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                                               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 Layer                   Hydrogel       Fabrics with Epidure
                                                   o Hydrophilicity
                                  High water       o Durability
                                                   o Softness
                                  content          o Hygroscopicity
                                  Neutral          o Antistaticity
                                                   o Soil guard
                                  Soft                property

                       Fiber      Antistatic       o Safety
6
        DURABILITY OF EPIDURE ON T/C AGAINST HOME LAUNDRY


          Textile: T/C
     Agent: Epidure -MF3
      Conc. of agent: 5%
                                     T/C(65/35) modified by Epidure-MF3
            Method
   Soak textile in the dilution
             ↓                               C1s Spectrum                       P2p Spectrum
          Pick-up: 80%
             ↓                           After 30 HL
                                                                                             After 30 HL
    Drying 100 , 2min
            ℃ (            )
             ↓                                                                                   Initial
     Curing 150 , 3min
            ℃ (            )                Initial
   Surface analysis of textile
X-ray photoelectron Spectroscopy           None-                                                None-
     ESCA3300 SHIMAZU
               、                          modified                                             modified
           P/C value
                                   300        295      290   285   280                                     390
                                                                                                           395
                                                                                                           400
                                                                                                           405
                                                                                                           410
                                             Binding Energy / eV                 Binding Energy / eV

                                     P/C value:                                 Eighty% of initial
                                     Initial     1.79×10-2                         Epidure has
                                     After 30 HL 1.51×10-2                    remained after 30 HL


                                   Epidure-MF has good durability against home laundry.
7
                                                 CYTOTOXICITY TEST FOR EPIDURE
Cytotoxicity test (Neutral 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.
              Cell living rate (%)




                                     120
                                                                                                        Epidure-MF3
                                     100                                                                Epidure-MF5

                                     80                                                                 Epidure-

                                     60                                                                 Ethano

                                     40                                                                 Detergen

                                     20                                                                 Shampoo

                                      0                                                                 SDS (surfactant)

                                      1000.0   100.0    10.0       1.0        1    01     001

                                                               Concentration (%)



                                                       Epidure-MF and CF have high biological safety.
8
                                   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


                                                                     MF3             MF5       CF72
                                                               1hr    24hr     1hr     24hr    1hr  24hr

             Negative     -   No reaction                          44     45     43      43    43    43
                         ±    Only redness                          1      0      0       0      0     0
             Positive    +    Redness, Infiltration, Small rash      0     0      0       0      0     0
                        ++     Redness, Infiltration, Rash, Blister 0      0      0       0      0     0
                        +++    Big blister                            0    0       0       0     0     0



2.   Results: All of Epidure were negative in this tests.


                                           Epidure-MF and CF have no irritation to human skin.
9
                                                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
of Test Solution II was less than that of Test Solution III.
                              Skin Irritation
                                  Score




                                                      Skin Irritation Score after 5 days
                                                5.2

                                                  2

                                                5.1

                                                  1

                                                5.0
                                                         Ⅰ              Ⅱ                Ⅲ
                                                  0
                                                             3FM         3FM+SDS               SDS


                                                               *SDS means sodium dodecyl sulfate.

                                                        Epidure-MF inhibits skin irritation based on SDS
10
                                              SKIN PROTECTION

Textile and Test method                                      Irritation
Textile: Cotton 100% and Cotton modified by 5% of                            90
Epidure-MF3                                                                                            retal ruoh 1;
Irritant: Sodium dodecyl sulfate (SDS)                                       80                            sruoh 42;
                                                                                                           sruoh 42;
                                                                                                           sruoh 42;
                                                                                                           sruoh 42;
①  Textiles 6 mm
           (       )φ    were put in the test
②  Ten micro litters of 0.1 0.5% aqueous SDS solution
                          ~                                                  70
were dropped on the textiles. The textiles were applied
                                                                             60
on the back of
   human (5 members).                                                        50
③   After 24 hours the textiles were taken off the back,
The redness was measured by naked eye one hour and                           40
24 hours later.
                                                                             30

                                                                             20
Evaluation: Redness was scored based on Japanese skin                        10
irritation evaluation.
★  Irritation index total score number of patients 100
                 =            /                     ×                        0
                                                             No irritation          % 0.3%
                                                                                  1.0        0.5   0.1% 0.3% 0.5%
Results                                                                           SDS SDS SDS SDS
                                                                                              SDS
                                                                                              SDS
                                                                                              SDS        SDS SDS
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                              Control     Textile modified by MF3
human skin from irritants.




