of a starch graft polyacrylate
hydrogel (IM 3900; supplied by Hoechst Celanese, Portsmouth, Va.)
and the resulting mixture was air entrained in a blender-like
mixing device for 30 seconds to ensure complete mixing. 1.2 grams
of a southern bleached kraft pulp sheet (NB 416; supplied by
Weyerhaeuser, Tacoma, Wash.) were fiberized in a Waring blender.
While the blender was running, 0.80 grams of the glycerin-treated
hydrogel were added to the fluff. The blender was then stopped and
the mixture was removed. The resulting product was examined by
light microscopy and revealed fibers with attached hydrogel
particles. Aliquots of the glycerin-treated hydrogel were blended
with fluff while increasing time elapsed between glycerin treatment
and attempted fiber attachment. Attempts to attach fiber, solely by
blending fiber with treated particles, are still successful after
10 weeks. Samples tested after longer time intervals are expected
to perform similarly.
EXAMPLE 10
[0134] 0.03 grams of dipropylene glycol (supplied by Aldrich,
Milwaukee, Wis.) were dropped onto 30 grams of a starch graft
polyacrylate hydrogel (IM 3900; supplied by Hoechst Celanese,
Portsmouth, Va.) and the resulting mixture was air-entrained in a
blender-like mixing device for 30 seconds to ensure complete
mixing. 1.2 grams of a southern bleached kraft pulp sheet (NB 416;
supplied by Weyerhaeuser, Tacoma, Wash.) were fiberized in a Waring
blender. While the blender was running, 0.80 grams of the
dipropylene glycol-treated hydrogel were added to the fluff. The
blender was then stopped and the mixture was removed. The resulting
product was examined by light microscopy and revealed fibers with
attached hydrogel particles.
EXAMPLE 11
[0135] A 900-gram amount of southern bleached kraft fluff pulp
sheet can be fed into a Fitz hammermill fitted with a
three-eighths-inch hole screen. The sheet can be defiberized,
shunted to an M & J airlay line, and airlaid into a web. As the
web emerges, target zones of the web may be dusted with particles
to which a 50% solution of lactose has been applied. The target
zones may be misted with water to raise the moisture content to
17-21%. The particles may comprise five gram aliquots of binder
containing starch graft polyacrylate hydrogel fines (IM 1000F;
supplied by Hoechst-Celanese of Portsmouth, Va.) which are sifted
onto the target zones. The web that would result contains target
zones with 5 grams of SAP attached to the fibers of each target
zone. Portions of the web that were not moistened would not adhere
the particles well. This is an example of applying the binder
containing particles to a target zone so that SAP primarily adheres
to the target areas where the binder was applied. Target-zone
application of SAP can be advantageous because it reduces the cost
of the product to provide SAP only in areas of a product where the
SAP is needed, for example, the crotch area of a diaper. Placement
of SAP in the area where a liquid insult is expected also decreases
the necessity for wicking liquid to a SAP impregnated region. This
is an advantage because the requirement for wicking can increase
liquid leakage in an absorbent product such as a diaper.
[0136] The binder may be sprayed onto the SAP, allowed to dry and
the SAP then deagglomerated by, for example, a hammermill or a
grinding apparatus. The binder could also be applied to SAP in
liquid form as the SAP is sifted onto the target zones, in which
case reactivation is not required as the wet binder adheres the SAP
in place as it dries.
XI. Binding Examples for Water-soluble Particles
[0137] Several examples are provided below to illustrate using
binders of the present invention to attach water-soluble particles
to southern bleached kraft pulp.
EXAMPLE 12
[0138] A 321 gram amount of NB-416 southern bleached kraft fluff
obtained from Weyerhaeuser Company (Tacoma, Wash.) may be
air-entrained in a blender-like mixing device. 5 grams of glycerin
(supplied by Dow Chemicals of Midland, Mich.) may be sprayed onto
288 grams of disodium ethylenediamine tetraacetic acid (EDTA)
(supplied by Mallinkrodt Chemical Works of St. Louis, Mo.) and the
binder containing particles added and mixed in the device. The
blender may be stopped, the product vacuumed out, and spread out in
a fume hood to dry overnight. The resulting product under scanning
electron microscope examination would have disodium EDTA particles
attached to fibers.
EXAMPLE 13
[0139] A 321 gram amount of HBA (a crosslinked high bulk fiber
available from Weyerhaeuser Company, Tacoma Wash.) may be
air-entrained in a blender-like mixing device. 5 grams of glycerin
(supplied by Dow Chemical of Midland, Mich.) may be sprayed onto
288 grams of sodium bicarbonate (supplied by J. T. Baker Chemical
Co. of Phillipsburg, N.J.) and added and mixed in the device. The
blender may be stopped, the product vacuumed out, and spread out in
a fume hood to dry overnight. The resulting product would contain
fibers with attached sodium bicarbonate particles.
EXAMPLE 14
[0140] An NB 416 pulp sheet (southern bleached kraft available from
Weyerhaeuser Company of Tacoma, Wash.) may be fed into a hammermill
and ground while simultaneously adding binder-coated polyacrylate
hydrogel (IM 3900, supplied by Hoechst Celanese of Portsmouth, Va.)
and binder-containing ammonium citrate to the mill at rates such
that the product contained 54% treated fiber, 42% IM 3900, and 4%
ammonium citrate. The binder may be present, for example, as 10% by
weight of the product. That mixture may be shunted to an airlay
device from M&J Machines (of Horsens, Denmark) and airlaid into
a continuous web. The resulting product would include fibers with
attached polyacrylate hydrogel and ammonium citrate particles.
EXAMPLE 15
[0141] A procedure similar to the one described in Example 13 may
be performed using Kitty Hawk (a thermobondable blend of southern
bleached kraft and polyethylene fibers available from Weyerhaeuser
Company of Tacoma, Wash.). The resulting product may be
thermobonded by passing the web through a through-air oven at
140.degree. C. for 0.5 minutes. The resulting thermobonded product
would have fibers with attached polyacrylate hydrogel and ammonium
citrate particles.
