Klucel HPC Booklet
Klucel HPC Booklet
Klucel HPC Booklet
and Chemical
Properties
Klucel
Klucel
Klucel
Klucel
hydroxypropylcellulose
Klucel
Klucel
Klucel
Klucel
Klucel
Klucel
Klucel
HERCULES INCORPORATED
Aqualon Division
Hercules Plaza
1313 North Market Street
Wilmington, DE 19894-0001
(302) 594-5000
www.aqualon.com
ORDER PLACEMENT INFORMATION
(800) 334-8426
KLUCEL HYDROXYPROPYLCELLULOSE
CONTENTS
PAGE
VISCOSITY IN ORGANIC SOLVENT
SOLUTIONS .................................................... 15
Viscosity and Precipitation Temperature
in Aqueous Alcohols...................................... 17
KLUCEL HYDROXYPROPYLCELLULOSE...... 2
APPLICATIONS .................................................. 3
CHEMISTRY ...................................................... 4
GRADES AND VISCOSITY TYPES.................... 5
PROPERTIES......................................................
MOISTURE ABSORPTION ..................................
POLYMER STABILITY..........................................
BURNOUT TEMPERATURE ................................
6
6
6
6
7
7
7
7
7
7
8
THERMOPLASTICITY MOLDING
AND EXTRUSION .......................................... 18
FORMULATION OF MOLDING
COMPOUNDS ................................................ 18
FILMS AND COATINGS ..................................
FILM PROPERTIES............................................
PLASTICIZERS FOR FILMS ..............................
ADDITIVE AND MODIFIER FOR FILMS
AND COATINGS ..............................................
SOLUTION CASTING FOR FILMS
AND COATINGS ..............................................
INSOLUBILIZING FILMS AND COATINGS........
PROPERTIES OF SOLUTIONS.......................... 9
AQUEOUS SOLUTIONS...................................... 9
Effect of Concentration and Viscosity Type .... 9
Rheology........................................................ 10
Effect of Temperature .................................... 10
Precipitation Temperature in Water .............. 11
Compatibility With Surfactants...................... 11
Addition of Certain Ionic Surfactants ............ 11
Effect of pH .................................................. 11
Effect of Inorganic Salts ................................ 11
Compatibility With Other Polymers .............. 12
Water-Soluble Polymers ............................ 12
Water-Insoluble Polymers.......................... 13
Viscosity Stability .......................................... 13
Hydrolysis and Oxidation .......................... 13
Biological Stability .................................... 13
Preservatives ................................................ 13
Surface and Interfacial Tension .................... 14
Recommended Defoamers........................ 14
19
19
19
19
19
19
20
20
20
20
20
APPENDIX ........................................................
METHODS OF ANALYSIS ................................
A. Moisture ..................................................
B. Viscosity in Water ....................................
B. Solution Preparation ..............................
B. Viscosity Determination ........................
C. Viscosity in Ethanol..................................
D. Ash Content ............................................
PRODUCT LISTING SUPPLEMENT ..................
21
21
21
21
21
22
22
22
23
KLUCEL HYDROXYPROPYLCELLULOSE
KLUCEL hydroxypropylcellulose (HPC) is a nonionic watersoluble cellulose ether with a remarkable combination of
properties. It combines organic solvent solubility, thermoplasticity, and surface activity with the aqueous thickening and
stabilizing properties characteristic of other water-soluble
cellulose polymers available from Hercules Incorporated,
Aqualon Division. KLUCEL films are flexible without plasticizers and non-tacky at high humidity.
The information in this booklet presents the physical and
chemical properties of KLUCEL as developed in our research
and plant facilities. Also included is information about the
behavior of KLUCEL with many of the materials that would be
used in most applications. A guide to regulatory status and
toxicological studies is provided for convenient reference.
The Appendix gives information about Aqualon test methods
for viscosity, moisture, and ash content.
To help the reader identify the versatile uses for this watersoluble polymer, a representative listing has been developed
and is presented on the following page. Many of these uses
for KLUCEL are discussed in detail in technical literature
available from your Aqualon sales representative by request,
and/or from our website at www.Aqualon.com.