                          The textile modified by Epidure protects human skin from irritants.
Fabrics treated with Epidure support natural healing of rough skin.
                      Wearing Time / Day                                        Wearing Time / Day
                                                           Damaged
              4        3       2        1       0                      4
                                                                       4
                                                                       4
                                                                       4        3
                                                                                3
                                                                                3
                                                                                3        2
                                                                                         2
                                                                                         2
                                                                                         2       1
                                                                                                 1
                                                                                                 1
                                                                                                 1     0
                                                                                                       0
                                                                                                       0
                                                                                                       0
                                                    0.0
                                                    0.0
                                                    0.0
                                                    0.0                                                    0.0
                                                                                                           0.0
                                                                                                           0.0
                                                                                                           0.0
                                                                                                       0.01
                                                                                                       0.01
                                                                                                       0.01
                                                                                                       0.01
                                                    0.5
                                                    0.5
                                                    0.5
                                                    0.5
                                                                                                       0.02       x
                                                    0.01
                                                    0.01
                                                    0.01
                                                                                                                 de
                                                                                                       0.03      In
                                                    0.51                                                         L
                                                                                                       0.04
                                                                                                                 W
                                                    0.02
                                                    0.02
                                                    0.02
                                                    0.02                                                         E
                                              WCKL Index                            t         noN
                                                                                    tnemtaert noN :    0.05
                                                                                                                 T
                           enalauqS :
                           enalauqS :
                           enalauqS :
                           enalauqS :
                               27FC
                                27FC
                               27FC                 0.52
                                                    0.52
                                                    0.52
                                                    0.52                              enalauqS :
                   100                                                      100            27FC        0
                                                                                                       0.06
                           -erudipE :
                           -erudipE :
                           -erudipE :
                           -erudipE :                                                 -erudipE :
                                                                                      -erudipE :
                                                                                      -erudipE :
                                                                                      -erudipE :
                  Normal                                                   Normal
                                                    0.03
                                                    0.03
                                                    0.03                                               0
                                                                                                       0.07
                                                           Recovered
                  Improvement of WCKL Index                                Improvement of TEWL Index
                              EPIDURE
     RECOVERY OF ROUGH SKIN BY WEARING OF FABRICS TREATED WITH
11
12
                                                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                    add SDS and
                            (NHEK)               Medium change       Epidure


                                                                                             Measurement of
                                                                                             Extra IL - 1α
                            48 h                24 h                24h




                                                                                                Inflammation
                                                SDS : 30µ g/l
                                                        µ
                     1600
                     1400
   IL - 1α (pg/ml)




                     1200
                     1000
                     800
                     600
                     400
                     200
                       0
                                   SDS           SDS+0.1% Epidure         SDS+0.5% Epidure        0.5% Epidure
13
          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
14
          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
15
                                                           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.




                                                     2.5
                            Water holding capacity




                                                      2
                               (relative value)




                                                     1.5
                                                                                       After washing
                                                                                       1 hour after washing with water
                                                      1

                                                     0.5

                                                      0
                                                           Hyaluronic acid   Epidure
16
                                                    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
17
EPIDURE-HM,                                                                                                                       PMB:
Homopolymer made from MPC monomer. NOF               has   two   types    of   40%   and     5%    aqueous   solution   (EPIDURE-HM-500).
INCI Name: F Polyphosphorylcholine Glycol Acrylate

EPIDURE-HM-500:
Copolymer     made     from    MPC     and      butylmethacrylate    of        hydrophobic        monomer;     5%       aqueous   solution
INCI Name: F Polyquaternium-51




                                               Chemical structure of EPIDURE-HM,HM-500




                                             Chemical structure of EPIDURE-PMB
18
                             QUALITY STANDARD

