Europaisches P a t e n t a m t ©

European Patent Office

© Publication number:

EUROPEAN

028

457

A2

Office europeen des brevets

©

0

PATENT

© Application number: 80303437.0 © Date of filing: 30.09.80

© Priority: 31.10.79 JP 139789/79 © Date of publication of application: 13.05.81 Bulletin 81/19 © Designated Contracting States: AT CH DE FR GB U

APPLICATION

© IntCI.3: A 61 B 01

K 7/48 F 17/00

© Applicant: KAO SOAP COMPANY LIMITED 1-1 Nihonbashi Kayaba-cho Chuo-ku Tokyo(JP) © Inventor: Tsutsumi, Hisao Ooaza Kokunou, No. 422-7 Miyashiro-machi Minamisaitama-gun Saitama-Ken(JP) @ Inventor: Hori, Kazumi 3-3-4, Honcho Koganei-shi Tokyo(JP) © Inventor: Kawano, Junichi 1-27-13 Nakashizu Sakura-shi Chiba-ken(JP) © Representative: Evans, David Charles et al, FJ. CLEVELAND & COMPANY 40-43, Chancery Lane London, WC2A UQ(GB)

© Cosmetic and emulsifier composition. A cosmetic composition comprising a cosmetic oil component, water and a specific emulsifier are disclosed. The specific emulsifier comprises a branched fatty acid cholesterol ester of the formula (I)

where R is a saturated aliphatic hydrocarbon group having a total of 11 to 23 carbon atoms and including at least one alkyl substituent group attached on the main chain inbetween the carboxyl-bonding position and the center of the main chain, and cholesterol; wherein said branched fatty acid cholesterol ester and said cholesterol are in a weight ratio of 90:10 to 10:90.

Field

of

Invention:

the

The p r e s e n t composition

relates

invention

and,

particularly,

to a novel

to

an emulsion

such

as creams

cosmetic cosmetic

type

composition. of

Description

are

Prior

Art:

Emulsion

type

cosmetics

classified

into

two t y p e s ,

namely

emulsion

wherein

an oil

component

type

is

material

oil

the

(W/0)

such

for

emulsifiers

accordingly On the a unique

(O/W)

cosmetic

base

an e m u l s i f i e r water

not

is

and

dispersed

bond

activity.

hand, with at

the

it

surface

systems,

active

to

acid

fatty acid

fatty

irritation

emulsion

agents

an o x y e t h y l e n e

a sorbitan

necessarily

other

such

ether,

sorbitan

cause

structure

and a double surface

of

lotions,

in w a t e r

the

as

wherein

non-ionic

alkyl

copolymer,

and a p o l y o x y e t h y l e n e these

an oil

use

stabilizing

used

been

polyoxyethylene block

pylene

or skin

component.

have mainly as

with

emulsion

type

As e m u l s i f i e r s there

in w a t e r

dispersed oil

in

a water in

the

the

ester,

ester. skin

oxypro-

However, and

they

are

satisfactory. is

known t h a t

a hydroxyl C-5 and

Cholesterol

is

group

cholesterol at

the

C-6 p o s i t i o n s , widely

having

C-3 p o s i t i o n exhibits

distributed

in

and,

nature in

all

almost

cholesterol to

the

keep

little

has

for

used

in

an a t t e m p t

for

cosmetics.

is

used

Publication

Patent

However,

have

derivatives

No.

most

amount

measures of

use

A need suitable ture

for

and give

and

the

a high

instance,

it

gives

outstanding it

cosmetics,

to

such

as

for

to

point-a-nd it

is

(Japanese

area

for

application to

which to

and

exist are the

normally

necessary

the

irritation

thus

cholesterol are

used,

cosmetics

the

1975).

are

continues

as

oxide

improve

cosmetics

of

is

derivatives

above m e n t i o n e d

melting

useful

ethylene

cholesterol

cholesterol

of

reformation

a technique

they

little

and

these

on the

when

in

Further,

an a c t i v i t y

a derivative

Accordingly,

therefore use

28501

of

room t e m p e r a t u r e .

special

obtain

an e m u l s i f i e r

as

of for

studies

oxide

the

and

it

cosmetics.

For

added

and

property

are

produced

to

an a l k y l e n e

oxide,

propylene

hydrophilic

at

been

wherein

reported or

recently

and

fat,

condition,

a material

of

distributed

processes.

Because

production

have

cholesterol a material

for

is

epithelial

property

a moist

skin.

suitable

the

There

in

it

body,

physiological

penetration

the

to

animal mention

to

in

surface

irritation

characteristics is

role

a mild

skin

the

not

systems

an i m p o r t a n t

plays

in

especially

in

to

some c a s e s ,

solid take the

is

restricted.

for

emulsifiers

liquid skin.

at

room

tempera-

SUMMARY OF THE INVENTION

an e m u l s i f i e r which

is

irritation

suitable at

liquid to

Another emulsifier

the

for

as

hereinafter

by p r o v i d i n g

object

of the

(I):

is

to

provide

cosmetic

compositions

and

little

invention

of g i v i n g

containing

of

gives

will

such

become

an e m u l s i f i e r fatty

acid

is

to

invention

provide

stable

an e x t r e m e l y

the

these objects

a branched

in

use

invention

skin.