EXAMPLE 16
[0142] In this example, sodium oxalate may be bound to the fibers
by the binders of the present invention. A pulp sheet may be
prepared as in Example 13. The pulp sheet may be conditioned at 90%
relative humidity for 4 hours and then fiberized in a Waring
blender. Particles of sodium oxalate with 10% binder may be added
to the blender and blending continued. The product would include
sodium oxalate in particulate form bound to the cellulose fiber by
the glycerin.
EXAMPLE 17
[0143] Fibers may be prepared as in Example 15, except with
aluminum sulfate (alum) substituted for sodium oxalate. The
resulting product would include alum bound to fibers.
EXAMPLE 18
[0144] A mixture of binders also may be used to bind particles to
the fibers. Fibers may be supplied as in Example 11, but the 5
grams of glycerin may be replaced with a mixture of urea and
glycerin. A 40/60 mixture (by weight) of urea and glycerin may be
mixed by dissolving urea in the glycerin, and heating the solution
to 70-80.degree. C. The heated binder mixture may then be applied
to the particles for binding particles to the fibers as in Example
11. The urea/glycerin mixture provides several advantages over the
use of glycerin alone. Urea lowers the cost of the binder, while
glycerin can soften the fibers. The mixture also provides
manufacturing advantages.
[0145] In other embodiments urea alone as well as the other binders
of the type specified in the foregoing detailed description of the
invention and combinations thereof may be used as the binder.
XII. Auxiliary Binder
[0146] As previously described, an auxiliary binder or additional
binder or binders can be used in addition to the non-polymeric or
polymeric binders or combinations thereof in accordance with the
present invention. However, the additional binder(s) is selected to
not react with the binder or binder combination of the present
invention in a manner which prevents this latter binder from having
the required functionality. Thus, the preferred auxiliary binders
are non-reactive in this way. In addition, polymeric and
non-polymeric binders of the invention may be combined with one
another and with other binders as long as they do not block the
desired functionality.
EXAMPLE 19
[0147] A 321 gram amount of a southern bleached kraft fiber
(NB-416, supplied by Weyerhaeuser) may be air entrained in a
blender like mixing device with 212.8 grams of a polyvinylacetate
latex (PN-3666H, supplied by H B Fuller of Minneapolis, Minn.). 438
grams of a water swellable polyacrylate hydrogel (Favorsab 800,
supplied by Stockhausen of Greensboro, N.C.) may be added to the
mixing device. The mixture may then be sprayed with 100 grams of a
50% solution of glycerin (supplied by Dow of Midland, Mich.). The
blender may then be stopped and the mixture vacuumed from the
blender and placed in a fume hood to air dry overnight. The dried
product may then be airlaid into a 6" diameter pad in a laboratory
padformer, pressed to a density of approximately 0.077 g/cc, and
thermobonded at 140.degree. C. for thirty seconds. The resulting
pads are expected to have about 40% bound SAP and improved tensile
strength as compared to untreated fluff with SAP and as also
compared to binder treated fluff with SAP without the auxiliary
binder.
[0148] Tensile strength would be highest with polyvinylacetate
alone, followed by a combination of polyvinylacetate and glycerin,
then glycerin alone. Lowest tensile strength would be with no
binder at all.
EXAMPLE 20
[0149] Binders of the present invention may be used to bind
particles to pulp fibers that contain synthetic thermobonding
fibers. In this example, KittyHawk pulp (available from
Weyerhaeuser Company) is a mixture of NB316 southern bleached kraft
and 22% polyethylene thermoplastic binder fibers. The KittyHawk
pulp is used to produce a pulp web, with SAP bound to the fibers as
described in Example 3. The web with adhered SAP is then passed
through a thermobonder to soften the polyethylene fibers and fuse
the fibers of the web to each other to increase web strength.
XIII. Spectroscopic Evaluations
[0150] Spectroscopic measurements were made of a binder treated
particle made according to the present invention. The results of
the NMR and IR studies are presented below.
A. NMR Analysis
EXAMPLE 21
[0151] The hydrogen nuclear relaxation time constants shown below
were measured by nuclear magnetic resonance spectrometry (NMR), and
reflect molecular motion at slow speeds (close to 45 kHz). Both of
the glycerin hydrogen signals show relaxation times that decrease
with age since glycerin was added to the SAP. This indicates that,
with age, glycerin motion keeps slowing down into the 45 kHz range.
This motional slowing most likely arises from binding of glycerin
into the SAP particles, causing the glycerin molecules to be more
tightly held in place. Since neither covalent nor ionic bonding is
operative in this composite, the binding would have to be the
result of hydrogen bonding involving glycerin and SAP.
[0152] Hydrogen Nuclear Relaxation, T.sub.1.rho.H, at 45 kHz
[0153] Sample: IM 3900 with ca. 15% glycerin.
[0154] T.sub.1.rho.H, msec (std. devn.)
3 Age, days Peak --OH, H.sub.2O Peak-CH.sub.2--, --CH 0 34 (11) 30
(6) 11 10.4 (0.5) 9.3 (0.4) 17 6.0 (0.4) 5.3 (0.5) 28 2.6 (0.2) 2.3
(0.1)
XIV. Activation
[0155] The binders of the present invention have the advantage of
being activatable from an inactive state on the particles by
addition of liquid, heating or by kinetic energy such as supply by
mechanical agitation. Hence, a liquid binder can be applied to
particles in the absence of the fibers to be bound. The binder is
then dried or allowed to dry, for example until the binder and
particles reach an equilibrium moisture content with ambient air.
Alternatively, the binder can be combined with particles as a
solid. At a later stage of processing, heat, kinetic energy,
pressure, or a liquid such as water is added to the particles
resulting in an activation of the binder. The particulates may then
be added to the fibers, and the binder secures the particulates to
the fibers. This subsequent processing of the fibers to attach the
particles can occur, for example, at a separate location from the
location where the fibers are produced. Therefore, manufacturers of
products can add particulates of interest (e.g., superabsorbent
particles or fibers; antimicrobial particles, etc.) at the place of
manufacture of the end products that incorporate the particles.
Also, more than one type of particulate material (including water
soluble and water insoluble particles) may be added, if desired.
