2
SUMMARY Similar structure as the polar group of phospholipid in human cell membrane o Epidure-MF and CF contain polymers obtained from 2-methacryloyloxyethyl phosphorylcholine (MPC). MPC polymers are applied to coating agent for medical devices, moisturizer for cosmetics, contact lenses and soaking solution for contact lenses. We are now supplying new biocompatible and hydrophilic skincare agents for fibers, fabrics and textiles. Hydrogel formation o MPC polymers form hydrogels contacting with water on fibers surface. o The hydrogels has high hygroscopicity and durability against home laundry. Skin protection, antistatic o The textiles modified by Epidure-MF and CF protects any skin from any irritants. o The textiles support the self-healing ability repairing damaged skin. o Epidure-MF and CF work also as an antistatic agent and an SR agent. Safety o Epidure-MF and CF are formed with safety compounds. They have no skin irritation.
3
PROPERTIES OF EPIDURE-MF AND CF Epidure-MF3 o Properties: mild anionic o Effect: skin protection, soil release, antistatic, hygroscopic, water absorbing o For PET or T/C Epidure-MF5 o Properties: mild anionic o Effect: skin protection, soil release, antistatic, hygroscopic, water absorbing o For PET Epidure-CF72 o Properties: mild cationic o Effect: skin protection, antistatic, hygroscopic, water absorbing o For Nylon or Cotton
*Each product contains 10-25% ethanol to prevent the gel formation.
4
EPIDURE (MPC) EPIDURE is a water-soluble polymer derived from 2-methacryloyloxy ethyl phosphorylcholine (MPC). MPC is a compound, which has the similar structure as the polar group of phospholipid in cell membrance. Various materials can be obtained with using MPC.
MPC polymer can be useful for artificial organs with forming cell membrane-like structure on the surface. Blood coagulation test of MPC polymer :
5
PROPERTIES OF EPIDURE-MF AND CF BASED ON HYDROGEL Problem of existing hydrophilic agents o Less Hydrophilicity o Less Softness o Less Durability against home laundry MPC Polymers forms hydrogel on fibers.
Hydrogel
Hydrogel Layer
Fiber
High water content Neutral Soft Antistatic
Fabrics with Epidure o Hydrophilicity o Durability o Softness o Hygroscopicity o Antistaticity o Soil guard property o Safety
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DURABILITY OF EPIDURE ON T/C AGAINST HOME LAUNDRY
Textile: T/C Agent: Epidure -MF3 Conc. of agent: 5% Method Soak textile in the dilution
T/C（65/35） modified by Epidure-MF3
C1s Spectrum
↓ Pick-up: 80% ↓ Drying（100℃, 2min） ↓ Curing（150℃, 3min）
P2p Spectrum After 30 HL
After 30 HL
Initial
Initial
Surface analysis of textile X-ray photoelectron Spectroscopy ESCA3300 SHIMAZU P/C value
、
Nonemodified
Nonemodified
300
295
290
285
Binding Energy / eV
P/C value: Initial 1.79×10-2 After 30 HL 1.51×10-2
280
390 395 400 405 410
Binding Energy / eV
Eighty% of initial Epidure has remained after 30 HL
Epidure-MF has good durability against home laundry.
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CYTOTOXICITY TEST FOR EPIDURE
Cell living rate (%)
Cytotoxicity test ďźˆNeutral red assay) Subjects were added to SIRC cells from cornea of rabbit. The neutral red solution was added to the cells after incubation. The cell living rate was calculated from the data of UV absorption spectrum.
120
Epidure-MF3
100
Epidure-MF5
80
Epidure-
60
Ethano
40
Detergen Shampoo
20 0
0.0001
SDS (surfactant) 0.001
0.01
0.1
1
10
100
Concentration (%)
Epidure-MF and CF have high biological safety.