APPLICATIONS
Specific Applications
Properties Utilized
Adhesives
Solvent-based
Hot-melt
Thickener
Thermoplastic
Aerosols
Binder
Coatings
Cosmetics
Burnout types
Electrical insulators
Ceramic glazes
Alcohol core-wash compounds
Matrix board manufacture
Encapsulation
Extrusion
Foods
Whipped toppings
Edible coatings for nuts and candies
Glaze for confections
Fabricated foods
Molding
Paint removers
Acid-based
Scrape-off and flush-off
Paper
Coatings
Pharmaceuticals
Tablet binder
Tablet coating
Modified release
Liquids and semisolids
Plastic foams
Thermoplasticity
Polyvinyl chloride
processing
Suspension polymerization
Printing
Miscellaneous
Cleaners (acid-based)
Polishes (aqueous- and solvent-based)
}
3
CHEMISTRY
An idealized structure for a portion of a hydroxypropylcellulose molecule with a molar substitution (MS) of 3.0 is
given in Figure 1.
Figure 1
Structure of Hydroxypropylcellulose (MS 3.0)
Grades of KLUCEL
Intended Market
Grade Designation
Industrial
Food
Personal Care
Pharmaceutical
Industrial
F
CS
F Pharm
Table I KLUCEL Viscosity Types, Viscosities (cps)(a), and Their Corresponding Molecular Weights
Industrial Grade
Viscosity Types
10
Mw(b)
H Industrial
M Industrial
G Industrial
J Industrial
L Industrial
E Industrial
1,275-3,500
3,500-7,500
125- 450
125-450
65-175
250-800
1,150,000
850,000
370,000
140,000
95,000
80,000
Viscosity Types
10
Mw(b)
H CS, HF Pharm
M CS, MF Pharm
GF, G CS, GF Pharm
JF, J CS, JF Pharm
LF, L CS, LF Pharm
EF, E CS
EF Pharm
1,500-3,000
4,000-6,500
150- 400
150-400
75-150
200-600
300-600
1,150,000
850,000
370,000
140,000
95,000
80,000
80,000
(a)
(b)
Viscosity Types
H CS, HF Pharm
M CS, MF Pharm
G CS, GF Pharm
J CS, JF Pharm
L CS, LF Pharm
E CS, EF Pharm
1,000-4,000
3,000-6,500
75- 400
75-400
25-150
10
Mw(b)
150-700
1,150,000
850,000
370,000
140,000
95,000
80,000
All viscosities are determined at 25C using a Brookfield LVF viscometer with spindle and speed combinations depending on viscosity level. See Appendix.
Weight-average molecular weight determined by size exclusion chromatography.
PROPERTIES
POLYMER STABILITY
Long-term storage stability of KLUCEL hydroxypropylcellulose
is affected by the initial molecular weight of the polymer
and storage conditions. Studies have shown that low- and
medium-viscosity types maintain an average of 97% of their
original viscosity after three years when stored at room
temperature with frequent exposure to the atmosphere.
Ash content,
calculated as Na2SO4, %
Moisture content
(as packed), %
pH in water solution
Moles of substitution
mesh
mesh
mesh
mesh
5.0 max
Food and Personal Care
Grades: 5.0-8.0
Pharmaceutical Grade:
5.0-7.5
Solubility in water(a)
Solubility in organic solvents
3.4 to 4.4
Bulk density, g/ml
Softening temperature
Burnout temperature
(1)
Fine x-grind Pharmaceutical Grade E and H viscosity types are available and
designated as EXAF Pharm and HXAF Pharm. Particle size specifications are:
min. 80% through 100 mesh
min. 90% through 80 mesh
min. 99.9% through 60 mesh
MOISTURE ABSORPTION
KLUCEL absorbs moisture from the atmosphere, as do other
water-soluble materials. The amount absorbed depends on
relative humidity and temperature of the environment. As
packed, moisture content of all grades does not exceed 5% by
weight, and is generally between 2% and 3%. It is suggested
that KLUCEL be stored in tightly closed containers and in a
dry atmosphere to prevent any increase in moisture content.
