Patentamt

J E u r o p European
a i s c h e Patent
s
Office

@ Publication number:

Office europeen des brevets

EUROPEAN

0 1 5 2
^ ^

9 8 2

PATENT A P P L I C A T I O N

Application number: 85200148.6

lnt CI.4: A 61 L 9 / 0 4

Date of filing: 07.02.85

<@) Priority: 17.02.84 NL 8400516

Date of publication of application : 28.08.85

Bulletin 85/35

@ Designated Contracting States: BE DE FR GB IT NL

Process for the preparation of air-freshener gels.

Process for the preparation of aqueous air freshener gels

having an increased perfume content of at least 5% and preferably more than 10% of the total weight of the gel by taking up the
perfume in finely divided, porous, water-insoluble, synthetic
polymer as the carrier and subsequently combining the thus
obtained perfume-laden carrier with an aqueous gel or with the
gelforming components.

@ Applicant: NAARDEN INTERNATIONAL N.V.,

P.O.Box 2 Huizerstraatweg 28, NL-1400 CA
Naarden-Bussum (NL)

Inventor: Traas, Petrus Cornells, Generaal

Krayenhoffstraat 123, NL-1 41 1 BC Naarden (NL)
Inventor: Roehl, Ernst-Ludwig, Frans Halslaan 13,
NL-1412 HS Naarden (NL)

Representative : van der Beek, George Frans et al,

Nederlandsch Octrooibureau Johan de Wlttlaan 15 P.O.
Box 29720, NL-2502 LS 's-Gravenhage (NL)

invention

The
of

ration

relates

air-freshener

Air-freshener
They

consist

from

which

the

perfume

extent,

which

freshener

air

air

fresheners

rial.

Since
in

soLubLe
geneously
also

used

is

gels

Aqueous
known

the

and

to

are,
of

of

types

or

matesparingly

therein,
solvents

perfume

carrier

homo-

as
such

as

gLycoL-ethers

are

water

has

However,

and

se,

and

vegetable

and

microbial

and

xanthan
starch

the

the

safe

toxicoLogicaLLy

the

divalent

or

Synthetic
as

the

maximum
content

but

above

in
about

and/or

syneresis

Liquid

from

example,

54/110,990
perfume

the
in

content

as

be

used

may

carragheen,

as

by

some

adding

salts

aLcohoL

poLyvinyL

gum,
In

AL or

Mg,

Ca,

agar,

gelatine,

derivatives.

such

agar

karaya

example,

increased

Limited

of

Cr.

also

can

of

about
it

6 X the
with

Aqueous

Japanese

be

strength

the

perfume

6 X);

gels

Patent

carragheen
53/088,334

at

in
a

and

exuding
are

the
perfume
decreases

greatly

perfume

they

Mostly,

given

that

appears

PubLished

agent:

perfume.
X is

10

gel

that

disadvantage
of

amount

practice

to

the

have

gels

get.

up

for

be

metals

occurs,

(gelling

as

ways

tragacanth,

also,

can

content

perfume

literature,

such

numerous

agent.

aqueous

contain

there

cellulose

such

geLLing

agents

gum,

and

polyvalent

Such
only

guar
and

polymers

in

gums

strength

geL

prepared

gelling

Like,

derivatives

cases

used

as

pectins,

alginates,

be

can

per

for

or

Life

known

many

organic

imparts

material.

base

can

time

amount

as

material.
cheap

thus

insoLubLe

aLcohoLs

products.

working

dispersed

GeLLed

carrier
it

be

must

polyhydric

that

advantage

used

generally

are

they

the

as

the
In

is

water

possible.

or

unit

per

obtained.

material,

and

released
contains.

gelled

water,

monohydric

carrier
The

prepa-

thus

consumer

atmosphere.
by

the

gels

evaporates

determined

perfumes

as

the

to

popular

sLowLy

the

to

considerable
an

are

gels

perfume

of

quantity

and

gels

for

a process

a perfume-containing

odour

a pleasant
the

of

to

as

described,

AppLications
sodium

(geLLing

Nos.