A further object

Briefly,

the

room t e m p e r a t u r e

capable

compositions

of

one o b j e c t

Accordingly,

is

to

an

emulsion.

provide

cosmetic

an e m u l s i f i e r . and

more

other readily

objects

of

apparent

the can

invention be a t t a i n e d

comprising: cholesterol

ester

of the

formula

the

chain

center

of

having

group

least

at

including

main

on the and

position

carboxyl-bonding

and

atoms

attached

substituent

hydrocarbon

aliphatic

23 c a r b o n

of 11 to

a total alkyl

a saturated

R is

where,

inbetween main

the

one the

chain;

and cholesterol; wherein cholesterol

the

branched

in

are

acid

fatty

of

ratio

a weight

cholesterol 90:10

and

ester

10:90.

to

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The c h o l e s t e r o l is

invention

where,

R is

a total

a branched by the

represented

derivative

formula

a saturated

of 11 to

substituent

inbetween

the

carboxyl

group

the

in

cholesterol

present

ester

(I):

aliphatic

23 c a r b o n

one alkyl

acid

fatty

be used

to

atoms,

hydrocarbon and

attached

bonding

group

including on the

position

main

and the

at

having least

chain center

of

the

chain.

main

Such compounds,

fatty

and

may be p r e p a r e d

they

used

normally fatty

acid

or

fatty

acid

and

for

the

its

derivative

Preparation

of

Application

Serial

these

As a branched material

starting acid (11

to

having are

14 to

carbon ester

atoms thereby

property. carbon

is

the

the

before

in

Docket

(13

not

hand, the

product

having

fatty

have

if

branched

fatty

24 carbon

atoms

19 carbon

acid

the will

those in

atoms

R)

atoms

is

most

less

than

12

acid

cholesterol

a sufficient one having not

the

as

However,

18 carbon

the branched will

the

12 to

to

the

63-005-0),

be used

useful.

one having

other

property.

U.S.

copending

by r e f e r e n c e .

to

of

having

fatty

No.

herein

(RCOOH)

R) are

atoms

the

used,

esterification.

in

disclosed

production

those

obtained

is

is

acid

fatty

used,

be

them may f i r s t l y

incorporated

a branched

On the

atoms

hydrophilic

is

atoms

and

If

preferred.

of

for

directly

filed

20 carbon

preferred,

A branched

derivative

ester,

23 carbon

cholesterol.

(Attorney's

for

cholesterol

from a b r a n c h e d

No.

of which

novel

are

methods

by s t a n d a r d

may be r e a c t e d

compounds

herewith

concurrently

esters

of an e s t e r

and

or e i t h e r o n e

a reactive

to

disclosure

production

cholesterol

esterification, converted

cholesterol

acid

branched

have

oleophilic more

than

24

a sufficient

The b r a n c h e d attached

group the

main

on t h e

Such

fat chemical

the

the

acid

having

of

following

where,

each

of

atoms

the

of

center is

acid

industry

main

the

readily

the

or

and

oil

and

be p r e p a r e d ,

an aldol

condensation

unsaturated

aldehyde to

obtain

and

12.to

acid

instance,

chain aldehyde

a branched

fatty

and r e p r e s e n t e d

a-position

a straight

R2 is

fatty

branched

is

available

(II)

represented

for

acid

fatty

there

hydrocarbon,

R1 and

in

the

at

R2 is

R1 and

The b r a n c h e d

oxidation

inbetween

fatty

industry,

formula

aliphatic

@-position

alkyl

one

a position

a branched

such

chain

a side

by the

carbon

and

least

at

industry.

petrochemical

saturated

at

petrochemical

As an example from

chain

branched

a saturated

from

available

have

must

position

carboxyl-attaching

chain.

acid

fatty

and then thus

a side

above

7 to

a branched

chain

formula

of

to

at

the

(II)

may

a straight

10 carbon

subjecting

obtained

number

18.

by s u b j e c t i n g

having

chain

branched total

the

having

by the

or

the

atoms

fatty

to

a-branched

hydrogenation

saturated

or

acid.

and

Preferred acid

fatty

a side

having

and

acid,

available

from

industry,

there

Such for

is

total

about m

tered

and

is

by the

as

referred

(U.S.

Emery

and

having

formula

the

chain

fatty

acid

fatty

chemical

fat

branched

a methyl

14., and

a by-product

to

acid".

for

2-heptyl

acid.

oil

following

branched

J.

acid (e.g.

sold,

acid,

5,7,7-

(III):

distribution

is

cen-

= n = 7.

a methyl

isostearic

acid

a fatty

are

a-position,

branched

of the

of m + n is

instance,

of o l e i c

the

of a s a t u r a t e d

the m a t e r i a l

represented

where the

at

decanoic

2-hexyl

As an example

chain

chain

branched

saturated

(1,3,3-trimethylbutyl)-octanoic

trimethyl-2undecanoic

of the

representatives

Amer.

in

this

in Oil

the

Industry

in

the

Chem.

specification

Inc.

form of etc).

is

production

The m e t h y l b r a n c h e d

instance,

acid

its

Soc., as

obtainable; of a d i m e r

51,522 "methyl

(1974)) branched

isostearic

acid

isopropyl

ester

is

The c h o l e s t e r o l not

restricted

may be e x t r a c t e d stances, the

for

this

be used

30 to

20 :

As the

such

carnauba

oil

a plant a. higher

oil.

