Trends in The Development of Superabsorbent Polymers For Diapers

Chapter 7
Trends in the Development

of Superabsorbent Polymers for Diapers
Fusayoshi Masuda
Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Publication Date: October 19, 1994 | doi: 10.1021/bk-1994-0573.ch007
Research Division, Sanyo Chemical Industries Limited, Kyoto 605, Japan
Superabsorbent p o l y m e r s have become an i m p o r t a n t

component of diapers during the last 10 years. World-wide
demand for these polymers is currently about 320,000 metric
tons annually. In this paper, we report the results of a study
relating diaper performance to the properties of the
superabsorbent polymer. W e found that absorbency under
load and gel stability are important polymer properties to
relate to diaper leakage and surface dryness. However, these
properties appear to approach an upper limit related to the
current chemical structure of cross-linked polyacrylates. O u r
data suggests a limit for absorbency under load of 35-40 m L / g .
Commercial production of superabsorbent polymer began i n Japan i n 1978,

for use i n feminine napkins. Although the super absorbents used today are
based on poly(acrylic acid), this early superabsorbent was a crosslinked
starch-g-polyacrylate (2), an improved version of the uncrosslinked starch
graft polymer developed i n the 1970's by M . O. Weaver and her associates
at the N o r t h e r n Regional Research Laboratory of the U n i t e d States
D e p a r t m e n t of A g r i c u l t u r e (2). After further development (3),
superabsorbent polymer was used i n baby diapers i n Germany and France
i n 1980. These first diapers used only a small quantity of superabsorbent
polymer, about 1-2 g per diaper, and the polymer was considered only a
supplement to fluff pulp which furnished most of the absorbency. In 1983,
a thinner diaper using 4-5 g polymer and less fluff was marketed i n Japan.
This was followed shortly by the introduction of thinner superabsorbent
diapers i n other A s i a n countries, the United States and Europe. M o r e
recently, diapers have become even thinner, relying on greater amounts of
superabsorbent polymer. Specialty markets for superabsorbents have also
developed i n agriculture, sealants, air-fresheners and toys.
0097-6156/94/0573-0088$08.00/0
1994 American Chemical Society
In Superabsorbent Polymers; Buchholz, F., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1994.
7. MASUDA
Superabsorbent Polymers for Diapers
89

Demand for Superabsorbent Polymers

Since the introduction of superabsorbent diapers i n Japan i n 1983, demand
for superabsorbent polymer has increased rapidly, Figure 1. The demand
for superabsorbent polymer i n Japan i n 1992 was about 32,000 metric tons.
The polymer was used mostly i n baby diapers, feminine napkins and adult
diapers. Baby diapers account for the bulk of the demand. Demand for
superabsorbents i n feminine napkins is fairly stable at about 1,000 metric
tons due to a mature market i n Japan. The demand for superabsorbent i n
adult diapers has been gradually increasing i n Japan. Currently, about onethird of the market for adult diapers uses superabsorbent polymer.
World-wide, the demand for superabsorbent polymer has increased
dramatically since 1986, and currently amounts to about 280,000 metric
tons per year (Figure 2). The largest consumption is i n the the United
States (130,000 metric tons per year), followed by Europe at 100,000 metric
tons and A s i a and Oceania at 20,000 metric tons. Based on the trend, we
expect demand for superabsorbent polymers to reach 350-400,000 metric
tons per year within a few years.
Application Methods in Baby Diapers
Superabsorbent polymer is added to baby diapers i n basically two ways:
layered or blended. The layered application is commonly adopted by
Japanese diaper manufacturers. In this method, powdered superabsorbent
polymer first is scattered onto a layer of fluff pulp. The fluff is then folded,
so that the polymer is located i n a centralized layer i n the absorbent
structure. This structure is covered with a non-woven fabric layer. In the
b l e n d e d a p p l i c a t i o n , the superabsorbent p o l y m e r first is m i x e d
homogeneously with the fluff pulp. Then the mixture is laid d o w n to give
the absorbent structure, which is subsequently covered with a non-woven
fabric. This method typically is adopted by American diaper makers.
In either method, containment of the powdered polymer within the
loose, porous structure of the diaper is a concern. A recent development i n
Japan is the use of thermally bondable fibers w i t h i n the absorbent
structure to help fix the superabsorbent i n place. In this method, some of
the fluff pulp is replaced w i t h thermally bondable fibers. The resulting
absorbent core is heat-cured to give additional structural stability.
The use of superabsorbents has allowed thinner and lighter diapers to
be made. The first superabsorbent diapers contained 55-60 g of fluff i n
addition to 1-2 g of polymer. Currently, diapers with less leakage use about
7 g of polymer per diaper and only 30-35 g of fluff.
Important Properties for Good Diapers
The first superabsorbent diapers were characterized by having improved
surface dryness after absorbing urine. Reduced incidence of urine leaks has
been added as an important performance parameter for current diapers.