Particles without the required functionality would not be bound in
the same manner.
[0156] It also has been found that some of the binders of the
present invention can be reactivated by mechanical agitation (the
application of kinetic energy). For example, glycerin binder may be
applied to particles such as SAP. The glycerin binder may be
allowed to dry overnight, and the binder-containing particles may
be mixed with fibers and then mechanically agitated to reactivate
the glycerin binder and bind the particles to the fibers.
Mechanical agitation may take place, for example, in a defiberizer
where a sheet or mat of fibers are defiberized while being
intimately mixed with the binder containing SAP. Hence, the binder
may be activated by providing heat, an activating fluid, or by
applying kinetic energy to the particles, or to the fibers in the
presence of the particles, or by adding the particles to the fibers
while activating fluid is on the fibers.
XV. Binder Activation Examples
[0157] Binder activation in the present invention allows binder to
be added to particles before the particles are added to the fibers.
The binder is subsequently activated by addition of liquid, heat,
or by kinetic energy such as resulting from agitation, and
particles are bound to the fibers. The binder containing particles
may be added to the fibers either before binder activation, after
binder activation, or simultaneous with activation. If binder
containing SAP and/or other particles are to be added to cellulose
fibers, for example, the binder containing particles may be applied
to a pulp sheet which is subsequently fiberized. An activation
liquid such as water may be added to the pulp before or after
fiberization, and the binder containing particles may be added
before or after water addition, or simultaneously with the water.
If binder containing SAP or other particles are added after water
addition, the particles should be applied to the fibers prior to
complete evaporation of the added water from the fibers. Water can
also be added as an activation liquid in other ways, such as by
very humid air, a fog or mist, or as steam.
[0158] Activation can be of all the fibers, or only portions of the
fibers, such as target zones or portions of the mat where
particulate binding is desired. The particles may be added to the
mat and adhered to the target zones of the mat upon activation. In
some embodiments, the binder is applied as a solid and heated
during a- later processing stage to activate the binder by
softening it such that it binds the particles to the fibers. The
particles may be added in a pattern corresponding to a desired
distribution (for example a non-homogeneous distribution) of
particles in the fibrous material. Most commonly, however,
activation is accomplished by using a binder solvent to moisten the
binder on the particles for application to a targeted area of the
product.
[0159] In yet other embodiments, the binder is applied to the
particles and then activated by applying kinetic energy to the
binder containing particles and fibers. Neat polypropylene glycol
(MW 2000) binder, for example, may be sprayed on particles and
allowed to air dry. These particles are then added to the fibers as
the fibers are mechanically agitated in a blender or defiberizer to
kinetically activate the binder and bind the particles to the
fibers. For kinetic activation, the binder may be added as a liquid
or a solid to the particles. In the case of liquid addition, the
liquid is allowed to air dry, and then reactivated by mechanically
agitating the fibers and binder.
[0160] Activation of the binder may be performed prior to adding
the particles, subsequent to adding the particles, or
simultaneously with addition of the particles. Once the binder is
activated, it adheres a substantial portion of the particles to the
fibers, wherein "a substantial portion" refers to about half of the
particles added. Of the particles that are adhered, at least half
of them (and more typically substantially all of them, e.g., over
90%) are adhered to the binder by non-covalent bonds, namely
hydrogen bonds or coordinate covalent bonds, and the binder is in
turn adhered to the fibers by hydrogen bonds.
[0161] The activating step may be performed after the curing step
is complete, if a curing step is to be performed.
[0162] The following example will illustrate several specific
applications of the activation process, and are not intended to
limit the invention to the disclosed methods.
EXAMPLE 22
[0163] 0.30 grams of urea (supplied by Aldrich, Milwaukee, Wis.)
were dissolved in a mixture of 9 milliliters of ethanol and 1
milliliter of deionized water. 1.0 milliliter of that solution was
dropped onto 30 grams of a starch graft polyacrylate hydrogel (IM
3900; supplied by Hoechst Celanese, Portsmouth, Va.) and the
resulting mixture was air entrained in blender-like mixing device
for 30 seconds to ensure complete mixing. The mixture was then
allowed to air dry for two weeks. 1.2 grams of a southern bleached
kraft pulp sheet (NB 416; supplied by Weyerhaeuser, Tacoma WA) were
fiberized in a Waring blender. While the blender was running, 0.80
grams of the urea-treated hydrogel were added to the fluff. The
blender was then stopped and the mixture was removed. The resulting
product-was examined by light microscopy and revealed no fibers
with attached hydrogel particles. However, an 18.5 gram sample of
the urea-treated hydrogel was air-entrained in a blender-like
mixing device and mixed with 0.51 grams of distilled water.
Attached particles were formed when 0.80 grams of the
water-activated urea-treated hydrogel were blended with 1.2 grams
of fluff fibers.
EXAMPLE 23
[0164] 0.30 grams of para-aminosaliciylic acid (supplied by J. T.
Baker, Phillipsburg, N.J.) were dissolved in a mixture of 9
milliliters of ethanol and 1 milliliter of deionized water. 1.0
milliliter of that solution was dropped onto 30 grams of a starch
graft polyacrylate hydrogel (IM 3900, supplied by Hoechst Celanese,
Portsmouth, Va.) and the resulting mixture was air-entrained in a
blender-like mixing device for 30 seconds to ensure complete
mixing. The mixture was then allowed to air dry for two weeks. 1.2
grams of a southern bleached kraft pulp sheet (NB 416; supplied by
Weyerhaeuser, Tacoma Wash.) were fiberized in a Waring blender.
While the blender was running, 0.80 grams of the
para-aminosalicylic acid-treated hydrogel were added to the fluff.
The blender was then stopped and the mixture was removed. The
resulting product was examined by light microscopy and revealed no
fibers with attached hydrogel particles. However, fibers with
attached particles were formed when a 1.2 gram sample of the pulp
sheet had been conditioned in a 90% relative humidity environment
for two hours before blending with the binder-treated hydrogel.