                             Standard
     Items     EPIDURE-                                     Testing method
                                 EPIDURE-PMB
                  HM
             Colorless liquid, scentless or a slight
Properties                                             Visual observation
             peculiar odor
Residue on                                             General testing method for
           43-48%            4-6%
drying                                                 JSCI
                                                       General testing method for
pH           4 -6
                                                       JSCI
                                                       General testing method for
                                                       JSCI
Viscosity    *500`3000cps **6`60cst
                                                       *: the 2nd method, **: the
                                                       1st method
Heavy                                                  General testing method for
             20ppm or less
metals                                                 JSCI, the 2nd method, 1g
                                                       General testing method for
As           2ppm or less                              JSCI, the 3rd method,
                                                       apparatus B, 1g
19
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
20
                                      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


                                      2.95

                                       2.9
                                MIU




                                      2.85


                                       2.8


                                      2.75

                                       2.7
                                             Healthy hair           Damaged hair          Epidure-A     Epidure-C


                                                            Figure 2. Friction coefficient of Hair
21
                                                       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

                                                 120


                                                 100
                           Tensile strength/gf




                                                 80

                                                 60


                                                 40


                                                 20

                                                  0
                                                         Healthy hair            Damaged hair         Epidure-A   Epidure-C


                                                                        Figure 3. Tensile Property of Hair
22
                                                      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

                                                3.5

                                                 3
                            static charge /kv




                                                2.5                                                                 Healthy hair
                                                                                                                    Damaged hair
                                                 2
                                                                                                                    Epidure-A
                                                1.5

                                                 1

                                                0.5

                                                 0
                                                      0   10    20     30     40      50    60       70   80   90
                                                                               Tim e/sec




                                                               Figure 4. Antistatic effect of Hair
23
                                                       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.
24
“EPIDURE-NR” and “EPIDURE-NA” have unique characteristics. They form nano scale
           lamella structures on an applied surface when they dry.


                    treatment




                                             drying
    Dispersion of
   Epidure-NR or                Skin, hair
    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                is    a   mixture   of   Butylene   Glycol   and   Glycerin
INCI names: Glycerin, Butylene Glycol, and Polyquaternium-61

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 60°C. While stirring water of 50 to 60°C, 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                                    fluorescence included



               Mix 30 mins at                   Mix 10 mins             Fluorescent probe
               at 50-60ºC                       at 50-60ºC



Epidure-NR
                                   Water

                                                                                  Water

1. Add Fluorescent probe        2. While stirring water of 50-60ºC       3. Inclusion of fluorescence
with to to Epidure-NR              add Epidure-NR with                      in Epidure-NR
                                   fluorescence included

                                                                 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           4. Observation under a microscope
                                                                        3.   Dry up




                          Epidure-NA with
                          fluorescent probe




     Non-treated                    Treated with fluorescent        Treated with Epidure-NR and
                                          probe only                      fluorescent probe




              100 gm                          100 gm                    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

                                                        Result
                    Item
                                          EPIDURE-NR         EPIDURE-NA
    Acute oral toxicity test               >2000mg/kg          >2000mg/kg
    Skin primary irritation test          Non-irritation      Non-irritation
    Human patch test                          negative           negative
                                      Table 1.

                            Item                               Result
    Acute oral toxicity test                                >2000mg/kg
    Mutagenicity test                                         negative
    Skin primary irritation test                            Non-irritation
    Continuous skin irritation test                         Non-irritation
    ocular irritation testing                                Very slight
    Skin sensitization testing                             Non-sensitization
    Human patch test                                          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.

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Epidure hydrogels protect and hydrate skin