90
SUPERABSORBENT POLYMERS
40
|
o
35
30
25
PI
T3
Feminine
Napkin
Adult Diaper
Baby Diaper
20
Ml
llllli
WW
K f

15
10
\ Mi
5
|
0
m
oo
ON
rt
oo
On
vn
oo
On
oo
On
f00s
O
oo
oo
On
On
OO
On
o
ON
ON
ON
ON
ON
ON
Year
Figure 1. Demand for superabsorbent polymer i n Japan, for feminine
napkins, adult diapers and baby diapers.
Year
Figure 2. Demand for superabsorbent polymers worldwide, by geographical
area.


7. MASUDA
91
Both are n o w considered as basic functions for modern diapers. A

important problem i n the design of new superabsorbent diapers is relating
the physical properties of the superabsorbent polymer to the performance
of the diapers containing the polymer. In order to clarify the relationship
between diaper needs and polymer properties, a coefficient study was done
(4).
First, we synthesized 30 samples of superabsorbent polymer having
different combinations of properties. T h e n the p o l y m e r s were
incorporated into a standard diaper model, using the layered application
method described earlier. Diaper dryness was determined by measuring
the moisture content of the diaper surface. Leakage data was accumulated
i n actual diaper usage tests. The polymers alone were evaluated with 40
different test methods, i n c l u d i n g free-absorbency, absorbing rate,
absorbency under load ( A U L ) and gel-strength. Figures 3-6 show the
important results of this study of the relationship between diaper
performance and polymer properties.
The free absorbency of the superabsorbent polymer was determined
by measuring the increase i n mass of one gram of polymer contained i n a
sealed tea-bag, after immersion i n saline solution for 60 minutes. W e
found no relationship between diaper dryness and the free absorbency of
the polymer. This is despite the widespread popularity of the free
absorbency test and claims that high free absorbency yields a better diaper.
The absorbency under load ( A U L ) of the polymer was determined by
measuring the volumetric take-up of saline into one gram of polymer that
was spread on one square centimeter of filter-glass and compressed under
a 20-gram weight. The saline solution was i n contact w i t h the polymer,
through the filter-glass, for 60 minutes. Figure 3 shows the relationship of
A U L to diaper dryness. W e found a good relationship between higher
A U L and improved diaper dryness.
Diaper dryness was also improved for polymers having higher reabsorbency of the sheared gel for saline solution. In this test, the polymer
is first swollen w i t h ten times its mass of saline solution and then
mechanically sheared. The sheared gel is then put into a tea-bag and
immersed i n saline solution. The increase i n mass is measured and the
reabsorbency is calculated per gram of dry polymer. The relationship is
shown i n Figure 4. Another good relationship was found between diaper
dryness and the elasticity modulus of the swollen gel. Elasticity modulus
was measured on gel swollen with 40 times its mass of saline solution.
Diaper leakage was determined from actual use-testing of the model
diapers. Of the 40 measures of performance of superabsorbent polymers
that we performed, only the stability of the gel to shear could be related to
diaper leakage. W e found that polymers that were more stable to shear
yielded diapers with less leakage. This correlation is shown i n Figure 6.
Gel-stability to shear was determined by measuring the elastic modulus of
the polymer gel, swollen to 40 times its mass of saline solution, both

92
100
90 r
r = .78
80
70
60
a
50
40

30
00
20 r
10 r
0
< i i 1 i i iIIi 1
1 1 1 1 1 1 1 1 1 1 II 1 1 1 1 i 1 u Q l I.I.I ...
10
15
20
25
30
35
40
Absorbency Under Load (mL/g)

Figure 3. Correlation of surface wetness of diapers to the absorbency under
load of the superabsorbent polymer used i n the diaper.
100
90
^ = .75
80
70
60
B
o
&
00
50
40
30
20
10
0
M i l l
1 1 ^
10 15 20 25 30 35 40 45 50
Re-absorbency of Sheared Gel (mL/g)

Figure 4. Correlation of surface wetness of diapers to the re-absorbency of
liquid by the sheared gel.