EXAMPLE 24
[0165] 30-gram samples of a starch graft polyacrylate hydrogel (IM
3900; supplied by Hoechst Celanese, Portsmouth, Va.) were treated
with either glycine, taurine, or ammonium citrate in a manner
similar to that described above in Example 23. While some
adjustments in the volumes of solvents used were necessary to
effect dissolution of the binders, binder add-on levels were held
constant and attachment attempts yielded similar results.
XVI. Thermoplastic Binders
[0166] An auxiliary binder also may be used to help bind fibers to
each other above the melting point of the auxiliary binder. The
auxiliary binder may be a solid thermoplastic material that is
applied to the fibers and softened by elevating the temperature
during the binding step to above the softening temperature of the
auxiliary binder. The auxiliary binder is thereby temporarily
softened, rendered more fluid (which for purposes of convenience
may be referred to as auxiliary binder melting) and subsequently
resolidified as the temperature cools, which thermoplastically
binds the fibers to each other, and the particles to the fibers.
The auxiliary binder may also contain a hydrogen bonding
functionality that hydrogen bonds the particles to the fiber.
Examples of auxiliary binders that are thermoplastic and also
contain hydrogen bonding groups include ethylene vinyl alcohol,
polyvinyl acetate, acrylates, polycarbonates, polyesters and
polyamides. Further information about the use of such auxiliary
binders can be found in U.S. Pat. No. 5,057,166.
[0167] The auxiliary or second binder can be added to the fibers,
either before or after particles containing a first binder, to help
bind the fibers to each other and provide additional binding
between the fibers and particles. A suitable second binder would be
a thermoplastic or thermosetting binder. In the case of
thermoplastic polymers, the polymers may be a material which
remains permanently thermoplastic. Alternatively, such polymers may
be a material which is partially or fully crosslinkable, with or
without an external catalyst, into a thermosetting type polymer. As
a few specific examples, suitable thermoplastic binders can be made
of the following materials: ethylene vinyl alcohol, polyvinyl
acetate, acrylic, polyvinyl acetate acrylate, acrylates, polyvinyl
dichloride, ethylene vinyl acetate, ethylene vinyl chloride,
polyvinyl chloride, styrene, styrene acrylate, styrene/butadiene,
styrene/acrylonitrile, butadiene/acrylonitrile,
acrylonitrile/butadiene/s- tyrene, ethylene acrylic acid,
polyethylene, urethanes, polycarbonate, oxide, polypropylene,
polyesters, and polyimides.
[0168] In addition, a few specific examples of thermoset binders
include those made of the following materials: epoxy, phenolic,
bismaleimide, polyimide, melamine/formaldehyde, polyester,
urethanes, urea, and urea/formaldehyde.
[0169] More than one of these materials may be used to treat the
fibers. For example, a first coating or sheath of a thermoset
material may be used followed by a second coating of a
thermoplastic material. The binder containing superabsorbent
particles or other particles are then typically adhered to the
outer binder material which should have the functionality as
explained above. During subsequent use of the fibers to make
products, the thermoplastic material may be heated to its softening
or tack temperature without raising the thermoset material to its
curing temperature. The remaining thermoset material permits
subsequent heating of the fibers to cure the thermoset material
during further processing. Alternatively, the thermoset material
may be cured at the same time the thermoplastic material is heated
by heating the fibers to the curing temperature of the thermoset
with the thermoplastic material also being heated to its tack
temperature.
[0170] Certain types of binders enhance the fire resistance of the
treated fibers, and thereby products made from these fibers. For
example, polyvinyl chloride, polyvinyl dichloride, ethylene vinyl
chloride and phenolic are fire retardant.
[0171] Surfactants also may be included in the auxiliary binder as
desired. Other materials may also be mixed with the auxiliary
binder to impart desired characteristics to the fibers. For
example, particulate material, such as pigments, also may be
included in the auxiliary binder for application to the fibers.
EXAMPLE 25
[0172] As previously described, an auxiliary binder can be used in
addition to the polymeric binders of the present invention. A 3210
gram amount of southern bleached kraft binder (NB-416, supplied by
Weyerhaeuser Company) may be air entrained in a blenderlike mixing
device and sprayed with 2128 grams of a polyvinyl acetate latex
(PN-3666H, supplied by H. B. Fuller of Minneapolis, Minn.). While
still mixing, 4073 grams of a water-swellable polyacrylate hydrogel
(IM 1000-60, supplied by Hoechst-Celanese of Portsmouth, Va.) with
580 grams of polypropylene glycol (supplied by Union Carbide of
Danbury, Conn.) may be added. The blender may be kept running and
the mixture shunted into a flash tube dryer. The dried product may
then be airlaid, for example, as a 16 inch wide web on a Danweb
airlay machine, pressed to a density of approximately 0.15 g/cc,
and thermobonded at 140.degree. C. for thirty seconds. The
resulting web would have 40% bound SAP and improved tensile
strength (as compared to untreated fluff with SAP).
XVII. Application of Binder
[0173] The binders of the present invention can be added to the
particles in any convenient manner. One such procedure is to spray
the binder or binders on to the particles as the particles are
conveyed past a sprayer on a conveyor belt or as the particles fall
through air, for example toward a web of fibers. The particles may
also be slurried with or immersed in binder. In this case, the
particles would typically be milled to break up agglomerations. For
solid binders, blending of the particles and binder may be
accomplished or the binder may simply be sprinkled onto or
otherwise comingled with the particles, followed by a fixation step
such as addition of heat or liquid. These particles can, while
still wet in the case of a liquid binder or following reactivation
of a liquid or solid, be combined with the fibers.
[0174] The particles can also be allowed to dry for later
reactivation with a reactivation fluid, such as a reactivation
liquid and combined with the fibers at that time. An example of
when it may be desirable to apply the binder to the particles and
thereafter activate the binder in the presence of fibers is when
the particles are added to fibers at a remote site from the site
where the fibers are produced. The remote or second location may
be, for example, a location where a manufacturer combines fibers
and particles into articles, such as absorbent articles. Particles
may be added from conventional volumetric feeders in a hammermill
or from injectors on a paper making line.
[0175] The invention is not limited to any specific mechanism for
combining the binder and particles.
