Natrosol Hidroxietilcelulosa
Natrosol Hidroxietilcelulosa
Natrosol Hidroxietilcelulosa
Hydroxyethylcellulose
A Nonionic Water-Soluble Polymer
Physical
and
Chemical
Properties
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Natrosol
Hydroxyethylcellulose
A Nonionic Water-Soluble Polymer
CONTENTS PAGE
NATROSOL HYDROXYETHYLCELLULOSE
A NONIONIC WATER-SOLUBLE POLYMER . . . . 2
A Guide to Where and Why Natrosol
Hydroxyethylcellulose Is Used . . . . . . . . . . . . . 2
CHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
GRADES AND VISCOSITY TYPES . . . . . . . . . . . 4
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
R-Grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
B-Grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Selected Types . . . . . . . . . . . . . . . . . . . . . . . . 4
PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Solubility in Water . . . . . . . . . . . . . . . . . . . . . . 5
Moisture Absorption . . . . . . . . . . . . . . . . . . . . . 5
Dermatology and Toxicology . . . . . . . . . . . . . . 5
FDA and EPA Status . . . . . . . . . . . . . . . . . . . . 6
Microbiological Information . . . . . . . . . . . . . . . . 6
Product Safety . . . . . . . . . . . . . . . . . . . . . . . . . 6
DISSOLVING NATROSOL HEC IN WATER . . . . . 7
Natrosol R-Grade . . . . . . . . . . . . . . . . . . . . . . 7
Solubility in Organic Solvents . . . . . . . . . . . . . . 8
PROPERTIES OF SOLUTIONS
OF NATROSOL HEC . . . . . . . . . . . . . . . . . . . . . . 9
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Effect of Concentration . . . . . . . . . . . . . . . . . 9
Effect of Blending . . . . . . . . . . . . . . . . . . . . . 9
Effect of Shear Rate . . . . . . . . . . . . . . . . . . 10
Effect of Mixed Solvents . . . . . . . . . . . . . . . 10
Effect of Temperature . . . . . . . . . . . . . . . . . 10
Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . 10
Viscosity Stability . . . . . . . . . . . . . . . . . . . . . . 11
Preservatives . . . . . . . . . . . . . . . . . . . . . . . . . 11
Use of Defoamers . . . . . . . . . . . . . . . . . . . . . . 12
Tolerance for Inorganic Salts . . . . . . . . . . . . . . 12
COMPATIBILITY WITH OTHER MATERIALS . . . .13
Latex Emulsions . . . . . . . . . . . . . . . . . . . . . . . 13
Cellulosic Water-Soluble Polymers . . . . . . . . . 13
Water-Soluble Resins . . . . . . . . . . . . . . . . . . . 13
Natural Gums . . . . . . . . . . . . . . . . . . . . . . . . . 13
Preservatives or Biocides . . . . . . . . . . . . . . . . 13
Surfactants and Detergents . . . . . . . . . . . . . . . 13
Defoamers . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Organic Solvents . . . . . . . . . . . . . . . . . . . . . . 13
PROPERTIES OF FILMS OF NATROSOL . . . . . . 16
Unplasticized Films . . . . . . . . . . . . . . . . . . . . . 16
Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Heat-Seal Characteristics . . . . . . . . . . . . . . . . 16
Solubility in Water . . . . . . . . . . . . . . . . . . . . . . 17
Insolubility in Organic Solvents . . . . . . . . . . . . 17
Resistance to Grease and Oil . . . . . . . . . . . . . 17
Photosensitivity . . . . . . . . . . . . . . . . . . . . . . . . 17
Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Insolubilizing Films of Natrosol . . . . . . . . . . . . 17
APPENDIXMETHODS OF ANALYSIS
FOR NATROSOL . . . . . . . . . . . . . . . . . . . . . . . . 18
Viscosity Determination . . . . . . . . . . . . . . . . . . 18
Moisture Determination . . . . . . . . . . . . . . . . 18
Solution Preparation . . . . . . . . . . . . . . . . . . 18
Viscosity Measurement . . . . . . . . . . . . . . . . 19
Ash Content . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Calculation . . . . . . . . . . . . . . . . . . . . . . . . . 19
QUALITY CONTROL, PACKAGING,
AND SHIPPING . . . . . . . . . . . . . . . . . . . . . . . . . 20
SOURCE AND DESCRIPTION OF
TRADEMARKED PRODUCTS . . . . . . . . . . . . . . 20
Hercules Incorporated, 1999.
