Epidure

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

High water

content

Neutral

Soft

Antistatic

Hydrogel Layer

Fiber

� Fabrics with Epidure o Hydrophilicity o Durability o Softness o Hygroscopicity o Antistaticity o Soil guard

property o Safety

6

Textile: T/C Agent: Epidure -MF3

Conc. of agent: 5% Method

Soak textile in the dilution ↓ Pick-up: 80% ↓

Drying（100℃, 2min） ↓

Curing（150℃, 3min） Surface analysis of textile

X-ray photoelectron Spectroscopy

ESCA3300、SHIMAZU P/C value

DURABILITY OF EPIDURE ON T/C AGAINST HOME LAUNDRY

Epidure-MF has good durability against home laundry.

T/C（65/35） modified by Epidure-MF3

C1s Spectrum P2p Spectrum

390395400405410

After 30 HL

Initial

None-

modified

280285 290295 300

After 30 HL

Initial

None-

modified

Binding Energy / eV Binding Energy / eV

P/C value:

Initial 1.79×10-2

After 30 HL 1.51×10-2

Eighty% of initial

Epidure has

remained after 30 HL

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.

Epidure-MF and CF have high biological safety.

0204060

80

100

120

0.0001 0.001 0.01 0.1 1 10 100Concentration (%)

Cel

l li

vin

g r

ate (

%)

Epidure-MF3

Epidure-MF5

Epidure-

Ethano

Detergen

Shampoo

SDS (surfactant)

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

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

Epidure-MF and CF have no irritation to human skin.

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

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.

*SDS means sodium dodecyl sulfate.

Epidure-MF inhibits skin irritation based on SDS

MF3 SDS+MF3 SDS

Sk

in I

rrit

atio

n

Sco

re

00.511.522.5 Skin Irritation Score after 5 days

Ⅰ Ⅱ Ⅲ

10

SKIN PROTECTION

The textile modified by Epidure protects human skin from irritants.

0

10

20

30

40

50

60

70

80

90

0.10.10.10.1% SDSSDSSDSSDS 0.3% SSSSDSDSDSDS 0.5SDSSDSSDSSDS 0.1%SDSSDSSDSSDS 0.3%SDSSDSSDSSDS 0.5%SDSSDSSDSSDS

；；；；1 hour later1 hour later1 hour later1 hour later；；；；24 hours 24 hours 24 hours 24 hours

No irritation

Irritation Textile and Test method Textile: Cotton 100% and Cotton modified by 5% of Epidure-MF3 Irritant: Sodium dodecyl sulfate (SDS) ① Textiles （6 mmφ） were put in the test ②Ten 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). ③ After 24 hours the textiles were taken off the back,

The redness was measured by naked eye one hour and 24 hours later.

Evaluation: Redness was scored based on Japanese skin irritation evaluation. ★Irritation index＝total score／number of patients×100 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.

Control Textile modified by MF3

11

RECOVERY OF ROUGH SKIN BY WEARING OF FABRICS TREATED WITH

EPIDURE

Fabrics treated with Epidure support natural healing of rough skin. 0.00.00.00.010.010.010.010.020.020.020.020.030.030.030.030.040.040.040.040.050.050.050.050.060.060.060.060.070.070.070.070.0

0000 1111 2222 3333 4444 Wearing Time / Day

T

E

W

L

In

de

x

：：：： Non treatmentNon treatmentNon treatmentNon treatment：：：： SqualaneSqualaneSqualaneSqualane：：：： EpidureEpidureEpidureEpidure----CF72CF72CF72CF72

Normal

100

0.00.00.00.05.05.05.05.010.010.010.010.015.015.015.015.020.020.020.020.025.025.025.025.030.030.030.030.0

0000 1111 2222 3333 4444

WCKL Index

：：：： SqualaneSqualaneSqualaneSqualane ：：：： EpidureEpidureEpidureEpidure----CF72CF72CF72CF72

Normal

100

Damaged

Improvement of TEWL Index Improvement of WCKL Index

Wearing Time / Day

Recovered

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.

SDS : 30µµµµ g/l

0

200

400

600

800

1000

1200

1400

1600

SDS SDS+0.1% Epidure SDS+0.5% Epidure 0.5% Epidure

IL -

1αα αα

(p

g/m

l)

Cultured keratinocyte add SDS and

(NHEK) Medium change Epidure

Measurement of

Extra IL - 1α

48 h 24 h 24h

Inflammation

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

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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.

0

0.5

1

1.5

2

2.5

Wa

ter

ho

ldin

g c

ap

ac

ity

(re

lati

ve

va

lue

)

Hyaluronic acid Epidure

After washing

1 hour after washing with water

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

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QUALITY STANDARD

Items

Standard

Testing method EPIDURE-HM

EPIDURE-PMB

Properties Colorless liquid, scentless or a slight peculiar odor

Visual observation

Residue on drying

43-48% 4-6% General testing method for JSCI

pH 4 -6 General testing method for JSCI

Viscosity *500�`3000cps **6�`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

As 2ppm or less General testing method for JSCI, the 3rd method, apparatus B, 1g

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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

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

2.7

2.75

2.8

2.85

2.9

2.95

3

3.05

Healthy hair Damaged hair Epidure-A Epidure-C

MIU

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

0

20

40

60

80

100

120

140

Healthy hair Damaged hair Epidure-A Epidure-C

Ten

sile s

tren

gth

/gf

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

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0 10 20 30 40 50 60 70 80 90

Time/sec

sta

tic c

harg

e /kv

Healthy hair

Damaged hair

Epidure-A

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.

Lamella phase formation

Figure 2

Dispersion of Epidure-NR or

Epidure-NA

Skin, hair

treatmen

t

dry

ing

Skin, hair

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

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

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

Fluorescence Epidure-NR with

fluorescence included

Epidure-NR

Water

Water

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

100 gm 100 gm 100 gm

Figure 5.

Epidure-NA with fluorescent probe

Non-treated Treated with fluorescent

probe only

Treated with Epidure-NR and

fluorescent probe

Epidure-NR with active components remains on hair even after rinsing with water

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 Result

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

１１１１. Contents and Storage

Contents: 16 kg

Storage: Store in a dark and cool place.

２２２２. Caution for use

Check compatibility with other agents before using Epidure.

Do the laboratory test before using Epidure in the factory.

３３３３. 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.