XVIII. Production of High Bulk Fibers
[0176] Production of high bulk fibers with intrafiber crosslinks is
known in the art. Processes for making such fibers are described in
EP 440 472 A1; EP 427 317 A2; EP 427 316 A2; and EP 429 112 A2, as
well as U.S. patent application Ser. No. 07/607,268 filed Oct. 31,
1990, and its published European counterpart. These high bulk
fibers may be used in the present invention, with particles bound
to them by the binders disclosed herein. Since methods of making
high bulk fibers are known, only a brief description of one such
process is given below.
A. Overall System
[0177] The apparatus 110 (FIG. 3) comprises a conveying device 112
for transporting a mat 114 of cellulose fibers or other fibers
through a fiber treatment zone 116; an applicator 118 for applying
a treatment substance such as a crosslinking substance from a
source 119 thereof to the mat 114 at the fiber treatment zone 116;
a fiberizer 120 for completely separating the individual cellulose
fibers comprising the mat 114 to form a fiber output comprised of
substantially unbroken cellulose fibers substantially without nits
or knots; and a dryer 122 coupled to the fiberizer for flash
evaporating residual moisture from the fiber output and for curing
the crosslinking substance, thereby forming dried and cured
cellulose fibers.
[0178] The mat 114 of cellulose fibers is preferably in an extended
sheet form stored in the form of a roll 124 until use. It is
normally not necessary that the cellulose fibers comprising the mat
114 be completely dry. Since cellulose is a hydrophilic substance,
molecules thereof will typically have a certain level of residual
moisture, even after air drying. The level of residual moisture is
generally 10% wt/wt or less, which is not detectable as "wetness."
FIG. 3 also shows that more than one supply, such as multiple rolls
124, of the mat 114 of cellulosic fibers can be simultaneously
processed using the present invention.
[0179] At the fiber treatment zone 116, sprayers or other
applicators 118 apply chemicals such as crosslinking agents to the
mat. Typically chemicals are applied uniformly to both sides of the
mat. The wetted mat passes between a pair of rollers 128 which
assist in distributing the chemicals uniformly through the mat.
Other applicators may also, of course, be used.
[0180] The crosslinking substance is a liquid solution of any of a
variety of crosslinking solutes known in the art. If required, the
crosslinking substance can include a catalyst to accelerate the
bonding reactions between molecules of the crosslinking substance
and cellulose molecules. However, many if not most crosslinking
substances do not require a catalyst.
[0181] Preferred types of crosslinking substances are selected from
a group consisting of urea derivatives such as methylolated urea,
methylolated cyclic ureas, methylolated lower alkyl substituted
cyclic ureas, methylolated dihydroxy cyclic ureas, and mixtures
thereof. A specifically preferred crosslinking substance would be
dimethyloldihydroxyethylene urea (DMDHEU). In addition,
crosslinking substances can be polycarboxylic acids, such as citric
acid. Crosslinking materials are known in the art, such as
described in the previously mentioned Chung patent, U.S. Pat. No.
4,935,022 to Lash, et al., U.S. Pat. No. 4,889,595 to Herron, et
al., U.S. Pat. No. 3,819,470 to Shaw, et al., U.S. Pat. No.
3,658,613 to Steijer, al., U.S. Pat. No. 4,822,453 to Dean, et al.,
and U.S. Pat. No. 4,853,086 to Graef, et al.
[0182] Suitable catalysts include acidic salts which can be useful
when urea-based crosslinking substances are used. Such salts
include ammonium chloride, ammonium sulfate, aluminum chloride,
magnesium chloride, or mixtures of these or other similar
compounds. Alkali metal salts of phosphorus-containing acids may
also be used.
[0183] In FIG. 3, the crosslinking substance applied to the mat 114
is obtained from a supply 119 thereof, such as a tank or analogous
vessel.
[0184] Crosslinked cellulose fibers are individual fibers each
comprised of multiple cellulose molecules where at least a portion
of the hydroxyl groups on the cellulose molecules have been
covalently bonded to hydroxyl groups on neighboring cellulose
molecules in the same fiber via crosslinking reactions with
extraneously added chemical reagents termed "crosslinking
substances" or "cross-linking agents." Suitable crosslinking agents
are generally of the bifunctional type which create covalently
bonded "bridges" between said neighboring hydroxyl groups.
B. Conveying Device
[0185] Referring further to FIG. 3, each mat 114 of cellulosic
fibers is conveyed by a conveying device 112, which carries the
mats through the fiber treatment zone 116. FIG. 3 also shows a
further portion of one type of conveying device comprised of a
first pair of rollers 126 and a second pair of rollers 128 for each
mat 114. The first and second pair of rollers 126, 128 are
particularly effective for urging the corresponding mat at a
substantially constant and controlled rate of speed.
C. Fiber Treatment Zone
[0186] Each mat 114 is urged by the first and second pair of
rollers 126, 128 through the fiber treatment zone 116 where the mat
114 is impregnated with a liquid crosslinking substance. The
crosslinking substance is preferably applied to one or both
surfaces of the mat using any of a variety of methods known in the
art useful for such a purpose, such as spraying, rolling, dipping,
or analogous method. Combinations of spray and roller applicators
can also be employed.
[0187] The crosslinking substance is typically applied in an amount
ranging from about 2 kg to about 200 kg chemical per ton of
cellulose fiber and preferably about 20 kg to about 100 kg chemical
per ton of cellulose fiber.
D. Fiberizer
[0188] The next subsystem following the fiber treatment zone is a
fiberizer 120 which serves to comminute one or more mats 130
impregnated with the crosslinking substance into individual
substantially unbroken cellulose fibers comprising a fiber
output.
[0189] Referring further to FIG. 3, a first conveyer fan 260 of
conventional design can be utilized for propelling the fibers from
the outlet 162 of the attrition device 132 through a conduit
262.
[0190] An optional component of the fiberizer 120 is a first
cyclone 264 or similar apparatus known in the art, utilized in a
conventional manner to concentrate the fibers passing out of the
outlet 162 of the attrition device 132. The first cyclone 264
receives the fibers through the conduit 262 coupled thereto.