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SKIN IRRITATION TESTS FOR EPIDURE Patch test using human of Epidure-MF and CF: Test methods (This tests were done by dermatologist.) Subjects: Age:19 to 61, Male and Female, Members: 43～45 Test sample and amount: undiluted Epidure, 0.01ｇ Patch test: A fin chamber having 0.01g of sample was put on the upper parts of their arms for 24 hours. After 24 hours, the chamber was removed. Then the skin surface was observed by naked eyes one hour and 24 hours later. Evaluation: ICDRG standards
1hr － ± Positive ＋ ＋＋ ＋＋＋
Negative
2.
MF3 24hr
No reaction 44 Only redness 1 Redness, Infiltration, Small rash 0 Redness, Infiltration, Rash, Blister 0 Big blister 0
45 0 0 0 0
1hr
MF5 24hr
43 0 0 0 0
43 0 0 0 0
CF72 1hr 24hr 43 0 0 0 0
43 0 0 0 0
Results: All of Epidure were negative in this tests.
Epidure-MF and CF have no irritation to human skin.
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SKIN PROTECTION BY EPIDURE-MF Inhibition of skin irritation based on SDS by Epidure-MF3 Methods: Following test solutions were put on the skin of hairless mice twice a day. After five days, the skin was observed and the condition was scored. Test Solution I
: 1% Epidure-MF3Test Solution II : 7.5% SDS aqueous solution and 1% Epidure-MF3
Test Solution III : 7.5% SDS aqueous solution Results: No skin irritation was observed on Test Solution I. The skin irritation
Skin Irritation Score
of Test Solution II was less than that of Test Solution III.
Skin Irritation Score after 5 days 2.5 2 1.5 1 0.5 0
Ⅰ
Ⅱ MF3
SDS+MF3
Ⅲ SDS
*SDS means sodium dodecyl sulfate. Epidure-MF inhibits skin irritation based on SDS
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SKIN PROTECTION Textile and Test method Textile: Cotton 100% and Cotton modified by 5% of Epidure-MF3 Irritant: Sodium dodecyl sulfate (SDS) Textiles 6 mm were put in the test Ten micro litters of 0.1 0.5% aqueous SDS solution were dropped on the textiles. The textiles were applied on the back of human (5 members). After 24 hours the textiles were taken off the back, The redness was measured by naked eye one hour and 24 hours later.
① ②
（
φ）
Irritation 90
；1 hour later ；24 hours
80
～
70 60
③
50 40 30 20
Evaluation: Redness was scored based on Japanese skin irritation evaluation. Irritation index total score number of patients 100
★
＝
／
10
×
0 No irritation
Results In the cases of any concentration of SDS, textiles modified by Epidure show smaller irritation index than control textiles. The textile modified by Epidure protects human skin from irritants.
0.1% 0.3%
0.5
0.1% 0.3% 0.5%
SDS SDS SDS SDS
Control
SDS SDS
Textile modified by MF3
The textile modified by Epidure protects human skin from irritants.
T E W L In de x
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RECOVERY OF ROUGH SKIN BY WEARING OF FABRICS TREATED WITH EPIDURE Improvement of TEWL Index 70.0
Improvement of WCKL Index
Recovered ：
Normal 100
60.0
EpidureEpidureCF72 ： Squalane
50.0
： Non treatment
30.0 ： Epidure EpidureCF72 ： Squalane
25.0
Normal 100
WCKL Index 20.0
40.0
15.0
30.0 10.0
20.0
5.0
10.0 0.0
0
1
2
3
Wearing Time / Day
0.0
4
0
Damaged
1
2
3
4
Wearing Time / Day
Fabrics treated with Epidure support natural healing of rough skin.