If

lanolin,

alcohol,

cholesterol above.

to

90 :

lanolin. the

10 :

In

amount

cholesterol

10 to

acid

hydrous oil, fatty

and a

containing

as the

be added

oil

there

paraffin,

a natural

a higher

fatty

used

liquid

olive

a substance is

of

Further,

invention

present

acid

component,

wax,

such as

a higher

fatty

ratio

oil

as

or s q u a l a n e ;

whale wax,

the

sub-

is

ester

90,

to

a n d

preferably

80.

cosmetic

a hydrocarbon ceresine

branched

in

it

by a

hydrous

content.

be used

a weight

as

cholesterol

to

in

be s u b s t i t u t e d

such

but

or marrow.

calculate

The e m u l s i f i e r the

brain

is

method,

natural

from

to

the

of

particular

cow's

necessary

of

cholesterol

from

is

basis

on the

a combination

70 :

it

invention

present

refined

cholesterol,

however,

the

or w h o l l y

may p a r t l y

containing

case,

and

dried

from

instance,

in

by any

prepared

or e x t r a c t e d

cholesterol

substance

that

to

be used

to

vaseline,

wax such

as

lanolin, camellia acid-, higher

may be m e n t i o n e d

may be r e d u c e d

bees'

wax, oil;

or j o j o b a oil,

or

various alcohol,

cholesterol,

component,

paraffin,

cotton esters

oil; obtainable

and s i l i c o n e such

the

amount

or

omitted,

as

hydrous

of t h e as m e n t i o n e d

The c o s m e t i c

by a usual

be p r e p a r e d

0.5

preferably the

mixing

preferably and

are

glycol,

possible

used

to

improve

vinyl

retaining

1,3-butylene

a viscosity

increasing

ethyl

cellulose, or

the

obtained and

choles--

oil

component,

90% by w e i g h t ,

to the

quality

e.g.

gum;

such

propylene

pyrrolidonecarboxylate;

polyvinylalcohol,

cellulose,

methyl

carboxy

polyvinylpyrrolidone,

cellulose,

gelatin,

an a n t i s e p t i c

agent

e.g.

ethyl

parahydroxybenzoate,

propyl

parahydroxybenzoate,

butyl

parahydroxybenzoate,

benzoate,

phenoxyethanol;

or

various

benzoic medicinal

and p e r f u m e s .

agents,

Further, active

surface

conventional agent

a polyoxyethylene fatty

or

which

of cosmetics,

parahydroxybenzoate,

sodium

of

components

glycerin,

e.g.

methyl

tragacanth

add v a r i o u s

methyl

acid,

by

90% by w e i g h t ,

to

cosmetic

20 to

sodium

agent

carboxy

carrageenan,

of

agent,

glycol,

polymer,

hydroxy

30% by w e i g h t ,

ester

0.1

may

emulsified.

is

as a m o i s t u r e

to

cholesterol

preferably

it

Further, normally

and

0.1

of an e m u l s i f i e r

50% by w e i g h t ,

mixed

invention

present

proportions,

predetermined

1 to

the

in which

acid

fatty

1 to 99% by w e i g h t ,

water,

are

method

5% by w e i g h t ,

to

branched

in the

terol

of

composition

acid

sucrose

ester,

fatty

acid

e.g.

fatty

emulsifiers

a polyoxyethylene acid

ester,

a polyoxyethylene ester,

such

a glycerin

as alkyl

a non-ionic ether,

a polyoxyethylene hydrogenated fatty

acid

sorbitan

castor ester,

oil, a

a

sorbitan

ester, acid

the

to

in

Furthermore,

sulfate, or

acid

such

chloride,

of

In the prepared, of

the

it

the case

agent

phoric

acid

are

present

present where

of

sulfate

the

effectiveness

useful

salt

metal

nitrate

of a f a t t y

distearate

stabilizing

the

with

together

or

W/0 t y p e

the

invention. cosmetic

and p r e f e r a b l e with

as

alkyl

ester

or

an a l k a l i

as

to

lecithin

sulfuric

composition is

as m a g n e s i u m sodium

aluminum

be used

such

invention

such

sulfate,

for

cosmetic

a W/O type

salt

multi-valent

a 0/W type

invention

The g e n e r a l the

impair

aluminum

and a

useful

is

present

active

to

an i n o r g a n i c

and may p r e f e r a b l y

emulsifier

agent

sulfate

alkyl

aluminum m o n o s t e a r a t e ,

as

active

phosphate

preparation

sulfate,

calcium monostearate, emulsion,

the

lecithin,

potassium

calcium

an a l k y l

alkyl

not

an e x t e n t

surface

invention.

present

composition,

ester,

a polyoxyethylene

or

be used

may also

acid

anionic

an

a polyoxyethylene

a soap, ester

and

ester;

phosphoric

an a l k y l

e.g.

of

acid

fatty

metal of

the

follows:

composition

combine

or an

acid salt

anionic

ester, of

cosmetic

the

alkyl

a fatty

is

emulsifier surface phosacid.

composition

of

The c o s m e t i c an emulsion from d r y i n g , prevent

milky

of a v a n i s h i n g

or

Having

generally

only

and are

composition

adapted

to

from

outside

for

a hair

may be i n

a cleansing

cream,

a cold

cream,

skin

skin

the

it

instance,

a hand

cream,

the

irritation,

and to m a i n t a i n

skin,

keep

is

a

cream,

a lotion.