Solutions in Water
Specific gravity, 2% solution
at 30C
Refractive index, 2% solution
Surface tension, at 0.1%
Interfacial tension, 0.1%
KLUCEL in water vs refined
mineral oil
Bulking value in solution,
(a)
1.010
1.337
43.6 dynes/cm
12.5 dynes/cm
0.04 (0.334) gal/lb (l/kg)
BURNOUT TEMPERATURE
KLUCEL has excellent binding properties. It is often used
as a temporary binder in production of ceramics, glazes,
refractories, and powdered metal products. This polymer is
vaporized, or burned out, over the temperature range of 250
to 500C in oxidizing, reducing, or inert atmospheres. The
very low ash content of the original KLUCEL and the complete absence of organic residues after firing ensure virtually
uncontaminated end products after burnout.
4%
12%
In the second step, the hot slurry is diluted with cold water
(room temperature or lower). Agitation is continued until all
particles are dissolved and solution is completely free of
gels. High-shear agitation is not necessary, and may be
undesirable because of the tendency for foaming and air
entrainment. In this dissolving step, the time factor is more
important than high shear when it comes to ensuring
complete solution of all gel particles.
Method 3
Dry-blend KLUCEL with any inert or nonpolymeric soluble
material that will be used in the formulation. Blending aids
separation of particles of KLUCEL at first wetting and
reduces the tendency to lump. For best results, KLUCEL
should be less than 20% of the total dry blend. This blend
is then handled as described in Method 2.
IN ORGANIC LIQUIDS
All types of KLUCEL have excellent solubility in a wide range
of polar organic liquids and give clear, smooth solutions at
ambient or elevated temperatures. There is no tendency for
precipitation of KLUCEL in hot organic solvents; this is in
contrast to its behavior in water solutions. Generally, the
more polar the liquid, the better the solution. Methyl and
ethyl alcohol, propylene glycol, dioxane, and Cellosolve are
some of the best organic solvents for all types of KLUCEL.
Table VIII, page 15, lists the type of solutions obtained with
G viscosity types in many organic liquids. The molecular
weight of the type of KLUCEL can have a marked effect on
solution quality in an organic liquid that is a borderline solvent
for KLUCEL.
In general, principles discussed for preparing water solutions apply when using organic solvents to make solutions
of KLUCEL. Methods 1, 2, and 3 described for preparing
water solutions can therefore be used to prepare solutions
of KLUCEL in organic solvents. The pre-slurry principle of
Method 1 can be employed through the use of nonsolvents
such as glycerin, aliphatics, aromatics, and others.
KLUCEL is compatible with a number of high-molecularweight, high-boiling waxes and oils, and can be used to
modify the properties of these materials. The addition of
KLUCEL to these systems will increase viscosity and
improve hardness and crack resistance to coatings.
Aliphatic and aromatic hydrocarbons and petroleum distillates are nonsolvents for KLUCEL. However, relatively large
quantities of these nonsolvents can be tolerated in a solution
if KLUCEL is first dissolved in a solvent that is miscible with
these nonsolvents. Examples of solvent-nonsolvent systems
are given in Table VIII. Figure 2 details the effect of solvent
composition on viscosity of a solution of G Industrial in a
toluene:ethanol system.
Figure 2
Viscosity of G Industrial Dissolved in Toluene-Ethanol
5,000
G Industrial, at 2%
1,000
500
KLUCEL Soluble
KLUCEL
Insoluble
100
PROPERTIES OF SOLUTIONS
AQUEOUS SOLUTIONS
At room temperature, solutions of KLUCEL can be prepared
in a wide range of viscosities, depending on concentration
and viscosity type used. Since solutions are non-Newtonian,
it is essential to standardize viscosity determination methods.
The method used in the control laboratory at Aqualon is
described in detail in the Appendix.
Figure 3
Effect of Concentration and Type of KLUCEL on Viscosity of Water Solutions
100,000
H Viscosity
Types
M Viscosity
Types
G Viscosity
Types
10,000
J Viscosity
Types
L Viscosity
Types
1,000
E Viscosity
Types
100
10
0
2
4
6
Solids Concentration of KLUCEL, wt%
10
12
14
Effect of Temperature
Viscosity of an aqueous solution of KLUCEL decreases as
temperature is increased. This effect is normal for polymers
in solution. This change in viscosity is illustrated in Figure 4
for H viscosity type and J viscosity type. As shown, viscosity
is halved as temperature is raised through 15C. This effect is
uniform up to the precipitation temperature (40 to 45C).