Natrosol hydroxyethylcellulose (HEC) is a nonionic water-
soluble polymer derived from cellulose. Like Aqualon
HYDROXYETHYLCELLULOSE
A NONIONIC WATER-SOLUBLE POLYMER
Table I A Guide to Where and Why Natrosol Hydroxyethylcellulose is Used
Types of Uses Specific Applications Properties Utilized
Adhesives Wallpaper adhesives Thickening and lubricity
Latex adhesives Thickening and water-binding
Plywood adhesives Thickening and solids holdout
Binders Welding rods Water-binding and extrusion aid
Ceramic glaze Water-binding and green strength
Foundry cores Water-binding
Coatings Latex paint Thickening and protective colloid
Texture paint Water-binding
Cosmetics Hair conditioners Thickening
Toothpaste Thickening
Liquid soaps and bubble bath Stabilizing
Hand creams and lotions Thickening and stabilizing
Laundry Aids Fabric finishes Film-former
Aerosol starches Film-former
Liquid cleaners Thickening and stabilizing
Miscellaneous Joint cements Thickening
Hydraulic cements Water-binding and set retarder
Plaster Water-binding
Caulking compound and putty Thickening
Printing inks Thickening and rheology control
Asphalt emulsions Thickening and stabilizing
Paper Coating colors Water-binding and rheology control
Size press solutions Water-binding and solids holdout
Pharmaceuticals Lotions and emulsions Thickening and stabilizing
Jellies and ointments Thickening and water-binding
Polymerization PVAC and acrylic latices Protective colloid and surface activity
PVC suspension Protective colloid and surface activity
Textiles Latex-back sizes Thickening
Glass-fiber size Film-former
Printing pastes Thickening and water-binding
3
CHEMISTRY
The Natrosol
HEC IN WATER
Natrosol is readily soluble in either hot or cold water. However,
as with most water-soluble thickeners, the particles have a
tendency to agglomerate, or lump, when first wetted with
water. Thus, the time required to achieve complete solution of
Natrosol is usually governed by the degree of lumping that is
allowed to develop during the solution process. In general, the
low-viscosity types are more easily dissolved than are the high-
viscosity types. Solutions of the H-type, for instance, should
not be prepared at greater than 2% solids concentration.
Aqualon has solved the problem of lumping and slow dis-
solving by producing a surface-treated grade of Natrosol,
known as the R-grade. This grade disperses without lump-
ing when added to water. After an inhibition period, the
dispersed particles begin to dissolve and smooth, lump-free
solutions are readily achieved.
All viscosity types are available in the R-grade.
Additional information on the dissolution characteristics of
the R-grade is given in the section entitled Natrosol R-Grade.
If the R-grade is not used, the following procedures are
suggested for the easiest and most efficient preparation of
solutions of Natrosol.
Method 1
Natrosol should be sifted slowly into the vortex of vigorously
agitated water. The rate of addition should be slow enough
for the particles to separate in water without lump formation,
but not so slow that the solution thickens appreciably before
all the solid is added. Agitation should be continued until all
of the swollen or gelatinized particles are dissolved to yield
a smooth solution.
Method 2
Excellent solution rates can be obtained by prewetting
Natrosol with a water-miscible organic liquid before the
powder is added to water. Anhydrous ethyl alcohol, higher
alcohols, and ketones are suitable for this use, as are other
organic liquids such as diethylene glycol monoethyl ether,
diethylene glycol monoethyl ether acetate, ethylene glycol
monobutyl ether acetate, or hexylene glycol. Ethylene glycol,
however, is not recommended, as it swells the particles
slightly so that they tend to stick together instead of
separating as the prewetting liquid is dissolved away.