not

intended

certain

to

of

for purposes

be l i m i t i n g

to

a further

invention,

by r e f e r e n c e herein

provided

are

this

described

be o b t a i n e d

can

which

examples

invention

cream,

lotion

understanding

present

any form,

a foundation

cream,

the

of

roughening

form

the

skin

the

protect

and may take

fresh, the

cosmetic

type

of

composition

unless

specific

illustration

otherwise

specified. Preparatory

Example

Into with

a reactor

a thermometer,

a stirrer

means,

Chemical

a reflux

Industries nitrogen

chloride

added

were

As the

temperature.

from time,

the

colourless, gas

condenser,

568 g (2.0

and s u p p l y i n g

proceeded,

a capacity

having

gas,

dropwise

reaction light

generation

from

addition

mixture yellow

was

the

observed.

acid

dark

fed.

of

at

room

chloride

a colour and at the

stirring

thionyl-

thionyl

brown,

During

made by

funnel

dropping

(5,7,7-

While of

and

funnel,

acid,

moles)

underwent to

and e q u i p p e d

a dropping

were

286 g (2.4

dropwise

2 liters

octanoic

Ltd.)

Co;,

of

isostearic

moles)of

(1,3,3-trimethylbutyl)

trimethyl-2Nissan

1

change the same

dropwise

the

addition

of

reaction

mixture

was m a i n t a i n e d

the

dropwise

addition

the

reaction

mixture

3 hours more

by an oil

under

removed

tillate

This

yield).

After

was

trimethyllbutyl)

held

at

and

about

60 to

70°C

that

there

substances

point

carried

was

for

confirming

pressure,

of

the After

room t e m p e r a t u r e .

low b o i l i n g

pressure

temperature

chloride

was f u r t h e r

bath.

112 to

at

at

thionyl

a reduced

a reduced

under

of

of gas,

generation

the

chloride,

thionyl

3 hours, for

about

was

no

were

a distillation

then

588 g of

out.

120°C/0.1

to

0.3

confirmed

to

be 5 , 7 , 7 - t r i m e t h y l - 2 - ( 1 , 3 , 3 -

octanoi.c

mmHg was

obtained

a dis(97%

chloride.

IR s p e c t r u m

(liquid

film

2970,

2920,

2875,

1795

1480,

1390,

1370,

1260,

method) (C = 0 s t r e t c h i n g 995,

1210,

930,

vibration), 790,

710,

600 cm-1

H1 -NMR spectrum 0.9

(s,

1.1

to

2.5

(m,

Preparatory Into with 571

the

24H, 2.0

δ

CN3-) 10H,

(m,

1H,

Example a reactor

same devices

g (2.0

(CC14 s o l v e n t ) :

moles)

2

having as

a capacity

employed

ofisostearic

in

acid

of

2 liters

Preparatory (2-heptyl

and

equipped

Example undecanoic

1,

acid

Chemical

by M i t s u b i s h i

made

and w h i l e

stirring and

supplying

chloride

moles)

of

thionyl

funnel

at

room t e m p e r a t u r e .

chloride colour the of

change

dropwise the

After

the

the

of

removed

of

under-a

lower

145 to

at This

point

pressure, was

that

151°C/0.25

was c o n f i r m e d

to

1.

to

same

During

temperature

room

temperature. for at

there

about

60 to

was

substances

out,

the

thionyl

the

and then

carried

dropping

of

addition

held

was f u r t h e r

the

from

chloride

thionyl

boiling

286 g ( 2 . 4

Example

at

fed,

were

underwent

chloride,

confirming

pressure

a distillate

(91% y i e l d ) .

mixture

reduced

a reduced

dropwise

was m a i n t a i n e d

After

gas,

dropwise

Preparatory

of

Ltd.) gas,

mixture

thionyl

addition

3 hours.

generation

As the

in

of

reaction

added

reaction

mixture

dropwise

about

under

addition

nitrogen

were

observed

as

reaction

3 hours, for

the

proceeded,

Industries

70°C

no m o r e

were

a distillation whereupon

0.3

549 g

mmHg were

be 2 - h e p t y l

obtained

undecanoic

chloride. IR s p e c t r u m

film)

(liquid

2960,

2925,

2850,

1460,

1380,

900,

1790 830,

H1 -NMR (CC14 s o l v e n t ) : 0.83 1.0 2.65

(t, to

6H, 2.0

(m,

720, δ

CH3CH2-)

(m,

1H,

(C

28H,

-CH2-)

CHCOCl)

= 0 stretching 700,

600 cm-1

vibration),

With equipped

the

about

lower

acid

in

Preparatory

boiling

230 g of a low b o i l i n g

(75% y i e l d ) .

was

pressure

carried

at

153

to

This

was

confirmed

and b e i n g

by the

formula

1.

which

170°C/1.0 to

to 3.0

and

considered a distillation 454 g

whereupon mmHg were

be methyl

in

the

removed

was

Then,

(III))

chloride After

were

out,

and

875

(Emery

thionyl

recovered.

3 liters

Inc.