[0191] Excess air can be recovered at the top 266 of the first
cyclone 264 and recycled as required through a conduit 268 to a
location upstream of the first conveyer fan 260 (if used). Such
additional air can be beneficial for easing the transfer of the
fibers through the first conveyor fan 260.
[0192] A disk refiner 268 is another optional component of the
fiberizer 120 which can be employed to effect additional separation
of fibers (removal of knots) if required. The disk refiner 268 is
of a type known in the art and comprises a disk refiner inlet 270
and a disk refiner outlet 272. A representative disk refiner 268 is
type DM36 manufactured by Sprout-Bauer, Incorporated of Muncie, Pa.
If the disk refiner 268 is used, the inlet 270 thereof is coupled
via a conduit 274 to an outlet 276 of the first cyclone 264.
[0193] A second conveyor fan 278 may optionally be utilized to urge
propagation of the fibers through a conduit 180 downstream of the
disk refiner 268. Excess air can be recovered from the top 266 of
the first cyclone 264 and routed via a conduit 281 to a tee 282
just upstream of the second conveyor fan 278.
[0194] Another optional component of the fiberizer 120 is a fluff
generator 290 which receives the fibers from the optional second
conveyor fan 278 through a conduit 284. The fluff generator is
described in detail below and in copending U.S. patent application
Ser. No. 07/607,157.
E. Dryer
[0195] Referring further to FIG. 3, a preferred embodiment of the
present apparatus 110 includes a dryer 122 which is utilized to
perform two sequential functions: remove residual moisture from the
fibers and cure the crosslinking agent. Preferably, the dryer 122
comprises a drying zone 373 for receiving fibers, e.g. from fluff
generator outlet 304 and for removing residual moisture from the
fibers via a "flash drying" method and a second drying zone 360,
362 for curing the crosslinking agent. In FIG. 3, the curing starts
in zone 360 and continues through zone 362.
[0196] The FIG. 3 embodiment shows that zone 373 is coupled to the
fluff generator outlet by a conduit 372 and to a source 374 of
heated air, typically produced by combustion of a supply of natural
gas 376 and fresh air 378. The temperature of heated air is
regulated to maintain the temperature of the drying zone 373 within
a range of about 200.degree. C. to about 315.degree. C. As the
fiber output passes into the drying zone 373, the wet fibers
comprising the fiber output are substantially instantaneously
exposed to the high temperature in this zone. Such rapid exposure
to high temperature imparts a "flash drying" effect to the fibers,
thereby causing rapid and thorough drying and separation of the
fibers. The passage time through the drying zone 373 is preferably
less than one second.
[0197] The FIG. 3 embodiment shows that the first zone 360 is
comprised of a first tower 364 comprised of a body portion 366, an
inlet 368, and a first tower outlet 370. The dryer zone 373 is
coupled via a conduit 372 to the outlet of the fluff generator
290.
[0198] In FIG. 3, the first tower 364 is shown preferably coupled
via a conduit 380 to a down tube 382, which is coupled via a
conduit 384 to a third conveyor fan 386 located at an inlet 388 of
a second tower 390. The third conveyor fan 386 transports the
fibers through the dryer which thereby pass into the second tower
390. As the fibers are lofted through the second tower 390, they
are still exposed to a curing temperature within a range of about
140.degree. C. to about 180.degree. C., which is sufficient to
effect curing of the crosslinking agent without scorching the dry
fibers. The lofting keeps the fibers separated until the
crosslinking reaction is complete. The curing temperature depends
upon the type of crosslinking material used to treat the fibers and
also is set at a level so as to not scorch the fibers during
curing. It should be noted that single stage dryers may also be
used.
[0199] The dried and cured fibers exiting the dryer outlet of tower
390 have an extremely low level of nits and virtually no knots.
Further, they are not discolored from scorching and the like, and
have a median fiber length substantially unchanged from the median
length of the fibers comprising the mat 14.
[0200] FIG. 3 also shows a second cyclone 400 of conventional
design coupled via a conduit 402 to the outlet of tower 390,
serving to concentrate the fibers passing therethrough in
preparation for collection. The resulting concentrated fibers can
be collected using any of a number of collection devices 408 known
in the art, such as fiber bagging devices.
EXAMPLE 26
THEORETICAL
[0201] In this example, non-woven fibrous mats were impregnated
with a crosslinking agent, fiberized, dried, and cured using the
apparatus as diagrammed schematically in FIG. 3.
[0202] Two 52-inch-wide mats of southern pine kraft wood pulp
fibers (type NB316 from Weyerhaeuser Company) and having a basis
weight of 680 g/m.sup.2 were fed to the apparatus. The mats were
impregnated using dimethyloldihydroxyethylene urea at a
concentration of about 5%, applied over both sides of each mat
using a combination of spray nozzles and impregnation rollers. The
loading level of crosslinking agent was about 4.5% w/w.
[0203] The treated fiber mats were fed at the rate of 8 meters/min
to the attrition device 32. The specific attrition device used in
this example was equipped with six mat inlets and a rotor having 16
rows of hammers as described above around the circumference of the
rotor. The rotor had a diameter of 30 inches and was rotated at an
angular velocity of 1200 rpm by an electric motor. Other rpm rates
have also been tested and have proven satisfactory, including
extremely high rpm rates.
[0204] Random samples of fibers were obtained from the output
attrition device and observed for nits. These samples were 2.6
grams and were consistently observed to have fewer than three nits
on the average with most samples having no nits. The attrition
device was flushed with water once every sixteen hours for cleaning
purposes.
[0205] A disk refiner was employed downstream of the attrition
device. This specific disk refiner was a DM36 refiner as previously
mentioned. A fluff generator as described in FIGS. 7-9 was also
employed in this downstream of the disk refiner. The temperature at
the dryer input in this example was within the range of 200.degree.