7. MASUDA
93

100
90 r
r =.67
80
70
CO
<D

I
1
GO
60
50 r
40
30
20
10
0 '- , , , I ,i i 1
0
2
4
i1 i ii1i
6
1i P i
10
12
2
Elasticity Modulus ( 1 0 dyne/cm )

Figure 5. Correlation of surface wetness of diapers to the elasticity
modulus of the swollen superabsorbent polymer.
a
3
50
55
60
65
70
75
80
85
90
Gel-stability Against Shear (%)

Figure 6. Correlation of leakage from diapers to the stability of the swollen
gel to shear.


94
before and after mechanical shearing. The fraction of the original elastic
modulus retained by the sheared gel is expressed as the percent stability.
The results of our study are summarized i n Table I. Diaper dryness is
closely correlated w i t h three polymer tests: absorbency under l o a d ,
reabsorbency of sheared gel and the elasticity modulus of the swollen gel.
A balance of these three factors appears important for improved diaper
dryness. Diaper leakage was closely correlated to the stability of gel to
shearing. The scientific meaning of these four tests has not yet been fully
investigated and more study is warranted. H o w e v e r , we think that
superabsorbent polymer for use i n baby diapers should have higher gel
strength and an ability to maintain the absorption capability against
shearing because the physical properties of the swollen gel are influenced
by the shear that accompanies the movement of a baby while the diaper is
i n use.
Table I. Superabsorbent polymer functions related to the performance of
diapers.
Diaper Needs
Superabsorbent
Polymer Functions
Correlation
Coefficient
Dryness
Absorbency Under Load

Re-absorbency of Sheared Gel
Elasticity Modulus
0.78
0.75
0.67
Less Leakage
Gel Stability against Shear
0.93
Trends in the Properties of Superabsorbent Polymers

W i t h our new insight into four polymer properties that are important for
dryness and less leakage, we w i s h to review the historical trends i n these
properties. W e measured the free absorbency and the absorbency under
load for a number of commercially available superabsorbent polymers. A s
shown i n Figure 7, older samples had higher free absorbency and lower
absorbency under load. More recently, the A U L has increased to about 30
m L / g while free absorbency has dropped to about 50 m L / g . Based o n
extrapolation of Figure 7, we think that A U L may be increased to 35-40
m L / g u s i n g conventional, or existing, technology. Because of its
demonstrated importance to diaper performance, it may be desirable to
have A U L as high as 50 m L / g . W e think a technical breakthrough is
necessary to achieve this value, however. The historical trend of gel
stability to shearing is shown i n Figure 8. Older samples had poor stability
to shear but this property has been gradually improved over time, with
recent samples having 70-90 % retention of modulus after shearing.
7. MASUDA
95
I
I
CO
0
O
0
N
0
O
0
S
0
O
0
N
0 0 C 3 0 0 0 0 0 0 0 O 0 N 0 N
O N G N O N O S O N C 3 N O N O S
O
O N
Year
Figure 7. Historical trends of the absorbent properties of superabsorbent
polymers.
100
90 0
80
0
T3
CO
70 -
o
oo
60 s
50
40
1982
o o o s
o cT
ooo
o
1
._l_
1984
1986
1988
1990
1992
Year
Figure 8. Historical trend of the stability of swollen gel to shear.