Example

material

chloride, were

a reduced

of

substances

point

acid

Industry

moles)

of

in P r e p a r a t o r y

isostearic

represented

520 g (4.4

as

a capacity employed

as

of

moles)

fatty

with

of a d i s t i l l a t e

stearic

devices

same

branched

be t h i o n y l

under

having

made by US Emery

same manner

reaction,

to

the

acid

reacted

were

a reactor

569 g (2.0

isostearic a methyl

of

use

with 1,

Example

3

Example

Preparatory

obtained

branched

iso-

chloride. IR s p e c t r u m

film method)

(liquid

2950,

2920,

2850,

1800

(C

1460,

1400,

1380,

950,

720,

H1 -NMR spectrum

(CCl4):

δ

0.6

to

1.0

(m,

CH3CH2- and

1.0

to

1.5

(m,

-CH2-)

= 0 stretching 680,

590

cm-1

vibration),

1.5

2.77

Into

and

added

nitrogen oil

4

a stirrer

in

gas, and

bath,

this

order.

the

reaction

212 g (0.70

then

Example

funnel

at

After

the

mixture

5 hours.

about this of

the

acid

by f i l t r a t i o n , reduced

190 to

200°C

50°C

3 hours.

the

heated

60 to

IR s p e c t r u m that

in

of

there

White

80°C and the

still

removing

the

filtrate

of 0.5 about

to

thus 0.7

5 hours.

were

a small of

removed a

heated

a temperature

this

at amount

under

obtained was

After

for

product

consisting

solvent

mmHg at

reaction

stirred

remained

precipitates

dropping

the

reaction

and a f t e r the

about

addition,

dropwise at

in

product

for

by

about

reaction

pressure

obtained

of

the

pressure,

a reduced

5,7,7-trimethyl

the

chloride.

chloride

pyridine

50°C by an

dropwise from

indicated

stage

to

added

of

The

pyridine

1 were

completion further

of

chloride

octanoic

a temperature

was

mole)

choles-

and s u p p l y i n g

heated

was

of

of

mole)

stirring

mixture

a reflux

mole)

g (0.73

65 g (0.82

and

While

2-(1,3,3-trimethylbutyl) Preparatory

281

and

3 liters funnel,

a dropping

means,

benzene

of

a capacity

having

a thermomether,

1100 m l o f

terol,

.

-CH2COCl)

a reactor

with

condenser

were

(t,

(m,

Example

Preparatory

equipped

2.0

to

treatment,

under of the

showed

IR s p e c t r u m

mixed with

benzene

acid

ml)

(1000

The benzene

upon

octanoic light

layer

465 g of acid

yellow,

(1000

and

benzene

the

the

The p r o d u c t

completely.

and

that

acid

obtained

m l)

and a d i l u t e d

dried

the

sodium

under

vigorously

hydrochloric layer

was

sulfate

a reduced

5,7,7-trimethyl-2cholesterol

then

was

benzene

with

removed

was

had d i s a p p e a r e d

thus

thereafter was

chloride

anhydride

ester

were

obtained

as

a viscous,

(96% y i e l d ) .

liquid

(liquid film

2950,

2900,

2870,

1720

1470,

1380,

1360,

1240,

H1 -NMR s p e c t r u m

method) (C = 0 s t r e t c h i n g 1220,

(CC14 s o l v e n t ) :

1160,

vibration),

1030,

(s,

3H,

steroid

structure

C-18 methyl

0.85

(d,

6H,

steroid

structure

side

chain

chain

methyl

4.40

to

24H, 2.5

(m,

group) C-26,

C-27

group)

methyl

1.0

1010 cm-1

δ

0.65

(s,

where-

pressure,

(1,3,3-trimethylbutyl)

IR s p e c t r u m

0.87

separated.

fatty

acid

side

group)

(m)

1H,

)

5.25

(m,

1H,

steroid

structure

C-6

olefin

proton)

Into

the

271

4,

Example

and

benzene, in

a reactor

with

equipped

this

212 g (0.70

While

the in

reaction

the

at

this

of

the

the to

addition

2 hours,

the

reaction

mixture

showed

stage acid

reaction

mixture

by means

of

acid liquid

the

cholesterol having

was

there

still

Preparatory

in

the

were

a low visc

Example

to

was 4 and

contain

obtained

sity

as

acid at

60 t o

a light

amount

treated then

no acid

(94% y i e l d ) .

chloride

a small

whereupon

456 g of 2 - h e p t y l

IR s p e c t r u m . ester

mixture

After

30°C.

IR s p e c t r u m

remained

same manner,

confirmed

held

The

the

temperature

25 to

was

gas,

obtained

from

of the

bath.

The r e a c t i o n

in

treatment

an oil

that

chloride.

same m a n n e r a s a heat

in

nitrogen

the at

dropwise

introduced

chloride

operation,

the

6 hours

were

dropwise

was m a i n t a i n e d

Preparatory 1500 mR. o f

supplying

of

about

80°C for

and

added

this

mixture

completion about

2 were

During

pyridine

undecanoic

2-heptyl

Example

funnel.

of

mole)

stirring

of

mole)

in

employed

as

of c h o l e s t e r o l ,

mole)

65 g (0.82

by P r e p a r a t o r y

of

same d e v i c e s

and

of 3 l i t e r s

a capacity

having

g (0.70

order.

dropping

5

Example

Preparatory

in

subjected

the chloride

undecanoic yellow

IR s p e c t r u m

film):