C. to 315.degree. C. The temperature at the second tower outlet was
within the range of 140.degree. C. to 180.degree. C. Crosslinked
fiber at the output of the dryer was produced at a rate of about
5000 pounds per hour. The particle binders and particles of the
present invention can be added before, after, or simultaneously
with curing. The term "curing in the presence of the binder" means
that the binder containing particles may be added before or
simultaneously with curing. Curing in the presence of the binder is
not usually a problem because the binder cannot participate in the
intrafiber crosslinking reaction, and the binder would not be
affected by the curing step. In certain situations, however, the
binder on the particles may also form covalent intrafiber
crosslinks. Polycarboxylic acids (such as citric acid), polyols
(such as propylene glycol) and polyamines (such as ethylene
diamine) may function as crosslinking agents, and may be consumed
during the curing step in the formation of covalent crosslinks.
Hence in the limited case in which the binder material on the
particles is also a crosslinking agent, steps should be taken to
prevent the binder from being consumed as a crosslinker in the
curing step. When the crosslinking material is not cured in the
presence of the binder, that is when the binder containing
particles are added after curing, no steps need be taken to inhibit
covalent bond formation.
XIX. Composite Absorbent Product
[0206] In accordance with the present invention, absorbent
structures or articles may be made from the fibers, with binder and
adhered particulates. These articles may be composite structures
(e.g., made of plural materials). For example, the articles may
have a core of plural types of fibers, or fiber layers, with or
without covering materials. These products are capable of absorbing
significant quantities of water and other fluids, such as urine and
other body fluids. Such products include, but are not limited to,
disposable diapers, sanitary napkins, incontinent pads, towels and
the like.
[0207] FIGS. 4-5 illustrate an absorbent pad structure which may be
formed from fibers of the present invention, whether or not they
are blended with other fibers. FIGS. 4 and 5 represent an absorbent
pad 410 having a heat embossed screen pattern 412. Pads having no
pattern may also be used. A pad having a cover sheet 414 and a
backing sheet 416 may be formed, for example, by placing a square
fiber piece cut from the sheet onto a corresponding precut backing
sheet. A corresponding precut cover sheet is placed over the top of
the fiber 418 on the backing sheet. This assembly may then be
adhesively bonded around a continuous margin 420.
[0208] With reference to FIGS. 6-7, an absorbent structure in the
form of a bandage is shown. A bandage 430 for application to a
wound to absorb blood and other bodily fluids is shown. An
absorbent pad 440 is securely mounted to an exterior or pad
mounting surface 434 of a backing strip 436. Fibers 441 are
contained in pad 440, and particles are attached to the fibers 441
in accordance with the present invention. Any suitable mounting or
securing means may be used to affix pad 440 to the surface 434 of
the strip 436. However, it is preferable for surface 434 to be
coated with an adhesive so that the pad 440 may be adhesively
mounted in place. An exemplary adhesive is ethylene vinyl acetate
adhesive. It is also desirable for the overall surface 438 of
backing strip 436 to be coated with a conventional adhesive.
Surface 438 is the surface which is affixed to the area Qf the skin
surrounding the wound. Conventional "peel-back" tabs may be used to
protect the adhesive coating and pad 440 until the bandage is to be
applied. This type of backing strip is well known in the art.
[0209] The backing strip 436 may be of any known flexible material
suitable for application to the skin. It is preferable for the
strip 416 to be of a material which is impermeable to the passage
of liquid so that fluid from a wound is contained by the bandage.
However, the strip 436 may be apertured or otherwise breathable to
permit air to reach the wound to promote the healing process. A
specific example of a suitable backing strip 436 is a polyethylene
film.
[0210] As in the other structures described, a variety of
combinations of antimicrobials and other particles may be used in
the fibers 441 of such a bandage. Again, however, the particles are
adhered securely in place when the particles have a hydrogen
bonding or a coordinate covalent bonding functionality, the fibers
to which these particles are bound have a hydrogen bonding
functionality, and wherein the binder is selected from the group
consisting of a polypropylene glycol, a polypropylene
glycol/polyethylene glycol copolymer, a polycarboxylic acid, such
as polyacrylic acid, a poly(lactone) polyol, such as
poly(caprolactone) diol, a polyamide, a polyamine, a polysulfonic
acid, and combinations thereof, and the polymeric binder has a
hydrogen bonding or a coordinate covalent bond forming
functionality on each repeating unit of the binder. Nonpolymeric
binders would include organic binders such as glycerin, a glycerin
monoester, a glycerin diester, ascorbic acid, urea, glycine,
pentaerythritol, a monosaccharide or a disaccharide, citric acid,
tartaric acid, taurine, dipropylene glycol, and urea derivatives
such as DMDHEU. Suitable saccharides include glucose, sucrose,
lactose, ribose, fructose, mannose, arabinose, and erythrose. Two
different particles, such as antimicrobials in particulate form,
may be adhered to the same fiber. In the alternative, each
different type of antimicrobial particle or other particle may be
adhered separately to different fibers. Also, blends of fibers may
be included in absorbent structures such as pad 366. For example,
these blends may include fibers with adhered antimicrobial (one or
more antimicrobials) particles and adhered superabsorbent
particles; fibers with one or more antimicrobial particles without
superabsorbent particles blended with fibers having adhered
superabsorbent particles with or without antimicrobial particles;
and combinations of such fibers with untreated fibers and/or binder
coated fibers without superabsorbent particles or antimicrobial
particles. In addition, other particles, such as anticoagulants or
hemostatics may be attached to the fibers.
[0211] The absorbent pad of bandage 430 may also include a cover
sheet that is typically made of any suitable material which will
readily permit the passage of liquid through the cover sheet to the
fibers 441, such as nonwoven fiber webs of fibers such as, for
example, rayon, nylon, polyester, propylene and blends thereof. One
specifically preferred cover sheet material is a 70 percent
rayon/30 percent polyester blend having a basis weight of 18
g/m.sup.2 from Scott Paper Company.
[0212] FIGS. 8 and 9 illustrate a conventional disposable diaper
550 with a core 552 which is comprised of fibers of the present
invention with adhered superabsorbent particulate materials. These
particulate materials may be confined to a target zone (for
example, the front or crotch portion of a diaper indicated at 556)
or of a heavier concentration in the target zone. This can be
accomplished by airlaying fibers of the present invention in such a
zone. Also, the core may be reactivated by melting the binder or
moistening the target zone with water. The superabsorbent particles
may be sprinkled on or otherwise applied to this wetted zone. As
the zone dries, the particles are adhered in place.