Method 3
Improved solution rates can be obtained by dry-blending
Natrosol with other dry materials (preferably insoluble) that
are to be added to the solution. This technique effectively
separates particles of Natrosol so that no lumping is
experienced when the dry mix is added to water.
NATROSOL R-GRADE
The special R-grade is designed to be added to water with-
out lumping, and thus greatly facilitates solution preparation.
The R-grade is widely used when higher viscosity types are
involved, or when the mixing equipment is inadequate to
handle the regular grades.
Figure 3
Natrosol R-grade disperses readily in water without lumping.
Within minutes the R-treatment dissolves and viscosity begins.
Some 28 minutes later, the viscous solution is clear. A 1% solution
of Natrosol 250 HR was used in water with a pH of 7.0.
8
Hydration of the Natrosol
HEC
Natrosol hydroxyethylcellulose differs from methylcellulose,
methylhydroxypropylcellulose, hydroxypropylcellulose, and
ethylcellulose in that Natrosol is soluble in both cold and hot
water. Thus, Natrosol does not display a cloud or precipita-
tion point and does not precipitate from aqueous solution at
elevated temperature.
Natrosol differs from carboxymethylcellulose in that it is non-
ionic. For this reason, Natrosol solutions are less affected by
pH change and are more tolerant of the presence of anions
and organic co-solvents.
VISCOSITY
Solutions of Natrosol are non-Newtonian in flow, since they
change in viscosity with rate of shear. Because Natrosol
is extensively used to modify the viscosity of solutions,
dispersions, emulsions, and the like, the effect of a number
of factors on solution viscosity will be discussed in detail.
The viscosity measurement method is given in detail in
the Appendix.
Effect of Concentration
When Natrosol is dissolved in water, the viscosity of the
aqueous solution increases rapidly with concentration, as
shown in Figure 6. The viscosity-concentration relationship
is nearly linear when viscosity is plotted vs. concentration
on a semilog basis.
Effect of Blending
Two viscosity types of Natrosol can be blended to obtain an
intermediate viscosity. Because viscosity is an exponential
function of concentration and degree of polymerization, the
viscosity resulting from blending is not an arithmetic mean.
A blending chart (VC-440), which is available from Aqualon,
can be used to determine the result of blending various
amounts of two viscosity types of Natrosol. Or, it can be
used to determine the amount of Natrosol required to
achieve a desired viscosity when blending two types of
known viscosity.
100,000
10,000
1,000
100
10
0 1 2 3 4 5 6
S
o
l
u
t
i
o
n
V
i
s
c
o
s
i
t
y
a
t
2
5
C
,
c
p
s
HH-Type
H4-Type
H-Type
MH-Type
M-Type
K-Type
G-Type
J-Type
L-Type
Natrosol 250 in Solution, % by wt
Figure 6
Effect of Concentration on Viscosity of Aqueous Solutions of Natrosol
10
As an example, it is desired to obtain a solution of Natrosol
C
,
c
p
s
Figure 8
Effect of Shear Rate on Viscosity of
Solutions of Natrosol
10,000
1,000
100
10
.001 .01 0.1 1.0 10 100 1,000 10,000 100,000
A
p
p
a
r
e
n
t
V
i
s
c
o
s
i
t
y
,
c
p
s
1.0% Natrosol 250HR
Shear Rate, reciprocal sec
Particle
Suspension
at Rest,
Film Sag
Under Gravity
Brookfield
Viscometer
Tumbling
or
Pouring
Brushing
Roll
Application
Spraying
2.0% Natrosol 250GR
3.0% Natrosol 250LR
11
Figure 9
Effect of Mixed Solvents on Viscosity of
Solutions of Natrosol
100,000
10,000
1,000
100
10
1.0
0.1
1.0 10 100 1,000 10,000 100,000
A
p
p
a
r
e
n
t
V
i
s
c
o
s
i
t
y
,
c
p
s
Shear Stress, dynes/cm
2
B
1
1% Natrosol 250HR
in Sucrose-Water
A
1
1%
Natrosol 250HR
in Water
BSucrose in Water
AWater