(Liquid

2950,

2930,

2850,

1730 (C

1465,

1380,

1365,

1260,

H1 -NMR s p e c t r u m

= 0 stretching

1160,

vibration),

cm-1

1050

(CC14 s o l v e n t ) : δ

0.68

(s,

3H,

steroid

structure

C-18 m e t h y l . g r o u p )

0.80

(d,

6H,

steroid

structure

side

methyl

group) structure

C-19 methyl

1.00 0.8

3H, steroid

(s,

1.1

to

(m,

6H,

branched

fatty

chain

acid

C-26,

C-27

group)

side

chain

CH3CH22.4

1.1

to

4.4

(m,

5.25

(m,

(m)

1H,

1H,

)

steroid

structure

C-6 o l e f i n

proton)

Into

a reactor

with

equipped

the

281

Example

4,

benzene

and

in

order.

this

25 to of

6

Example

Preparatory

having

While

branched

methyl

of p y r i d i n e

stirring,

keeping

funnel.

After

reaction

mixture held

further

at

the

confirmed

in

by the

no acid

the

were

branched

obtained

as

as

a viscous,

mole)

obtained from

the

dropping

By t h i s

the

in P r e p a r a t o r y

light

heat

completely, reaction mixture

The r e a c t i o n

acid

the

and was

3 hours

that

by

addition,

proceeded

isostearic

at

temperature

8 hours.

IR spectrum

chloride.

introduced

dropwise

reaction

same manner

and 460 g of methyl ester

about

esterification

contained

1500 ml o f

the

dropwise the

Preparatory

were

chloride

50°C for

at

80°C for

70 to

and

treated

heated

was

the

mixture

added

and

212 g (0.70

gas,

isostearic

completion of

treatment, it was

nitrogen

3 were

Example

in

employed

mole)

30°C and s u p p l y i n g

the

as

of c h o l e s t e r o l ,

mole)

g (0.73

100 g (1.27

Preparatory

was

devices

same

3 liters

of

a capacity

Example

4

cholesterol

yellow

liquid

(94%

yield). IR s p e c t r u m

(liquid

film):

2950,

2920, 2850,

1730

( C =0

1460,

1370,

1000

cm-1

1160,

stretching

vibration),

H1 -NMR s p e c t r u m

(CC14 s o l v e n t ) :

δ

0.70

(s,

3H,

steroid

structure

C-18 methyl

0.80

(d,

6H,

steroid

structure

side

structure

C-19 methyl

methyl 1.00

(s,

0.80

to

2.0

2.2

(t,

2H,

4.4

(m,

1H,

5.25

steroid

1.0

to

(m,

C-26,

C-27

group)

3H,

1.0

chain

group)

(m,

6H,

branched

fatty

acid

group)

CH3CH2- a n d

(m)

1H,

-CH2-CH2-C00-)

steroid

structure

C-6 o l e f i n

proton)

1

Example

tests

Emulsion

the

of

emulsifiers

wherein

products,

the

emulsifying conducted

tests

0.3

composition

the

heated

vaseline,

The m i x t u r e

added,

mixture.

In t h i s

water

at

the

added

the

to each

while

and

initial

were

in

following

in

tested,

accordance

The r e s u l t s

are

and

with

shown

there

point,

of added was

occurs, the

the

was the

W/0 cream was the

amount

appeared water,

emulsifying

1.

g of

mixture.

water

determined

following

in Table

9.7

to

emulsifying

However, when

a certain

manner:

a homogeneous

a homogeneous

stage.

separation

was added

thereby

The maximum amount (g) phase

the

ion-exchanged

stirring,

compared.

powers

obtain

to

of t h e

use

and c o m p a r a t i v e

be t e s t e d

operation,

composition

calculated

cooled

exceeded

separation. which

to

and s t i r r e d then

was

gradually

formed

were

with

invention

present

The e m u l s i o n g of

conducted

were

of

a phase

beyond with

respect

power was

formula:

above

From the emulsifying branched with

acid

cholesterol,

of each used

for

the

to

following

fixed

back

(I)

power

which

was

and

the

skin.

The

cut

be t e s t e d

hair

of each of

immediately

guinea

pigs

once

and 24 hours the

it

every after

following

is

for

a day

before

in

to

the

left

four

cut

at

prior

to

of

skin,

a healthy of t h e

skin

exposed

of a disc is.

This

Evaluation

days.

final

standards:

it

in

hair

amount

the

the

investigate

7 hours

shape as

application the

were

having

A proper

pig,

2 cm, and

pigs

cutter

applied

was

to

in

conducted

were

guinea

guinea

be used

products

tests

White

manner:

to

repeated

of

comparative

the

to

respect

to

esters

on a f i x i n g - b o a r d .

a diameter

basis

cholesterol

12 h a i r

tests.

tested

acid

by an e l e c t r i c a l

backs

substance

was

formula

lanolin

out with

carried

were

invention

irritation

the

the

emulsifying

hydrous

or

the

purpose.

tests

fatty

present

were

the

the

by combining

of

ester

that

apparent

2

branched

the

is

improved

with

compared

component

same

Animal

their

remarkably

as

it

results,

cholesterol

individual

Example

the

is

power

fatty

test

the

having operation was made

substance

application

on

on t h e

to be

(Whether

not t h e r e

or

The

added

up for

of

each

point

The r e s u l t s

and edema were

appearance

erythema

independently

edema)

appears

other,

and

both

evaluations

evaluations. are shown

in

Table

evaluated

2 .

