PLASTICIZER FOR MASTICS, PLASTISOLS AND ADHESIVES
FIELD OF THE INVENTION
The invcntion rclatcs to a functionalizcd hydrocarbon-containing cut:
5 in particular I:~-c!~-~)x:j~lsitchda.t can be used as a p1asticizc:r in the
formulation of mastics, plastisois and adhesives.
The invention also rclatcs to the mastic, plastisol and adhesive
compositions comprising said plasticizer.
The present inverition also rc:latcs t.o t.hc use of said plasticizer for
10 rcducing the phcnomcnon of I:>l(:~dirli~n; rnastlc-s, plastisols and adhcsivcs.
TECHNICAL CONTEXT OF THE INVEIIJTION
Numerous products arc uscd in construction materials, for example
for floor covcrings, mastics or also sanitary seals. The addition of plasticizers
is common in cer~ain families of mastics such as the hybrid mastics (based
15 on siliconizcd modified polymers), acrylic mastics, polyurethane mastics,
plastisols (PVC paste) and ccrtain adhcsivcs. A plasticizer is a molcculc or an
oligomer, in the solid statc or in the more or less viscous liquid statc, added
to the formulations of different typcs of materials in order to makc them
more flexible, more resistant, morc resilient or casicr to handle.
20 An ideal plasticizer is compatible with the polymer matrix in order to
prevent thc phcnomcna of migration and bleeding, has low volatility, can bc
extracted only with difficulty by the liquids that will bc in contact with the
plasticized material, it performs \vcll with regard to ccrtain pr-opcrtics such
as flexibility, resistance to impact, cold, heat and h a s good electrical
25 rcslstivity. I t docs not bcccrnc ox~dizcd and remains non-toxic, odourlcss,
colourless and inexpensive
The phthalates arc. products very commonly uscd as a p1astic1zc.r. But
the pressure of incrcaslngly strlngcnt rcgulations restricts their uses In
many countries due to thelr danger to human health. Alternatives to then
30 use are now therefore necessary and much sought-after.
On the othcr hand, rcccnt regulatory constraints 1mposc.d by
limitations on volatile organic compounds or VOCs in construction matcrlals
are also to be taken into account. In fact, these compounds have a tcndcncy
to evaporate and/or degrade either immediately or over tlme and to be a
35 source of emissions that are often toxic to the environment and morc
particularly to human and animal health. Thcsc cmissions affecting cvcryday
lifc constitute a significant source of pollution inside homes, offices and
administrative buildings and any enclosed spacc with limited ventilation.
These emissions may be greatest when the materials are applied, but there
may also be a longer-term effect due to residual volatility over time or even
linked to the gradual degradation of the covering or of the adhesive or mastic
composition.
Hydrocarbon-containing fluids of the gas oil, kerosene or whit(: spirit
type can also be used as a secondary plasticizer in different formulations
including polymers or resins, This is the case for the mastics or PVC pastes.
But their use is now limited by their lower compatibility in the polymer
compared with phthalatcs. Phenomena of surface migration, bleeding, and
surface appearance dcfects that have been noted prevent the production of
formulae without phthalatcs containing only hydrocarbon-containing fluids.
Due to the increasing regulatory constraints, a technical solution is
required in order to allow the replacement of the phthalates in stable and
economically advantageous formulations of construction materials with a
low VOC content.
One of thc main objectives of the applicant is therefore to propose a
novel phthalate-free plasticizer, for the formulation of construction materials
and materials intended for the automotive sector such as mastics, plastisols
or certain types of adhesives.
Another of the objectives of the applicant is to obtain a plasticizer with
a non-VOC nature, for thc formulation of construction materials, materials
based on resins or materials used in the automotive sector such as mastics,
plastisols or certain types of adhesives.
Another objective of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives having satisfacton
resistance to UV radiation.
Another objective of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives having satisfactory
hardening, in particular according to the standard DIN IS0 7619 (for
mastics).
Another objectivc of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives which exhibit no
bleeding.
Another objcctivc of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives having satisfactory
drying, i.e. drying in less than 24 hours for a film with a thickness of 2 mm.