96

Trends in Process Control of Superabsorbent Polymers

Polyacrylate superabsorbent polymer has been i n commercial production
for ten years. The absorbency parameters are not the only features that
have changed over this time. A s shown i n Figure 9, the level of residual
acrylic acid has dropped from over 1000 p p m in 1983 to around 100 p p m i n
1992. F i g u r e 10 shows that the extractable p o l y m e r fraction of
superabsorbent, comprising l o w molecular weight and slightly crosslinked
polyacrylate, has also decreased over time. M o r e stringent raw material
specifications b y the diaper producers contributed to the current
superabsorbents having reduced amounts of fines (particles less than 50
microns) and a narrower particle size distribution (Figure 11).
2000
1800
1600
&
1400
g
o
1200
1000
800
J;
600
400
200
0
1982
1984
1986
1988
1990
1992
Year
Figure 9. H i s t o r i c a l trend of the content of residual monomer i n
superabsorbent polymers.
Conclusion
We have found that absorbency under load and stability of the gel against
shear are important properties of superabsorbent polymers and relate
strongly to diaper performance. However, these properties appear to be
approaching a limit related to the current chemical structure of crosslinked polyacrylates. Because of the market requests for a thinner diaper,
more superabsorbent polymer and less fluff is being incorporated into
diapers. This approach limits the m a x i m u m amount of superabsorbent
polymer i n a diaper to about 10 g/piece, and this requires that the
absorbency under load be increased. A target for A U L of 35-40 m L / g is
probably achievable using current technology, but an A U L of about 50
m L / g is probably necessary to get a much thinner diaper. The future efforts
7. MASUDA
97
\
c
e
_ o
CD
C
o
o
E
o o
o
er
.1
_J_
1984
sQO
G
O
o
0
1982
1986
Q fihHHIh
1988
1990
1992
Year
Figure 10. Historical trend of the content of extractable p o l y m e r i n
superabsorbent polymers.
20
O
18 -
16 -
14 _ O O
CO
12 -
10 8 -
o
o
o
o
e3-
6 -
o
o
4 o
2 -
J_
1982
1984
1986
1988
1990
1992
Year
Figure 11. Historical trend of the content of fine particles (less than 50 um)
in granular superabsorbent polymers.

98
of manufacturers to i m p r o v e the p r o d u c t i o n and engineering of

superabsorbents should make possible higher performance and even
lower levels of residual monomer, extractables and fines i n the product.
Literature Cited
1.
2.

3.
4.
Masuda, F.; Nakamura, A . ; Nishida, K . U S 4,076,663 (1978).

Weaver, M. O.; Bagley, E. B.; Fanta, G . F.; Doane, W . M. U S 3,981,100
(1976).
M a s u d a , F. Superabsorbent Polymers, E d . Japan Polymer Society,
Kyoritsu Shuppann, 1987, 24-50.
Chambers, D . R.; Fowler, H. H.; Fujiura, Y.; Masuda, F. U S 5,145,906
(1992).
RECEIVED July 27,
1994


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Chapter 7

Trends in the Development

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Research Division, Sanyo Chemical Industries Limited, Kyoto 605, Japan

Superabsorbent p o l y m e r s have become an i m p o r t a n t

Commercial production of superabsorbent polymer began i n Japan i n 1978,

In Superabsorbent Polymers; Buchholz, F., et al.;

Superabsorbent Polymers for Diapers

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Demand for Superabsorbent Polymers

In Superabsorbent Polymers; Buchholz, F., et al.;

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

In Superabsorbent Polymers; Buchholz, F., et al.;

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Superabsorbent Polymers for Diapers

Both are n o w considered as basic functions for modern diapers. A

In Superabsorbent Polymers; Buchholz, F., et al.;

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Absorbency Under Load (mL/g)

Re-absorbency of Sheared Gel (mL/g)

In Superabsorbent Polymers; Buchholz, F., et al.;

Superabsorbent Polymers for Diapers

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Elasticity Modulus ( 1 0 dyne/cm )

Gel-stability Against Shear (%)

In Superabsorbent Polymers; Buchholz, F., et al.;

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Absorbency Under Load

Gel Stability against Shear

Trends in the Properties of Superabsorbent Polymers

Superabsorbent Polymers for Diapers

In Superabsorbent Polymers; Buchholz, F., et al.;

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Trends in Process Control of Superabsorbent Polymers

Superabsorbent Polymers for Diapers

In Superabsorbent Polymers; Buchholz, F., et al.;

of manufacturers to i m p r o v e the p r o d u c t i o n and engineering of

Downloaded by UNIV OF ARIZONA on December 5, 2012 | http://pubs.acs.org

Masuda, F.; Nakamura, A . ; Nishida, K . U S 4,076,663 (1978).

RECEIVED July 27,

In Superabsorbent Polymers; Buchholz, F., et al.;

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