were

confirmed

It was branched

the

that

acid

fatty

they

are

results

cholesterol

do not

invention,

present

by the

these

esters

irritate

useful

extremely

of

the

to

skin

tests

that

be used

in

and

an e m u l s i f i e r

as

the

for

cosmetics. 3

Example

An O/W e m u l s i f i c a t i o n of the

use tive

to

be

tested,

heated

to

70°C and

room t e m p e r a t u r e ,

kept

and

the

stirred.

the

state

immediately

separation

state

one day

Emulsified

Separation

as

oil, 2 of

was the

compara-

conducted of

parts

cooling in

emulsion

after

after.

and

its

the

a test

in

the

the

com-

water

ion-exchanged

put

with

investigated

were

After

emulsion

to

were

tests

53 p a r t s

of

was

invention

of o l i v e

The e v a l u a t i o n

evaluation

oil

present

25°C.

at

respect the

the

45 p a r t s

manner:

position were

of

olive

The e m u l s i f i c a t i o n

products.

following

to

emulsifiers

of

mixture tube

and

was made w i t h

preparation

The s t a n d a r d s

for

and the

follows:

states

states

A:

homogeneous

B:

coarse

C:

immediately separated l e f t to stand s t i l l ,

-:

no s e p a r a t i o n

+:

coagulated observed

O/W e m u l s i o n emulsion

particle

upon

being

observed

phase

by c r e a m i n g

++:

+++:

The r e s u l t s a r e

shown

c o a g u l a t e d phase phase o b s e r v e d s e p a r a t i o n into an oil p h a s e in Table

3.

and

coalesced

a water

phase

and

From the combination and

of

results the

cholesterol

emulsifying tional

according

and

Cream

acid

the

present

to

other

is

it

tests.,

fatty

to

superior

power

4 Skin

these

branched

emulsifier

Example

of

apparent that

cholesterol

ester exhibits

invention,

combinations

a

of a c o n v e n -

cholesterol. (W/O t y p e )

(Composition)

(Method

for

preparation) 1 to

Components Components mixture

7 to

9 were

was added

emulsified. a homogeneous

6 were

After

to

heated

the

and heated

and mixed

mixture

cooling,

emulsion.

mixed

at

75°C,

of components

conponent

to 7 0 ° C . and 1 to

10 was added

this 6 and

to

obtain

an

The s k i n a luster,

stable

being

feeling

a good

compatibility

thus

cream

was

a long

period

the

skin

the

to

application

upon to

for

obtained

without

a W/O type of

skin

giving

cream and

time, with

having

giving

a good

a sticky

or o i l y

feeling. 5 Milky

Example

lotion

(O/W t y p e )

(Composition)

(Method

for

preparation)

Components 6 and

Components mixture

was

1 to

7 were

added

stirring,

thereby

cooling,

component

emulsion.

5 were heated

to

the

heated

mixture

emulsifying 8 was

to

added

the to

to 75°C and m i x e d . 75°C and mixed,

of

components

combined obtain

and

1 to

mixture.

this

5 while After

a homogeneous

fine

having and skin

giving without

giving

6 Cleansing

Example

with

feeling

a sticky Cream

an 0/W type

was

stable

being

texture, a good

obtained

thus

The e m u l s i o n

for

or o i l y

of

time,

compatibility

to

the

feeling.

(W/0 t y p e )

(Composition)

(Method

for

preparation)

Components Components

7 to

1 to

6 were

10 were

mixed

lotion

period

a long

a good

milky

mixed

and

and

heated

heated to

to 75°C.

75°C. The

of

mixture

components combined obtain

1 to

6 while

a luster,

giving

a good

Example

cream

being

feeling

compatibility

to

7 Foundation

(Composition)

cooling,

added

to

thereby

the

of

mixture

the

emulsifying

component

11 was added

to

emulsion.

a homogeneous

having

10 was

stirring,

After

mixture.

The c l e a n s i n g

good

7 to

components

thus

stable when the

cream

obtained for

applied

was

a long to

skin. (O/W t y p e )

the

a W/O type

period skin,

of time with

a

cream and

for

(Method

preparation)

at

and mixed

70°C,

components

3 and

emulsifying

the

thereto

components

again.

After

4 to

The f o u n d a t i o n was an 0/W type

with

a mixture

was

at

70°C,

thereby

To the

mixture

and

added,

time

to

from

herein.

thus

having and

a good

stirred

15 was

added

of

at

kept

and mixed to

obtain

fine

giving

described

one of o r d i n a r y

the

spirit

can

had a l u s t e r

obtained texture, a good

compatibility

and m o d i f i c a t i o n s

departing forth

cream

now f u l l y

Having

changes

and mixed

stirring

mixture.

component

cream

of

period

be a p p a r e n t

heated

emulsion.

a homogeneous

application

heated

7 were

cooling,

10 were

while

11 t o . 1 4 combined

70°C,

a long

and 8 to

1, 2

Components

this skill

being

feeling the

to

the

be made t h e r e t o

or scope

of

the

stable

for

upon

skin.

invention, in

and

art

it

will

that

many

without

invention

set

1.