  • 1.
  • 2. 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. 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. 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. 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 Layer Hydrogel Fabrics with Epidure o Hydrophilicity High water o Durability o Softness content o Hygroscopicity Neutral o Antistaticity o Soil guard Soft property Fiber Antistatic o Safety
  • 6. 6 DURABILITY OF EPIDURE ON T/C AGAINST HOME LAUNDRY Textile: T/C Agent: Epidure -MF3 Conc. of agent: 5% T/C(65/35) modified by Epidure-MF3 Method Soak textile in the dilution ↓ C1s Spectrum P2p Spectrum Pick-up: 80% ↓ After 30 HL After 30 HL Drying 100 , 2min ℃ ( ) ↓ Initial Curing 150 , 3min ℃ ( ) Initial Surface analysis of textile X-ray photoelectron Spectroscopy None- None- ESCA3300 SHIMAZU 、 modified modified P/C value 300 295 290 285 280 390 395 400 405 410 Binding Energy / eV Binding Energy / eV P/C value: Eighty% of initial Initial 1.79×10-2 Epidure has After 30 HL 1.51×10-2 remained after 30 HL Epidure-MF has good durability against home laundry.
  • 7. 7 CYTOTOXICITY TEST FOR EPIDURE Cytotoxicity test (Neutral 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. Cell living rate (%) 120 Epidure-MF3 100 Epidure-MF5 80 Epidure- 60 Ethano 40 Detergen 20 Shampoo 0 SDS (surfactant) 1000.0 100.0 10.0 1.0 1 01 001 Concentration (%) Epidure-MF and CF have high biological safety.
  • 8. 8 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 MF3 MF5 CF72 1hr 24hr 1hr 24hr 1hr 24hr Negative - No reaction 44 45 43 43 43 43 ± Only redness 1 0 0 0 0 0 Positive + Redness, Infiltration, Small rash 0 0 0 0 0 0 ++ Redness, Infiltration, Rash, Blister 0 0 0 0 0 0 +++ Big blister 0 0 0 0 0 0 2. Results: All of Epidure were negative in this tests. Epidure-MF and CF have no irritation to human skin.
  • 9. 9 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 of Test Solution II was less than that of Test Solution III. Skin Irritation Score Skin Irritation Score after 5 days 5.2 2 5.1 1 5.0 Ⅰ Ⅱ Ⅲ 0 3FM 3FM+SDS SDS *SDS means sodium dodecyl sulfate. Epidure-MF inhibits skin irritation based on SDS
  • 10. 10 SKIN PROTECTION Textile and Test method Irritation Textile: Cotton 100% and Cotton modified by 5% of 90 Epidure-MF3 retal ruoh 1; Irritant: Sodium dodecyl sulfate (SDS) 80 sruoh 42; sruoh 42; sruoh 42; sruoh 42; ① Textiles 6 mm ( )φ were put in the test ② Ten micro litters of 0.1 0.5% aqueous SDS solution ~ 70 were dropped on the textiles. The textiles were applied 60 on the back of human (5 members). 50 ③ After 24 hours the textiles were taken off the back, The redness was measured by naked eye one hour and 40 24 hours later. 30 20 Evaluation: Redness was scored based on Japanese skin 10 irritation evaluation. ★ Irritation index total score number of patients 100 = / × 0 No irritation % 0.3% 1.0 0.5 0.1% 0.3% 0.5% Results SDS SDS SDS SDS SDS SDS SDS SDS SDS 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 Control Textile modified by MF3 human skin from irritants. The textile modified by Epidure protects human skin from irritants.
  • 11. Fabrics treated with Epidure support natural healing of rough skin. Wearing Time / Day Wearing Time / Day Damaged 4 3 2 1 0 4 4 4 4 3 3 3 3 2 2 2 2 1 1 1 1 0 0 0 0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.01 0.01 0.01 0.01 0.5 0.5 0.5 0.5 0.02 x 0.01 0.01 0.01 de 0.03 In 0.51 L 0.04 W 0.02 0.02 0.02 0.02 E WCKL Index t noN tnemtaert noN : 0.05 T enalauqS : enalauqS : enalauqS : enalauqS : 27FC 27FC 27FC 0.52 0.52 0.52 0.52 enalauqS : 100 100 27FC 0 0.06 -erudipE : -erudipE : -erudipE : -erudipE : -erudipE : -erudipE : -erudipE : -erudipE : Normal Normal 0.03 0.03 0.03 0 0.07 Recovered Improvement of WCKL Index Improvement of TEWL Index EPIDURE RECOVERY OF ROUGH SKIN BY WEARING OF FABRICS TREATED WITH 11
  • 12. 12 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 add SDS and (NHEK) Medium change Epidure Measurement of Extra IL - 1α 48 h 24 h 24h Inflammation SDS : 30µ g/l µ 1600 1400 IL - 1α (pg/ml) 1200 1000 800 600 400 200 0 SDS SDS+0.1% Epidure SDS+0.5% Epidure 0.5% Epidure