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SUPPRESSING ROUGH SKIN FORMATION The experimental rough skin formation and suppression test was performed using the cultured keratinocyte. Applying a sodium dodecyl sulfate solution (SDS) for 24h caused Inflammation of IL-1 α such as rough skin, however these phenomena were prevented by applying EPIDURE simultaneously. Cultured keratinocyte (NHEK) Medium change
add SDS and Epidure
Measurement of Extra IL - 1α 48 h
24 h
24h
SDS : 30µ µ g/l
Inflammation
IL - 1α (pg/ml)
1600 1400 1200 1000 800 600 400 200 0 SDS
SDS+0.1% Epidure
SDS+0.5% Epidure
0.5% Epidure
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PROTECTION THE SURFACE OF CUTICLE FROM DAMAGE When shampooed hair was tied up, the surface of the cuticle was lifted. On the other hand, the surface of the cuticle whose hair was applied with EPIDURE was not lifted up. EPIDURE is effective for protecting hair, with developing smoothness.
(A) After shampoo
(B) Applying Epidure after shampoo
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PREVENTION OF THE CUTICLE SURFACE FROM DAMAGE Hair damaged by 10 times of bleaching and EPIDURE-C treated hair, which was prepared by soaking the damaged hair in 1% EPIDURE solution, were observed under SEM (Photographs 1 and 2). Lifting up of cuticle was prevented effectively by EPIDURE-C .
Picture 1. Damaged Hair
Picture 2. EPIDURE-C treated Hair
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WATER RETENTION CAPABILITY Though EPIDURE has a high hygroscopicity and moisture retention capability, the biggest difference compared with Hyaluronic acid is that the hygroscopicity and moisture retention capability are retained even after rinsing with water.
Water holding capacity (relative value)
2.5 2 1.5
After washing 1 hour after washing with water
1 0.5 0 Hyaluronic acid
Epidure
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SUSTAINABILITY EPIDURE is not easily removed from the surface of the skin. This was demonstrated that coating of EPIDURE labeled by fluorescence to the skin equivalent remained even 3 hours after rinsing with large amounts of PBS solution.
EPIDURE has been proven for safe with conducting following tests. 1. Acute toxicity test 2. Continuous skin irritation test 3. Phototoxicity test 4. Acute eye irritation test 5. Human patch test 6. Skin primary irritation test 7. Maximization sensitization test 8. Skin photosensitization test 9. Mutagenicity test
EPIDURE-HM, Homopolymer made from MPC monomer. NOF INCI Name: F Polyphosphorylcholine Glycol Acrylate EPIDURE-HM-500: Copolymer made from MPC INCI Name: F Polyquaternium-51
and
has
two
types
butylmethacrylate
of
of
40%
and
5%
hydrophobic
Chemical structure of EPIDURE-HM,HM-500
Chemical structure of EPIDURE-PMB
aqueous
solution
monomer;
5%
17 PMB: (EPIDURE-HM-500).
aqueous
solution
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QUALITY STANDARD Standard Items
Properties
EPIDUREHM
EPIDURE-PMB
Colorless liquid, scentless or a slight peculiar odor
Residue on 43-48% drying
4-6%
Testing method
Visual observation General testing method for JSCI
4 -6
General testing method for JSCI
Viscosity
*500Â `3000cps **6Â `60cst
General testing method for JSCI *: the 2nd method, **: the 1st method
Heavy metals
20ppm or less
General testing method for JSCI, the 2nd method, 1g
2ppm or less
General testing method for JSCI, the 3rd method, apparatus B, 1g
pH
As
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EPIDURE-A,C We introduce " EPIDURE-A " and " EPIDURE-C ", which are new products of the EPIDURE series and were developed for hair-care products. New EPIDURE can restore damaged hair (damage caused by repetitive bleaching etc.) into healthy hair by adhering to the hair fibers and moisturizing the hair since the EPIDURE polymers contain all cationic, anionic and hydrophobic monomers as shown in Figure 1. EIPIDURE-A
EIPIDURE-C
Figure 1. Chemical structures of EPIDURE-A and EPIDURE-C
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FRICTION COEFFICIENT OF HAIR Friction coefficients were measured using a friction tester KSE-SE (Kato Tech Co,ltd.) for healthy hair, hair damaged by 10 times of bleaching, and EPIDURE-A and -C treated hair, which was prepared by soaking the damaged hair in 1% solution of EPIDUREA or C (Figure 2). From the resultant friction coefficients, which show the smoothness of hair, EPIDURE-A and -C treatment was found to improve the smoothness up to that of the healthy hair.