Figure 10
Nomograph for Estimating the Viscosity of Solutions
of Natrosol HEC at Varying Temperatures
10,000
E
x
a
m
p
le
100,000
70
1,000
100
10
10,000
1,000
100
10
60
50
40
30
20
10
Viscosity at
Higher Temp-
erature, cps
Viscosity at
Lower Temp-
erature, cps
Difference in
Tempera-
ture, C
Figure 11
Effect of pH on Viscosity of Solutions of Natrosol
10,000
pH of Solution
V
i
s
c
o
s
i
t
y
a
t
2
5
C
,
c
p
s
2,000
1,000
500
100
50
40
30
20
10
2 4 6 8 10 12
1% Natrosol 250HR
1% Natrosol 250MR
3% Natrosol 250LR
1% Natrosol 250GR
Effect of pH
Solutions of Natrosol undergo little viscosity change over the
pH range of 2 to 12. However, solutions possess the greatest
viscosity stability in the pH range of 6.5 to 8.0. Below pH 3,
solutions may show some drop in viscosity resulting from
acid hydrolysis. This is common to all water-soluble polysac-
charide polymers, and is accelerated by high temperature
and high acidity. Under highly alkaline conditions, some
oxidative degradation may occur, accelerated by heat and
light, that will lower the viscosity. See Figure 11.
VISCOSITY STABILITY
Natrosol HEC does not degrade when properly stored in
closed containers. Nine lots of Natrosol, viscosity grades M,
H, H4, and HH, were monitored over a period of a year for
viscosity stability. Average viscosity retention was 93%.
If Natrosol is kept in inventory for extended periods, Aqualon
recommends checking the viscosity at least once per year.
PRESERVATIVES
Natrosol HEC, particularly the B grades, is more resistant
to biological attack than are some other water-soluble gums
and polymeric materials. This better resistance is an impor-
tant factor in its use in latex paints.
Since solutions of Natrosol are not immune to biological
attack, it is recommended that a preservative be added
when the solutions are to be stored. As a convenience,
some preservatives that have been found effective in labora-
tory tests are listed in Table V, along with the names of their
manufacturers, in the case of proprietary products.
12
It is suggested that advice be obtained from the producers of
the preservatives as to the kind and amount of preservative
to be used in specific compositions for various end products.
For use in cosmetics and pharmaceuticals, particular care
should be exercised, both in the selection of an acceptable
preservative and in the maximum quantity used. The same
is true where Natrosol
250
(a)
HEC
10% Salt 50% Salt
Salt Solution (Saturated)
Aluminum nitrate C C
Aluminum sulfate C P
Ammonium chloride C C
Ammonium nitrate C C
Ammonium sulfate C P
Barium nitrate C C
Borax C C
Calcium chloride C C
Calcium nitrate C C
Calcium sulfate C C
Chromic nitrate C C
Chromic sulfate C C
Diammonium phosphate C P
Disodium phosphate P P
Ferric chloride C P
Ferric sulfate C C
Magnesium chloride C C
Magnesium sulfate C P
Potassium ferricyanide C C
Potassium ferrocyanide C P
Potassium metasulfite C C
Silver nitrate C C
Sodium acetate C C
Sodium carbonate P P
Sodium chloride C C
Sodium dichromate C C
Sodium metaborate C P
Sodium nitrate C P
Sodium perborate C C
Sodium sulfate P P
Sodium sulfite C P
Stannous chloride C C
Trisodium phosphate C P
Zinc chloride C C
Zinc sulfate C P
(a)
The H (high) viscosity types were used in this compatibility study.
Key: C = Compatible
P = Precipitate
13
Natrosol
sodium
carboxymethylcellulose (CMC) type 7H.
WATER-SOLUBLE RESINS
The nonionic Natrosol has a wide tolerance for water-soluble
resins. As shown in the table, solutions with Elvanol may
show synergistic viscosity increase, as evidenced with
anionic polymers such as CMC.
NATURAL GUMS
Natrosol HEC has excellent compatibility with natural gums.