  • 13. 13 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
  • 14. 14 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
  • 15. 15 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. 2.5 Water holding capacity 2 (relative value) 1.5 After washing 1 hour after washing with water 1 0.5 0 Hyaluronic acid Epidure
  • 16. 16 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
  • 17. 17 EPIDURE-HM, PMB: Homopolymer made from MPC monomer. NOF has two types of 40% and 5% aqueous solution (EPIDURE-HM-500). INCI Name: F Polyphosphorylcholine Glycol Acrylate EPIDURE-HM-500: Copolymer made from MPC and butylmethacrylate of hydrophobic monomer; 5% aqueous solution INCI Name: F Polyquaternium-51 Chemical structure of EPIDURE-HM,HM-500 Chemical structure of EPIDURE-PMB
  • 18. 18 QUALITY STANDARD Standard Items EPIDURE- Testing method EPIDURE-PMB HM Colorless liquid, scentless or a slight Properties Visual observation peculiar odor Residue on General testing method for 43-48% 4-6% drying JSCI General testing method for pH 4 -6 JSCI General testing method for JSCI Viscosity *500`3000cps **6`60cst *: the 2nd method, **: the 1st method Heavy General testing method for 20ppm or less metals JSCI, the 2nd method, 1g General testing method for As 2ppm or less JSCI, the 3rd method, apparatus B, 1g
  • 19. 19 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
  • 20. 20 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 2.95 2.9 MIU 2.85 2.8 2.75 2.7 Healthy hair Damaged hair Epidure-A Epidure-C Figure 2. Friction coefficient of Hair
  • 21. 21 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 140 120 100 Tensile strength/gf 80 60 40 20 0 Healthy hair Damaged hair Epidure-A Epidure-C Figure 3. Tensile Property of Hair
  • 22. 22 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 3.5 3 static charge /kv 2.5 Healthy hair Damaged hair 2 Epidure-A 1.5 1 0.5 0 0 10 20 30 40 50 60 70 80 90 Tim e/sec Figure 4. Antistatic effect of Hair
  • 23. 23 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.
  • 24. 24 “EPIDURE-NR” and “EPIDURE-NA” have unique characteristics. They form nano scale lamella structures on an applied surface when they dry. treatment drying Dispersion of Epidure-NR or Skin, hair Epidure-NA Skin, hair Lamella phase formation Figure 2
  • 25. 25 TRANSMISSION ELECTRON MICROSCOPIC OBSERVATION OF A CASTING FILM OF EPIDURE-NA SHOWS FORMATION OF LAMELLA STRUCTURE. Figure 3.
  • 26. 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 is a mixture of Butylene Glycol and Glycerin INCI names: Glycerin, Butylene Glycol, and Polyquaternium-61 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 60°C. While stirring water of 50 to 60°C, 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. 27 Epidure-NR with Fluorescence fluorescence included Mix 30 mins at Mix 10 mins Fluorescent probe at 50-60ºC at 50-60ºC Epidure-NR Water Water 1. Add Fluorescent probe 2. While stirring water of 50-60ºC 3. Inclusion of fluorescence with to to Epidure-NR add Epidure-NR with in Epidure-NR fluorescence included Figure 4
  • 28. 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 4. Observation under a microscope 3. Dry up Epidure-NA with fluorescent probe Non-treated Treated with fluorescent Treated with Epidure-NR and probe only fluorescent probe 100 gm 100 gm 100 gm Epidure-NR with active components remains on hair even after rinsing with water Figure 5.
  • 29. 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. 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 Result Item EPIDURE-NR EPIDURE-NA Acute oral toxicity test >2000mg/kg >2000mg/kg Skin primary irritation test Non-irritation Non-irritation Human patch test negative negative Table 1. Item Result Acute oral toxicity test >2000mg/kg Mutagenicity test negative Skin primary irritation test Non-irritation Continuous skin irritation test Non-irritation ocular irritation testing Very slight Skin sensitization testing Non-sensitization Human patch test negative
  • 31. 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.