Friction coefficient of hair 3.05 3
MIU
2.95 2.9 2.85 2.8 2.75 2.7 Healthy hair
Damaged hair
Epidure-A
Figure 2. Friction coefficient of Hair
Epidure-C
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TENSILE PROPERTY OF HAIR Tensile strength test of the test samples was conducted using the same treatment methods as in the friction test (Figure 3). The strength of damaged hair was recovered by EPIDURE-A and -C treatment
Tensile property of hair 140
Tensile strength/gf
120 100 80 60 40 20 0 Healthy hair
Damaged hair
Epidure-A
Figure 3. Tensile Property of Hair
Epidure-C
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ANTISTATIC EFFECT OF HAIR For healthy hair, hair damaged by 10 times of bleaching, and EPIDURE-A treated hair, which was prepared by soaking the damaged hair in 1% EPIDURE solution, the static charges of the hair specimens were measured using SIMCO electrostatic field meter after rubbing the specimens with PET film for 30 times; and we monitored decreases in static charge in the course of time. (Figure 4) EPIDURE-A treatment reduced the static charge of the hair, thus it is expected to prevent static flyaway of the hair.
Antistatic effect of hair 4.5 4
static charge /kv
3.5 3 Healthy hair
2.5
Damaged hair 2
Epidure-A
1.5 1 0.5 0 0
10
20
30
40
50
60
Tim e/sec
Figure 4. Antistatic effect of Hair
70
80
90
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PRODUCTS EPIDURE-A Copolymer made from MPC, sodium methacrylate (anionic monomer) and butyl methacrylate; 5% aqueous solution. INCI name: polyquaternium-65 EPIDURE-C Copolymer made form MPC and -2-hydroxv-3-methacryloyloxypropyltrimethylammnonium chloride (cationic monomer) ; 5% aqueous solution. INCI name: polyquaternium-64 EPIDURE-NR-NA NOF Corporation started the sales of “EPIDURE-NR” and “EPIDURE-NA”, which have new functions and concepts. Produced using EPIDURE-S (Fig.1) as the main ingredient, EPIDURE-NR is a solution of polymers in multivalent alcohol. EPIDURE-NA is dispersion of nano-particles of polymer (Ave. particle size: 50nm) in water.
Figure 1.
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“EPIDURE-NR” and “EPIDURE-NA” have unique characteristics. They form nano scale lamella structures on an applied surface when they dry.
Skin, hair
drying
treatment
Dispersion of Epidure-NR or Epidure-NA
Skin, hair Lamella phase formation
Figure 2
25
TRANSMISSION ELECTRON MICROSCOPIC OBSERVATION OF A CASTING FILM OF EPIDURE-NA SHOWS FORMATION OF LAMELLA STRUCTURE.
Figure 3.
26
The new products are effective cosmetic ingredients for skin care and hair care. They restore and protect healthy skin and hair.
EPIDURE-NR 5% EPIDURE-S solution in multivalent alcohol, which INCI names: Glycerin, Butylene Glycol, and Polyquaternium-61
is
a
mixture
of
Butylene
Glycol
and
Glycerin
Characteristics EPIDURE-NR: Encloses and reserves active components stably, Forms lamella structure on the skin surface and protects the skin, and Increases the penetration efficiency of active components. (Demonstration of Reserving effect) EPIDURE-NR can enclose oily active components such as Vitamins. The enclosed ingredients were confirmed to remain on the hair surface. Here, the model material used as an active component was florescent oil. Fluorescence was incorporated in EPIDURE-NR. Observations under a fluorescent microscope of damaged hair that was immersed into the EPIDURE-NR showed fluorescence.