PRESERVATIVE OR BIOCIDES
A variety of preservatives can be used with Natrosol. No
unusual effects were observed with use of those shown in
Table VII.
SURFACTANTS AND DETERGENTS
Natrosol has excellent tolerance for anionic, nonionic,
amphoteric, and cationic surfactants. No unusual effects
were observed. Representative materials from each of these
groups are shown in the table.
DEFOAMERS
Silicone-in-oil dispersions, silicone emulsions, and organic
defoamers can all be used with Natrosol with no unusual effects.
PLASTICIZERS
Water-soluble plasticizers generally do not adversely affect
the quality of solutions of Natrosol.
ORGANIC SOLVENTS
Although Natrosol is insoluble in most common organic
solvents (see page 17), it will tolerate relatively high concen-
trations of many water-miscible polar solvents. Examples of
a number of compatible systems combining Natrosol, water,
and organic solvents are given in Table VII.
COMPATIBILITY WITH OTHER MATERIALS
14
Table VII Effect of Formulation Additives on Properties of
Solutions of Natrosol
HEC
SOLUBILITY IN WATER
Films of Natrosol
HEC
VISCOSITY DETERMINATION
There are frequent occasions when, in addition to chemical
analysis, an accurate determination of the viscosity of a
solution of Natrosol is needed. As explained on page 9,
the apparent viscosity of a solution of Natrosol depends
on a number of factors, and if reproducible results are to
be obtained, a closely standardized method of solution
preparation and viscosity determination must be followed.
The standardized Aqualon method for determining viscosity
of Natrosol solutions specifies the Brookfield viscometer.
(2)
The spindle guard supplied with this instrument should be
used for all determinations.
Solution volumes specified should not be less or they may
not cover the appropriate Brookfield spindle.
The preparation of the solution is critical, in that the Natrosol
must be completely dissolved in order to obtain a significant
measurement. To determine the proper amount of polymer, a
moisture correction must be made. This correction compen-
sates for the moisture in Natrosol and bases the viscosity
measurement on dry Natrosol. The viscosity measurement
test must be rigidly standardized because the viscosity read-
ing obtained is dependent on rate of shear, temperature,
amount of agitation prior to measurement, and elapsed time
between agitation and measurement. The method used in
Aqualon laboratories is therefore given here in detail.
Moisture Determination
1. Weigh duplicate samples of 5 g to the nearest 0.001 g
into previously dried and weighed moisture cans
with covers.
2. Place the samples in a gravity convection oven main-
tained at 105 0.5C and heat for 3 hours. Cool in
a desiccator and weigh.
3. Return the samples to the oven for 45 minutes; cool and
weigh as before. If the second dried weight is not within
0.005 g of the first, repeat the 45-minute oven periods
until two subsequent weighings are in agreement. Then,
using the lowest dried weight obtained, calculate % mois-
ture as follows:
Original sample wt dry sample wt
100 = % moisture
Original sample wt
Solution Preparation
Immediately after portions of the sample of Natrosol are
taken for moisture determination, portions of the same
undried Natrosol should be taken for the viscosity solution
(1)
Several analytical procedures are contained in ASTM D2364, Standard Test
Methods for Hydroxyethylcellulose. Copies are available directly from
ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
(2)
Brookfield LVT, Brookfield Engineering Laboratories, Middleboro,
Massachusetts.
preparation. The moisture sample and solution sample
weighings should be carried out practically together to
ensure that the moisture content of the respective portions
is the same at the time of weighings.
Table XII Approximate Weights
for Solutions
Natrosol, Type Sample Weight, g Solution Concentration, %
L, J 13.0 5
E, G, K, M 5.2 2
MH, H, H4, HH 2.3 1
1. Weigh the required amount of Natrosol (see Table XII), to
the nearest 0.005 g, into a clean weighing bottle. Mini-
mize exposure of the sample to the air during weighing
and transfer to avoid moisture pickup.
2. For medium- and high-viscosity types, carefully (to
avoid any sample loss from dusting) transfer the bulk of
the sample to a 12-oz, screw-cap, widemouthed bottle.