Rheology
Solutions of KLUCEL are exceptionally smooth-flowing and
exhibit little or no structure or thixotropy. However, solutions
are pseudoplastic under conditions of high rates of shear
and will show a temporary decrease in viscosity while under
shear. The viscosity returns to the original value when the
shear is removed. The lower the molecular weight of
KLUCEL and the lower the shear rate, the less will be
this decrease in viscosity experienced under shear.
Figure 4
Effect of Temperature on the Viscosity of Aqueous Solutions of KLUCEL
10,000
H Viscosity Type,
at 1%
Precipitation Temperature
1,000
Cooling
Heating
KLUCEL
Precipitates
J Viscosity type,
at 5%
100
0
10
20
30
Temperature, C
10
40
50
60
70
Effect of pH
KLUCEL HPC is a nonionic polymer, and viscosity of water
solutions is not affected by changes in pH. The viscosity of
solutions remains unchanged as pH is varied over the range
of 2 to 11.
Precipitation
Temperature, C
41
38
30
41
36
32
20
7
11
Water-Soluble Polymers
KLUCEL is compatible with most natural gums and synthetic
water-soluble polymers. Solutions in water are homogeneous,
and films cast from these solutions are uniform. The following
have been tested and found to be compatible:
Aluminum sulfate
Ammonium nitrate
Ammonium sulfate
Calcium chloride
Disodium phosphate
Ferric chloride
Potassium ferrocyanide
Silver nitrate
Sodium acetate
Sodium carbonate
Sodium chloride
Sodium nitrate
Sodium sulfate
Sodium sulfite
Sodium thiosulfate
Sucrose
Salt Concentration,
% by weight
2
10
50
C
C
C
C
I
C
C
C
C
C
C
C
C
C
C
C
I
C
I
C
C
C
C
C
I
C
C
I
I
I
C
C
I
C
I
I
C
(a)
12
Table VI Blends of KLUCEL HPC and Other Water-Soluble Polymers: Effect on Viscosity
Polymer Blend (1:1)
Concentration, %
Viscosity Types
J and NATROSOL 250J HEC
M and NATROSOL 250M
H and NATROSOL 250H
H and AQUALON CMC-7H
5
2
1
1
Initial
After 24 Hours
235
6,250
2,320
2,220
240
5,900
2,440
4,400
235
5,600
2,440
3,860
Water-Insoluble Polymers
KLUCEL is compatible with many natural and synthetic
latexes available as emulsions in water. KLUCEL is soluble
in the aqueous phase, and uniform films and coatings are
obtained upon drying.
Biological Stability
The high level of substitution of KLUCEL improves resistance
of this polymer to degradation by cellulase enzymes produced by molds and bacteria. However, water solutions are
susceptible to degradation under severe condtions, and a
viscosity decrease may result. If prolonged storage is contemplated, a preservative is recommended.
Viscosity Stability
Water solutions of KLUCEL possess best viscosity stability
when pH is held between 6.0 and 8.0, and when the solutions
are protected from light, heat, and action of microorganisms.
KLUCEL in water solution, like other water-soluble polymers,
is susceptible to both chemical and biological degradation.
This degradation generally results in reduction of molecular
weight of the dissolved polymer, with an accompanying
decrease in viscosity of the solution. Some loss of solution
clarity may occur in cases of severe biological degradation.
Sodium benzoate
Sorbic acid and its potassium, sodium, and calcium salts
Sodium propionate
Methyl and propyl parahydroxybenzoate
13
14
KLUCEL, wt%
Surface
Tension,
dynes/cm
(mN/m)
Interfacial Tension
vs Refined Mineral Oil,
dynes/cm
(mN/M)
0 (water)
0.01
0.1
0.2
74.1
45.0
43.6
43.0
31.6
12.5
Methyl acetate
Methyl ethyl ketone
Methylene chloride
Naphtha:ethanol (1:1)
Tertiary butanol
Xylene:isopropyl alcohol
(1:3)
C. INSOLUBLE
Aliphatic hydrocarbons
Benzene
Carbon tetrachloride
Dichlorobenzene
Kerosene
Trichloroethylene
Xylene
(a)
Methyl chloroform
Mineral oils
Soybean oil
Toluene
Gasoline
Glycerin
Linseed oil
15
Solvent
H at 1%
(b)
L at 9%
E at 10%
Water
Methanol
Methanol:water (3:7 by weight)
2,100
800
270
85
360
80
25
275
75
Ethanol
Ethanol:water (3:7)
1,600
210
500
65
255
(b)
145
130
570
420
(b)
50
1,240 (b)
400
(a)
G at 2%
(b)
Acetone
Methylene chloride
Methylene chloride:methanol (9:1)
4,500
5,000
Chloroform
Propylene glycol
Ethylene chlorohydrin
6,000
470
(b)
(b)
6,640
430
2,560
5,020
310
(B)
Viscosities shown are presented only as typical values. Some variation in these viscosities will be obtained from lot to lot of each type of KLUCEL.