Inclusion of the fluorescent probe (active components) into EPIDURE-NR. It dissolves into water by mixing for 30 min at 50 to 60째C. While stirring water of 50 to 60째C, just add EPIDURE-NR to which fluorescence is included. With this simple method, nano particles are formed. There is no need to use ultra high-presser homogenizer (ex. microfluidizer).
27 Epidure-NR with fluorescence included
Fluorescence
Mix 30 mins at at 50-60ยบC
Mix 10 mins at 50-60ยบC
Fluorescent probe
Epidure-NR
Water Water 1. Add Fluorescent probe with to to Epidure-NR
2. While stirring water of 50-60ยบC add Epidure-NR with fluorescence included
3. Inclusion of fluorescence in Epidure-NR
Figure 4
28 Microscopic photographs of: 1) non-treated damaged hair, 2) fluorescence dissolving in water from surfactant-treated hair, and 3) inclusion of fluorescence in EPIDURE-NR treated hair. 1. Immerse hair on Epidure-NA
2. Rinse off with water 3.
4. Observation under a microscope Dry up
Epidure-NA with fluorescent probe
Non-treated
100 gm
Treated with fluorescent probe only
100 gm
Treated with Epidure-NR and fluorescent probe
100 gm
Epidure-NR with active components remains on hair even after rinsing with water
Figure 5.
29 Only EPIDURE-NR treated hair showed strong fluorescence. This shows that EPIDURE-NR with active components remained on the hair even after the hair was rinsed with water. This is likely because the active component in EPIDURE-NR was included in the newly formed lamella structure on the hair. 2.EPIDURE-NA 1% EPIDURE-S water dispersion. EPIDURE-S is added to 9.5% Glycerin, 9.5% Butylene Glycol and 0.25% PCA Ethyl Cocoylarginate, which is a preservative. INCI names: Water, Glycerin, Butylene Glycol, Polyquaternium-61 and PCA Ethyl Cocoylarginate (Characteristics) EPIDURE-NA Repairs damaged hair by forming lamella structure on the hair, Makes the hair antistatic, and Protects the hair from discoloring. (Demonstration of the repair efficacy of damaged hair) We observed the wetting effect under a high power microscope. A drop of water on the surface of a healthy hair fiber Damaged hair by bleaching Damaged hair that was treated with hair care ingredient solutions (active conc. 0.05%)
Epidure-NA treated hair Figure 6.
30 Damaged hair showed decreases in contact angle with water from that of healthy hair. Because the lipid phase at the outermost surface on the hair fiber was damaged, the hair surface became hydrophilic. On the other hand, EPIDURE-NA treated hair showed high repellency similar to that of healthy hair. EPIDURE-NA restored the hair fiber to be hydrophobic again by forming a lamella structure on the hair. The damaged hair was restored into healthy hair. 3.Safety Safety of EPIDURE(R)-NR and EPIDURE(R)-NA Item Acute oral toxicity test Skin primary irritation test Human patch test
Item Acute oral toxicity test Mutagenicity test Skin primary irritation test Continuous skin irritation test ocular irritation testing Skin sensitization testing Human patch test
Result EPIDURE-NR EPIDURE-NA >2000mg/kg >2000mg/kg Non-irritation Non-irritation negative negative Table 1. Result >2000mg/kg negative Non-irritation Non-irritation Very slight Non-sensitization negative
31
METHODS FOR USE １.
Contents and Storage Contents: 16 kg Storage: Store in a dark and cool place.
２.
Caution for use Check compatibility with other agents before using Epidure. Do the laboratory test before using Epidure in the factory.
３.
Examples of use Padding （MF3、MF5）
Epidure conc.: 3-10% Pick –up: 70-100% Drying: 100℃, 2 min. Setting: more than 140℃, 2 min.
Soaking （CF72）
Epidure conc.: 3-10%owf Temp: 30-40℃ pH control: 4-7 Anionic water-soluble PET finishing agents in addition give the textile softness and durability.