Add 10.0 ml of 80% tert-butanol and allow to stand for
5 to 10 minutes. Make sure the entire sample is thor-
oughly wetted. Low-viscosity-type samples readily dis-
solve without the addition of tert-butanol. Medium- and
high-viscosity-type samples are more readily dissolved
with the inclusion of tert-butanol. This is particularly
important for samples that are not R-treated, because
lumping can occur.
Calculate the amount of water required to obtain the
desired solution concentration, using Equations a and
b for 1% and 2% solutions, respectively. The weight of
water required is reduced by the weight of tert-butanol
added (8.31 g). From the determined % moisture, calcu-
late the water to be added for the respective viscosity
solutions as follows:
a. For 1% viscosity solution:
Wt of undried Natrosol (99 % moisture) 8.3 =
Wt of
water
b. For 2% viscosity solution:
(Wt of undried Natrosol
(98 % moisture)
) 8.3 =
Wt of
water
2
3. For low-viscosity types, calculate the amount of water
required to obtain a 5% solution using Equation c.
c. (Wt of undried Natrosol
(95 % moisture)
) =
Wt of
water
5
19
Place the calculated amount of water into a 12-oz,
screw-cap, widemouthed bottle. While stirring in a constant-
temperature bath with mechanical agitation, using an
anchor-type stirrer, sprinkle the sample into the side of the
vortex. When the sample is completely dissolved, stir at high
speed for an additional 10 to 15 minutes.
Viscosity Measurement
Select from Table XIII the Brookfield spindle-speed combina-
tion corresponding to the viscosity type of Natrosol
HEC
being tested.
Attach the selected spindle to the instrument, which is then
set for the corresponding speed.
If the solution has been stirred in a constant-temperature
bath, determine the viscosity of the Natrosol immediately
after removing it from the stirrer. If it has not been stirred, in
a constant-temperature bath, cap it tightly and place it in a
25C constant-temperature bath for 30 minutes. Remove it
from the bath and shake it vigorously for 10 seconds.
Being careful not to trap air bubbles, insert the Brookfield
viscometer spindle into the solution. After allowing the spin-
dle to rotate for 3 minutes, stop the instrument and read the
dial. To determine the solution viscosity in centipoises, multi-
ply the dial reading by the factor in Table XIII that corre-
sponds to the speed and spindle used.
ASH CONTENT
The sample is charred over a low Bunsen flame to remove
the bulk of the volatile matter, cooled, and moistened with
sulfuric acid. The excess acid is evaporated, and the ashing
is completed in the normal way. The sulfate ash is calculated
to percentage.
Procedure
Weigh a 2- to 3-g sample to the nearest 0.001 g into a pre-
viously ignited and tared platinum or porcelain dish of about
75-ml capacity.
Table XIII Brookfield Spindle and
Speeds for Viscosity
Determinations
Spindle
Type of Spindle Speed, Maximum
Natrosol No. rpm Factor Reading, cps
E, L 1 30 2 200
J or G 2 60 5 500
K 3 30 40 4,000
M 4 60 100 10,000
MH 3 30 40 4,000
H or H4 3 30 40 4,000
HH 4 30 200 20,000
High concen- 4 12 500 50,000
tration of the
above types 4 6 1,000 100,000
Ignite it over a low Bunsen flame and allow it to burn, with
only occasional application of heat, until most of the car-
bonaceous material has burned off.
Cool and moisten the entire residue with 1:1 sulfuric acid.
Evaporate the excess acid over a low Bunsen flame slowly,
so as to avoid spattering, and complete the ignition by plac-
ing the sample in a muffle at 800 to 850C for 30 minutes or
until the ash is free of carbon. Cool, desiccate, and weigh.
Calculation
g of residue 100
= Ash as Na
2
SO
4
g of sample
Duplicate results should agree within 0.05%.
20
QUALITY CONTROL, PACKAGING, AND SHIPPING
To ensure quality control, plant production is both completely
automated and visually inspected. In addition, tests are con-
ducted throughout the production cycle to keep the impor-
tant properties of each lot within specification limits.
Natrosol
HF Hydroxypropylcellulose Aqualon
Kymene