stearate,
agent:

bacterial
52/136,893
2-4

hol,

cgelling
% of

5 % of

salt,

and

(geLLing

agent:

describes

the

trivalent

metals

the

of

use

% of
of

content
supposed

to

examples
Patent

do

reveal

not

contain

only

range

% of

based

gels

is

0.25-30
One

30

% of

be

Longer
these
of

and

A few
fier

it

that
to

the

is

bution

of

Patent

AppLication

gels

cannot

nonionic

in

used,

at

10

emulsifier

No.

% of

is

for

high

to

than

gels

a geL

with

are

assist

an

con-

no

can

Moreover,
the

preparation
(up

needed.
applications

phase.

% of

of

emulsidistri-

Japanese
that

perfume

amount

to

there-

and

homogeneous

reports

2-3

pure

starch

a quantity

aqueous

in

these

temperatures

patent

add

to

The

% of

geL

perfume.

apparatus,

the

added

10

When

stable

that

52/070,035

more

of

content

7 atmospheres),

order
in

report

needed.

is

advisable

perfume
contain

indeed

des-

X.

abovementioned

perfume
the

of

is

complicated

76/12909

content

does

to

used.

perfume

solution

(up

examples

agent.

0.5-5

also

the

being
No.

locust

can

again

perfume

disadvantage

the

and

gelling

this

amylose

of

carragheen

the

amylose

pressures

reLativeLy

report

for

even

the

have

of

as

the

amylose

produced

describes

75/02596

AppLication

examples

but

requisite

170C)
fore

% of

gels

the

the

perfume.

here

amylose

expensive)

70

taining

of

% of

but

preferably

perfume,

thus

(and

but

X,

2.5

perfume,

that

states

description

perfume,

No.

% of

are

% of

description

3.3

which

gels

the

Patent
on

AppLication

to

than

more

to

up

a perfume

10

to

up

mixtures

Patent

gels.

contain

can

show

perfume

aqueous

of

perfume

gels

only

also

salts

and

aqueous

NetherLands

to

NetherLands
cribes

AppLication

76/11041

No.

these

examples

according

10

to

up

the

on

which

flour,

that

AppLication

based

gels

contain

Patent

in

agents

similar

able

be

NetherLands
bean

aLco-

polyvinyl

carboxymethylcellulose/At

reports

Equally,

describes

aqueous

French

AppLication

gelling

perfume,

4 X.

the

and

carboxymethylcellulose

as

76/02254
while

Patent

description

20

to

up

in

and

perfume)

perfume).

NetherLands

Though

% of

carragheen

agent:

perfume),

2,293,976

No.

1-10

polysaccharide,

which

aqueous
unless
is

0.5-

1.5

times

fume
it
a

of
in

true

in

ent

The

of

carboxylic

acids,

This

mixture

many

cases

for

example

for

the
be

only

is

in

handled
the

is

It

freshener

content

and

hence

perfume

release

of

total
pared

by

porous,
material
carrier
referred
a

of
has

first

only

unit

to

of

have

Life

working

time.

By

in

present

the

of

found

been

the

up

thereafter
and

that

can

perfume

a higher
perfume

10

content

a
% of

the

in

an

the

carrier

materials,

polymer

which

has

hold

a perfume

in

general

have

a predominantly

polymer

should

its

an

is

hydrophobic

polymers

possible

Since

have
used

of

wiLL

polymer
to

perfumes

character,
be

use

structure

a predominantly
can

be

Preferably,

synthetic

open-pore

pores.

preferably
The

it

carrier

mixture

geL.

aqueous

pre-

divided,

the

as

hereinafter

which

be

can

finely

this

incorporating

perfume,

gels

poLymer

As

character.

or

increased

than

in

perfume

material.

phobic

In

used

context,

such

synthetic

"premix",

also

Like.