XX. Densification
[0213] The products such as described above, as well as webs of the
fibers of the present invention, can also be densified by external
application of pressure to the web. The web could be densified by
passing it through a set of calendar rolls set at 60 and 90 pli
(pounds per linear inch, as in a calendar press) respectively to
yield sheets with increased densities. Densification may
alternatively be provided by compaction rolls or presses.
Densification is preferably performed to produce a product that has
a density of about 0.05 to 0.7 g/cc, more preferably 0.1 to 0.3
g/cc.
[0214] An example of densification using some of the binders of the
present invention is given below:
EXAMPLE 27
[0215] Any of the products of the present invention can be formed
into 550 gram/square meter sheets, six inches in diameter, in a
laboratory padformer. Those pads may then be passed through a set
of calendar rolls set at 60 and 90 pli, respectively to yield
sheets with densities of 0.3 and 0.5 g/cc.
EXAMPLE 28
[0216] A 5 gram amount of polypropylene glycol is diluted with 5
grams deionized water. The resulting solution is sprayed on 438
grams of IM 1000F (supplied by Hoechst-Celanese, of Portsmouth,
Va.). The binder containing particles are then added to 321 grams
of an intrafiber crosslinked cellulose fluff (HBA from Weyerhaeuser
company of Tacoma, Wash.) that was air entrained in a blender like
mixing device. The resultant mixture may then be vacuumed from the
blender and spread on a counter to dry overnight. Then 550
gram/square meter handsheets, six inches in diameter, can be made
in a laboratory padformer. Those pads may then be pressed at 2000
and 3000 psi (or 60 and 90 pli in a calendar roll), respectively,
to yield densified sheets.
XXI. Particulate Binding
[0217] FIG. 10 illustrates an isolated, enlarged cellulose fiber
600 with SAP particles 602 bound to it by a binder of the present
invention. This drawing illustrates an example of the SAP retaining
its discrete particulate form following binding to the fibers. Some
particle to particle fusion may occur in accordance with this
invention, but maintenance of a discrete particulate form excludes
formation of a completely confluent film in which the
particles-lose their particulate identity. Such a confluent film
produces gel blocking that interferes with efficient liquid
absorption into the fibers.
[0218] The shown fiber 600 is elongated, and has an aspect ratio
(ratio of length to width) of about 10:1 to 5:1, preferably about
10:1.
[0219] FIG. 11 shows the particles 602 distributed substantially
uniformly throughout the depth 604 of a pad 606. The particles are
also shown adhering to all the surfaces of the pad. Particles may
be distributed in any desired pattern throughout the pad in
accordance with this invention, and need not necessarily adhere to
all surfaces or be distributed throughout the volume of the mat, or
distributed uniformly.
[0220] As can be seen from FIGS. 10-11, the particles are not
encapsulated by the binders, but are instead chemically bound or
fused to the fiber at the interface between the particle and fiber.
The particles and fibers of the present invention are not
encapsulated with the binder. Moreover, the binder does not
agglomerate the fibers together, and in many embodiments does not
bind fibers to each other. Discrete individual particles retain
their identity on the surface of the fibers, instead of being
subsumed in a thermoplastic encasement around the fiber and
particle.
XXII. Fiber Mixtures
[0221] The fibers of the present invention, such as fiber 600, can
be mixed with other types of fibers, such as disclosed in U.S. Pat.
No. 5,057,166. The latex coated fibers of that patent can be mixed
with the fibers of the present invention to produce an absorbent
product that has characteristics of both types of fibers.
XXIII. Additional Binder Characteristics
[0222] U.S. Pat. No. 3,903,889 discloses a process for adhering
absorbent particles to pulp fibers using syrup, honey, and other
polysaccharides such as dextrins. An essential requirement of these
adhesive agents is that they must possess the property of being
permanently pliable, and not rigidifying into a brittle film. The
binders of the present invention, in contrast, are capable of
functioning as a binder after solidifying into a rigid crystalline
material. Even the binders of the present invention that do not
rigidify into a solid (such as glycerin and PPG) are very
hygroscopic, and can be present on fibers having a total water
content of no more than 15%, or even 12%. This is in contrast to
the adhesives such as honey and corn syrup disclosed in U.S. Pat.
No. 3,903,889 that are not hygroscopic. Polysaccharides (such as
corn syrup, honey and dextrins) are excluded as binders from some
embodiments of the invention because they remain tacky upon drying.
Tacky binders make processing and handling the binder-treated
particles difficult. The polysaccharide polymers are also excluded
from nonpolymeric embodiments of the binder of the present
invention. Moreover, the nonpolymeric saccharides such as
monosaccharides and disaccharides, lack some of the high viscosity
and tacky-adhesive physical properties of polysaccharides such as
corn syrup and honey. The nonpolymeric saccharides of the present
invention may be solids, which avoid the viscosity and handling
problems associated with corn syrup and honey.
[0223] As used in this application, a particle that is soluble in
water will completely dissolve at least log of the particle in 300
ml water at 25.degree. C. A particle that is sparingly soluble in
the binder will completely dissolve no more than about 5 g of the
particle in 300 ml of the binder at 25.degree. C.
[0224] Some of the binders of the present invention are also water
soluble. A binder that is soluble in water will completely dissolve
at least log of the binder in 300 ml water at 25.degree. C.
[0225] By applying binder to particles, the properties of the
fibers are minimally impacted by the binder as the binder is
substantially confined to the contact areas between the particles
and fibers. Also, the quantities of binder required to adhere
particles to the fibers is substantially reduced over the quantity
required if the binder is applied to the fibers. For example,
strong bonds exist even when 0.1% binder is applied to
particles.
[0226] Having illustrated and described the principles of the
invention in many preferred embodiments, it should be apparent to
those skilled in the art that the invention can be modified in
arrangement and detail without departing from such principles. We
claim all modifications coming within the spirit and scope of the
following claims.
* * * * *