Borderline solvent for the particular type of KLUCEL. Solutions are granular and may be hazy.
16
175
14,600 (b)
17,000 (b)
>10,000
1,110
Figure 5
Viscosity of Aqueous Alcohol Solutions (G viscosity types
at 2% concentration by weight)
1,000
Ethanol-Water
Methanol-Water
Propylene glycol performs similarly to methanol, and elevation of precipitation temperature falls on the same curve.
Other water-miscible organic liquids, which are good solvents
for KLUCEL, will also function to elevate precipitation
temperature of the polymer in the system.
100
10
0
20
40
60
80
Water Content of Aqueous Alcohol
Solvent, % by weight
Precipitation Temperature, C
Figure 6
Precipitation Temperature of KLUCEL in Aqueous Alcohols
Boiling Points
Ethanol-Water
Methanol-Water
17
100
18
FILM PROPERTIES
All films of KLUCEL are characterized by the following
outstanding properties:
Excellent flexibility
Lack of tackiness at high humidity
Good heat sealability
Barrier to oil and fat
19
PACKAGING,
REGULATORY STATUS,
TOXICOLOGY, SAFETY
PACKAGING
KLUCEL HPC is shipped in fiber drums with a polyethylene
inner liner containing 100 lbs net.
PRODUCT SAFETY
KLUCEL is a flammable dust when finely divided and
suspended in air. An explosion can occur if the suspended
dust is ignited. Proper design and operation of facilities and
good housekeeping practices can minimize this hazard.
REGULATORY STATUS
Food grade, designated with a F, complies with the requirements of the US FDA for direct addition to food for
human consumption, as specified in the Code of Federal
Regulations, Title 21, Section 172.870. Food grade Klucel
also conforms to the specifications for hydroxypropylcellulose
set forth in the Food Chemicals Codex.
CASRN:
CAS Name:
20
9004-64-2
Cellulose 2-hydroxypropyl ether
APPENDIX
METHODS OF ANALYSIS
All types of KLUCEL HPC meet certain specifications for
moisture, viscosity, and ash content. Detailed descriptions
are given of Aqualon methods for determining these values.
A. Moisture
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 maintained at 105 0.5C. Heat for 3 hrs. Cool in a desiccator
and weigh.
3. Return the sample to the oven for 45 min. Cool and weigh
as before. If the second dried weight is not within 0.005 g
of the first dried weight, repeat the 45-min oven periods
until two subsequent weighings are in agreement. Then,
using the lowest dried weight obtained, calculate percent
moisture as follows:
Original
sample weight dry sample weight
Original sample weight
(Weight of KLUCEL, g)
x (98 % moisture)
x 100 = % moisture
= Weight of water, g
2
B. Viscosity in Water
As explained on page 9, the apparent viscosity of a solution
of KLUCEL depends on a number of factors. If reproducible
results are to be obtained, a closely standardized method
of solution preparation and viscosity determination must
be followed.
(Weight of KLUCEL, g)
x (95 % moisture)
= Weight of water, g
5
(Weight of KLUCEL, g)
x (90 % moisture)
= Weight of water, g
10
3. Add the calculated amount of distilled water to a
16-oz bottle.
4. Stir the water with a mechanical agitator to create a
vortex, and slowly sift the KLUCEL into the vortex over a
15 to 30-sec period to ensure good dispersion. An anchorshaped stirrer turned by a compressed-air or electric
motor has been found to be satisfactory. After the solution
appears to be complete, stir it for an additional 10 to 15
min at high speed. Be careful to avoid loss of solution.