provide

and/or

more

carrier

can

to

"increased

the

and

the

perfumery,

solution

an

as

synthetic

as

small in

invention

water-insoluble

any

such

components

in

porous,

used

which

like,

odour.

the

organic

the

desired

pulverulent,

is

of

gel.

taking

as

constitu-

esters,

customary

the

preferably

the

material

the

nitriles,

generaLLy

which

gels

water-insoLubLe,
and

the

and

supplied

of

meant,

now

of

concretes
a

a -

more

Longer

per
is

weight
It

5 % and

Least

at

or

object

air

there

of

to

depends

solution.

aqueous

content"

spread

diluent

one

composition

which

origin,

balsams,
to

or

and

natural

contains

because

perfume

a mixture

ketones,

of

intended

solvent

Moreover,

solubility

means

ethers

oils,

a perfume
of

quantity

nature

here

products

is

the

aldehydes,

resin

oils,

of

X.

geL

aqueous

per-

perfume.

aLcohoLs,

contain

10

of

degree
on

"perfume"
as

an

the

case

as

amount

into
the

which

high

as

the

hence

the

term
such

ethereal

that
on

and

compounds,
also

be

can

cases

water

components

can

get

extent

in

perfume,

homogeneously

considerable

perfume

the

all

mixed

be

of

amount

content

is

can

the

addition

in
the
hydropoly-

for

mers,

polymers
of

the

whether
of

the

it

the

with

can

or

or

so-called

more

formed

thus

the

In

is

where

mixing,
SuitabLe

thereof

and

polymer

matrix

filled

with

taking

Specification

cation

61,701

in

and

which
by

preparation
in

perfume
in

example,
European

Literature

the

of

example

the

the

in

1,576,228,

thereof,

vacuum.
for

up

for

described,

Patent

under

porous

pores

for

perfume,

processes

for

of

types
the

obtained,

polymers,
are

fitled

time

same

preparation

appropriate

processes

pores

other

structure

or

The

of

polymer

material

prepolymers.

case
the

or
mono-

the

for

base

one

types

more

at

processes
be

of

some

before

added,

are

of

or

of

case

polymer

mixture

monomer

one

the

In
the

condensation

type,

preferably

be

afterwards

simple

is

perfume

perfume.

polymers
porous

polymers.
to

polymer
the

poLyaLkene

polymerisation,

and/or

mers

the

oxidat.ion

or

polymers,

during

of

example

cited

the

British

Patent

Appti-

these

publi-

in

cations.
The
prepared

for
already

therein.

with

be

Some

gelling

salt

of
the

replaced

cular

the

to

or

not

more

perfume

In

for
of

is

the

the

economic

premix

methyl-

as

be

combined
agent.

can,

if

desired,

solvents,

in

parti-

geL
such

as

to

like,

ethanol,

the

this

extent
action

satisfactory

replacement
since

reasons,

than

perfume
the

the

general,

determined
in

such

crosslinking

aLcohoLs

from

example,

carboxymethylcellu-

as

for

and

expensive

amount

invention
of

and

applicited

for

ceLLuLose

are

agents

patent

are,

be

can

and

Literature

organic

glycol

used.

the

metal
used

detract

and

advantageously

polyhydric

inadvisable,
are

be

known

geLLing

agents

can

polyvalent

agent

The
amount

in

modified

and

ethylene
do

geLLing

the

and

water-miscible

by

these

solvents
to

monohydric

however

patents

gelting

agents

water

isopropanol,
that

the

invention

are

the

as

hydroxyethyLceLLuLose

of

A part

suitable

carragheen

cellulose,
Lose.

mentioned,

Very

agar,

agar

such

in

example,

which

agents

gels,

the

to

according

geLLing

aqueous

for

described,
cations

using

by

customary

gels

aqueous

of
is

organic

water.

present
by,
and,

on

in

a geL

the

one

on

the

according
hand,

other

the
hand,

the

amount

of

not

subject

in

premix

to

basic

any

Limited

by

fact

mixture

the

viscosity

The

maximum

the

the

This

gel.

but

restriction

that

in

the

Last
is

preparation

increases

with

is

amount
in

practice

of

the

get
of

amount

increasing

piemix.
determined

fore

of

ability
is

the
that

required

should

be

moulds,
ated

a maximum

of

a gel.