A cosmetic

weight

of an e m u l s i f i e r ,

water;

wherein

where a total

the

R is of

a saturated 11 to

30% by

to

and

component

comprises

cholesterol

and

aliphatic

23 carbon group

carboxyl-bonding

chain,

oil

0.1

ester

of

the

(I):

substituent

alkyl

acid

fatty

comprises

a cosmetic

emulsifier

said

a branched formula

which

composition

atoms

attached

position

hydrocarbon and. including on the

and the

main

center

having

group at

least

chain of the

one

inbetween main

cholesterol: wherein and

said

said

cholesterol

2.

a total

of 13 to 3.

the

the

The

the

formula

where

the

The

wherein

R in

sented

by the

where

each

saturated of

as

in

a hydrocarbon

claimed

to

Claim

10:90. 1,

having

group

Claim

in

a hydrocarbon

of m + n is

total

4.

claimed

90:10

group

2, w h e r e i n

represented

by

(III)

about

centered

is

(I)

as

of

ester

atoms.

composition

formula

is

(I)

19 carbon

ratio

a weight

composition

formula

R in

cholesterol

acid

fatty

in

are

The c o s m e t i c

wherein

R in

branched

14,

and

the

distribution

is

m = n = 7. cosmetic

the

composition

formula

(I)

formula

(II)

R1 and

R2 is

of

aliphatic

carbon atoms

in

is

R2 is

claimed

a hydrocarbon

a straight

hydrocarbon R1 and

as

or

group

and

12 to

18.

in Claim group

branched the

total

2,

repre-

chain number

5.

cosmetic

The

wherein

the

total

formula

(II)

is

6.

saturated

octyl

Ri and

saturated

10.

formula

4,

R2 in

the

(II)

are

in

Claim

each

4 or

a branched

group. claimed

as

Claim

in

a 2-heptyl

The

cosmetic 0.1

fatty

acid

90% by w e i g h t

99% by w e i g h t 11.

1,

hydrocarbon

composition undecyl

cosmetic

are

each

4 or

a straight

group.

as

claimed

in Claim

1,

claimed

in

1,

group.

composition

cholesterol

of the

0.3 acid

50% by w e i g h t

90% by w e i g h t

(II)

as

to 30% by w e i g h t

The c o s m e t i c

fatty

formula

Claim

of a t o t a l and

ester oil

Claim of

the

cholesterol,

component

and

0.1

1 to

of w a t e r .

comprises

branched

the

in

as c l a i m e d

composition

aliphatic

comprises

branched

to

R1 and

claimed

as

composition

R2 in

The c o s m e t i c R is

wherein

which

Claim

a 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-

The c o s m e t i c

9.

to

in

atoms

in

group.

5, w h e r e i n

which

the

hydrocarbon

The c o s m e t i c

8.

chain

carbon

composition

R2 in

R1 and

R is

wherein

claimed

as

16.

aliphatic

7.

of

number

The c o s m e t i c

5, w h e r e i n

composition

to

5% by w e i g h t

cholesterol

of the

of w a t e r .

claimed

in

Claim

of a t o t a l

of

the

composition

cosmetic

as

ester oil

and

cholesterol,

component,

and

10,

1

20 t o

An e m u l s i f i e r

12.

a branched

cholesterol

acid

fatty

comprising:

composition

ester

of

the

formula

(I)

where

R is

total

of

alkyl

substituent

the

a saturated

11 to

aliphatic

23 carbon group

carboxyl-bonding

hydrocarbon and

atoms attached

position

including

on the

and

the

main

center

having

group

least

at

chain of

a

one

inbetween

the

main

chain,

and cholesterol; wherein said

said

cholesterol 13.

branched

are

in

R in

a total

of

the

13 to

ratio

a weight

The e m u l s i f i e r

wherein

acid

fatty

formula 19 carbon

composition (I)

is

cholesterol

ester

of

10:90.

as

90:10 claimed

a hydrocarbon

atoms.

to in

group

and

Claim having

12,

The e m u l s i f i e r

14. wherein

R in

by the

formula

where

of m + m is m = n=

about

wherein

R in

by the

formula

group

Claim

13,

represented

14,

the

and

distribution

is

(I)

is

as

claimed

a hydrocarbon

in

group

Claim

13,

represented

(II)

R1 and

saturated

aliphatic

of carbon

atoms

16.

a hydrocarbon

composition

formula

the

of

each

is

in

7.

The e m u l s i f i e r

15.

where

(I)

claimed

as

(III)

total

the

centered

formula

the

composition

R2 is

hydrocarbon

in

R1 and

The e m u l s i f i e r

wherein

the

total

formula

(II)

is

a straight

number 16.

R2 is

group

and

12 to

18.

composition of

or b r a n c h e d

carbon

the total

as. claimed

atoms

chain

in

in

R1 and

number

Claim

15,

R2 in t h e

The e m u l s i f i e r

17. 15 or

16 w h e r e i n saturated

branched 18. wherein octyl

The

R is

R2 in

aliphatic

emulsifier

as

claimed

in C l a i m

(II)

each

formula

the

hydrocarbon

composition

are

a

group.

as

claimed

in

Claim

12

a 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-

group. 19.

or

R1 and

composition

The e m u l s i f i e r

16 wherein chain

straight 20. wherein

R1 and

R2 in

saturated

The e m u l s i f i e r

R is

composition the

formula

aliphatic

claimed

(II)

are

in

Claim

each

15

a

hydrocarbon group.

composition

a 2-heptyl.undecyl

as

group.

as

claimed

in

Claim

12