5. When the solution is complete, cover the mouth of the
bottle with cellophane and screw the cap on securely.
Place it in a constant-temperature bath (25 0.2C) for
30 min, or for as long as necessary to adjust the solution
temperature to 25 0.2C.
Solution Preparation
Immediately after taking portions of the KLUCEL polymer
sample for moisture determination, portions of the same
undried KLUCEL should be taken for viscosity solution
preparation. Weighings of moisture and solution samples
should be carried out practically together to ensure that the
moisture content of the respective portions is the same at
time of weighings.
The standardized Aqualon method for determining the
viscosity of solutions of KLUCEL specifies use of the
Brookfield viscometer, Model LVF (Brookfield Engineering
Labs, Stoughton, Massachusetts; 4 spindles, 4 speeds
covering the range 0 to 100,000 cps).
21
Viscosity Determination
6. While the solution is in the constant-temperature bath,
select from Table XIII below the Brookfield spindle-speed
combination corresponding to the viscosity type of
KLUCEL HPC being tested. Determine the viscosity of
the KLUCEL within 2 hrs after removing it from the stirrer.
If the solution stands longer than 2 hrs, return it to the
stirrer for 10 min, place it in a bath for 30 min, and then
determine viscosity.
7. Remove the bottle from the constant-temperature bath
and stir the solution by hand for 10 sec, using a stirring
rod. Avoid shaking or vigorous stirring, as this will increase
air bubbles, which interfere with viscosity measurement.
8. Immediately insert the appropriate Brookfield viscometer
spindle into the solution and start the spindle rotating.
Allow it to rotate for 3 min before taking the reading.
9. Stop the instrument and read the dial. Multiply the dial
reading by the factor corresponding to the speed and
spindle used. The result is the viscosity of the solution
in centipoises.
C. Viscosity in Ethanol
The viscosity of ethanol solutions of KLUCEL is determined
in the same manner as for aqueous solutions, but with the
following modification:
1. To minimize evaporation of the ethanol, the bottle may be
capped and mechanically shaken to accomplish solution
of the KLUCEL instead of stirring the solution by hand.
2. Repeat steps 5, 6, 7, 8, and 9 as described in the Viscosity
in Water procedures.
D. Ash Content
The ash components of KLUCEL are sodium salts. Determination of these is complicated by the presence of certain
anticaking agents, which contribute to the total ash. The ash
method is referenced in the National Formulary, current edition.
Table XIII Sample Weights of KLUCEL, and Brookfield Spindle and Speed for Viscosity Measurement
Viscosity
Type
Concentration, %
rpm
E
L
J
G
M
H
10
5
5
2
2
1
Brookfield Settings
Sample Wt, g
Spindle No.
25.0
11.0
11.0
5.2
5.2
2.3
30
30
60
60
60
30
22
2
1
2
2
4
3
Chemical Identity
Manufacturer
Antifoam AF
Dimethylpolysiloxane materials
Aqualon CMC
Sodium carboxymethylcellulose
Hercules Incorporated
Benecel MC
Methylcellulose
Hercules Incorporated
Butyl Cellosolve
Carbowax 1000
Polyethylene glycol
Cellosolve
Colloid 581-B
Rhne-Poulenc, Inc.
Defoamer 1512
Silica-type defoamer
Hercules Incorporated
Methyl Cellosolve
M-Pyrol
N-methyl-2-pyrrolidone
GAF Corporation
Myvacet
Acetylated monoglyceride
Myverol
Monoglyceride
Natrosol HEC
Hydroxyethylcellulose
Hercules Incorporated
Nopco KFS
Proprietary blend of hydrocarbon oil, fatty acids, wax, and nonionic surfactants
Henkel Corporation
Nopco NDW
Proprietary blend of hydrocarbon oils, silicone, nonionic surfactants, and metallic soaps
Henkel Corporation
Omadine
Sodium 1-hydroxpyridine-2-thione
Olin Chemicals
23
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otherwise, (ii) the completeness, definitiveness, or adequacy of such information for users or other purposes, (iii) the quality of such products, except
that such products are of Hercules standard quality. Users are advised to make their own tests to determine the safety and suitability of each product
or product combination for their own purposes. Read and understand the Material Safety Data Sheets (MSDSs) before using these products.
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