If,

into

paration,

of

filled

means

then

by

substantially
The

determined
solid,
what

carrier
of

requirement

it

is

or

Lumpy.

needed

to

the

those

as

mentioned

case

of

the

customary

Patent

Patent

contain

some

carriers,

even

In
add

in

gel,

some

premix
an

HLB

as

fatty

sation
ethylene

is

are

achievable.
is

premix

of

be

must

is

premix

some-

polymeric
the

on

carriers

polymeric
in

the

the
of

contents

aboveand

1,576,228
premix
In

perfume.

it
of

to

assist

the

value

of

is

90-95

in

most

case

of

can
the
% in

9 or

acid

esters

products

of

the

the
contains

premix

damp,

it

can

be

emulsifier

in

the

preparation

more
of

Preferably,
for

used

are

polyethylene

alkylphenols

or

advisable

distribution

homogeneous

mixture.

geL

when

especially

cases,

amount

order
in

X of

perfume

that

perfume

small

75-90

pre-

porosity.

example,
61,701,

incorpor-

possibLe.

are

much

of

mixture

the

depends

Specification

AppLication

readily

so

for

described,

it

pressure,

the

requirement
degree

If

under

premix

amount

its

the

package

gel

the

if

on

cases
premix

this

the

the

minimum

The

meet

British

European

that

by

into

be

in

made,

of

content

disadvantage

no

the

can

contents

and

polymer
In

such

the

though
damp

type

perfume

and

poured

works

which

maximum
by

is
and

premix

higher

be

premix

use

stirrers,

apparatus

process-

preparation

X of

however,

heavy-duty
of

35

there-

preparation.

easily

can

about

the

is

used
the

to

as

after

it

that

be

to

preparation,

for

immediately

Liquid

so

during

avaiLabLe

is

premix

requirements

mixture

gel

which

apparatus

the

by

of

amount

of

emulsifiers

glycols,

and

aLcohoLs

to

be

prepared

with

simple

means

and

the

the
having

purpose,

oxide.
A geL

of

this

fatty

to

such

condenwith

at

containing
of

account
a

the

which

with

carrier

polymeric

referred

here

avaitable

is

the

PreferabLy,
for

sifier,
as

the

quickLy

quently

sotidifies.

at

sufficiently
these

ration

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An

to

room
Long

similar

the

gels

gels

according

with

the

to

foLLowing

salt,

and

agent

where

an

the

room

this

the

temperature

and

remain

according
of
the

to

perfume

invention

recipe:

then

added

mixtures
and

are

subse-

can
be

the
which
was

be

mixture

get

known

also

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is

emul-

temperature.

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methods

coLourant.

the

geL

types
they

amount

constituents,

temperature

temperature,

that

and

premix

pre-

and,

agent

other

Many

elevated
at

The

appropriate,

and

also

are

a desired

preservative

thereafter.

time

and

example

geLLing

gel

However,

prepared

water,

the

mixture,

form.

with

in

up

premixes

with

moulds

cooling

Such

from

differing

homogeneous

mixing

and,

at

into

poured

products,

taken

ready-to-use

beforehand,

prepared

and

in

out

such

beforehand

gelling

possible

as

On

ALL

premix

invention

giving
a

for

have

table:

carried

se

taking

general

after

metal

water,

mixed

are

preferably

be

mixed

appropriate,

except

in

is

per

premix.

appropriate

emulsifier,

where

the

as

in

foLLowing

geL

is

material,

to

the

the

perfume

commercially

where

mix,
of

the

methods,

to

the

to

therefore,

provisos,

known

according

that,

these

of

methods

wiLL

premix

conforms

preparation

accordance
except

% of

abovementioned

composition

The

35

most

which
into

poured

used

for

Liquid
for

the

can
a
moulds.

prepa-

invention.
can

be

prepared

used
in

in

the

accordance

The
the
is

examples

in

no

EXAMPLE

restricted

way

of

powders

AG,

(a
(75

powder

the

abovementioned

in

vacuo.

This

gave

sequentLy

mixed

with

4.5

g of

in

moulds
of

25

EXAMPLE

II

% were

and

0.4

cellulose

of

USA)
added,

with

warmed

powder

to

of

Dow
good
in

80C,

On

this

obtained.

cooling

freshener

to

to

gels

was

having

sub-

carragheen,
were
750C.

about

thoroughly
This

room

25

somewhat

stirred

was

was

which

CaCl2.2H20
to

with

components

g of

warming

added

mixture

2.2

g of

Marine

g of

methyLparabene

with

was

mixture

2.5

g of

0.5

two

powder

water.

water,

the

Germany)

Laden

were

mixing
damp

of

fiLLed

was

temperature,
a perfume

con-

obtained.

of

carragheen

and

the

air

A mixture
for

g of

warm.

stable

by

polymer

RepubLic

space)

somewhat

above

and

while

and

tent

g of

homogeneous

stiff

62.2

solution

viscous

perfume

described

premix

into

invention

porous

FederaL

X void

chloroacetamide

dissolved

for

trademark

Obernburg,

of

until

the

and

thereto.

AccureL

Enka

poLypropyLene

The

invention

illustrate

to

solely

I
5 g of

0.3

the

to

according

process

intended

are

GeLcarin

CoLLoids

MethoceL

E 50

AFG 75

trademark

Chemical

USA,

MidLand,

stirring,

to

a solution

66.3

while

g of

water.

trademark

SpringfieLd,

Inc.,
(a

(a
for

Mich.,

The

of

0.1

N.J.,

methyl-

USA)

was

g of
mixture

whole

was

stirring.

28.6

g of

Polytrap

(a

trademark

Laden

with

perfume,

of

Wickhen

for

porous

Products

Inc.,

polymer
Big

Pond

Road,

Huguenot,

perfume

content

Artypon

NP-14

of
(a

USA)

N.Y.,
70

% by

trademark

Werke

Germany).

The

hot

Gelcarin

powder

and

the

poLymer

homogeneous
poured
ture,
% were

into
stiff

Grunau,

mixture

was

moulds

while

and

obtained.

stable

nonionic

ILLertissen,
solution

whole

gets

On

having

with

FederaL

2.4

g of

to

cooling
a perfume

of

the

thoroughly
was

of

RepubLic

added

was

which

obtained,

having

emulsifier

stirred

was

warm.

powder
mixed

were

weight
for

Chemische

poLymer

untit

subsequently
to

room
content

temperaof

20

1.

which

ner

gels

the

perfume

the

taken

combined
components.

2.

Process
a

is

3.

Process

in

that

before

used

the
or

4.

during

Least

5.

according

is

Air
to

CLaim

carrier
to

added

water-

material
with

or

that

is
the

and
subgel-

characterised

in

synthetic

material.
CLaim
to

the

1 or

characterised

2,

base

polymer

material

polymerisation.
to

one

or

that

an

emulsifier

is

used

in

the

according
that

freshener
one

1,

in

obtained

geL

in

in

carrier

freshe-

porous,

water-insoluble,

according

Process

characterised

6.

the

divided,
thus

aqueous
to

according

Process
at

an

porous,

perfume

characterised
of

as

the

as

material

according

pulverulent,

polymer

finely

polymer
with

forming
that

in

air

aqueous

characterised

perfume,

carrier

perfume-laden

sequently

a
up

synthetic

of

preparation

contain

is

insoluble,
the

for

Process

or

to

a gel

more

of

of

having

CLaims
an

HLB

preparation

of

a geL.

one

of

CLaims

or

more

consisting

obtained

gels

more

CLaims

value
1-4,

of

using
1-5.

1-3,

the

process