Another objective of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives having a suitable
dynamic viscosity, i.e. a viscosity compriscd between 2,000 and 8,000 Pa.s
at 23°C (Rheometrc Physica Rheolab - Needle 24 - speed: 1 rpm.).
Anothcr objectivc of the applicant is to propose a plasticizcr allowing
the formulation of mastics, plastisols and adhcsivcs having a satisfactory
skin-formation time, i.e. a skin formation tlme at ambient temperature
compriscd between 5 and 60 minutes.
Another objectlvc of the applicant is to propose a plasticizcr allowing
the formulation of mastics, plastisols and adhesives having a good shear
resistance according to the standard DIN EN 14293 (for mastics).
Another objectivc of the applicant is to propose a plasticizcr allowing
the formulation of mastics, plastisols and adhcsivcs having a suitable
modulus of elasticity according to the standard DIN 53504 or according to
the standard DIN 52455- 1 (for mastics).
Anothcr objective of the applicant is to propose a plasticizcr allowing
the formulation of mastics, plastisols and adhesivcs having good tensile
strength according to the standard DIN 53504 (for mastics).
Another objective of the applicant is to propose a plasticizer allowing
the formulation of mastics, plastisols and adhesives having satisfactory
elongation at break according to the standard DIN 53504 (for mastics).
Anothcr objective of the applicant is to propose a plasticizcr allowing
the formulation of mastics, plastisols and adhcsives having a satisfactor?
elastic rccovcry according to the standard DIN EN IS0 7389 (for mastics).
SUMMARY OF THE INVENTION
These objectives arc achieved due to a novel type of plasticizcr. The
invention therefore relates to a plasticizcr for mastics, plastisols, and
adhesivcs comprising at least one hydrocarbon-contain~ng cut characterized
in that the hydrocarbon-containing cut 1s functionallzcd, in particular
functionalizcd by at least one group comprising a hcteroatom, such as the
oxygen, sulphur, phosphorus and/or iiltrogcn atoms.
Preferably, the invention relates to a plasticizcr for mastics, plastisols,
and adhesives comprising a hydrocarbon-containing cut functionalized by at
least one group comprising an oxygen atom.
Preferably, the invention relates to a plasticizcr for mastics, plastisols.
and adhesives comprising a hydrocarbon-containing cut functionalizcd by at
least one group selected from the hydroxyl, ester, carboxylic acid and/or
ketone groups.
Preferably, the functionalizcd hydrocarbon-containing cut mainly
comprises hydroxyl groups.
Preferably, the f~lnctionalized hydrocarbon-containing cut comprises
from 1 to 20 mole '%I hydroxyl groups, preferably from 5 to 10'/;1.
Preferably, the hydrocarbon-containilzg cut is a hydrotreated,
hydrocracked and/or catalytically cracked hydrocarbon-containing cut or an
5 olefinic hydrocarbon-containing cut.
Preferably, the hydrocarbon-containing cut is a de-aromatizcd and/or
desulphurized hydrocarbon-containing cut or an olefinic hydrocarboncontaining
cut.
Preferably, the hydrocarbon-containing cut has a boiling point comprised
10 between 210 and 400°C.
Preferably, the hydrocarbon-containing cut has a kinematic viscosity at
40°C comprised between 1 and 22 mm'/s according to the standard ASTM
D445.
Preferably, the hydrocarbon-containing cut has a pour point ranging
15 from -40 to +lO°C according to the standard ASTM D97.
Preferably, the hydrocarbon-containing cut has a content of aromatic
compounds measured by UV spectroscopy less than 300 ppm, preferably
less than 200 ppm.
Preferably, the plasticizer comprises lcss than 1°/o by weight of phthalates
20 with respect to the weight of plasticizer.
A subject of the invention is also a composition of mastics, plastisois or
adhesives comprising:
- at least one polymer selected from the group consisting of a polyether
comprising two silane-type terminal functions, a polyurethane comprising
23 two silane-type terminal functions or a mixture thereof, a polyvinyl chloride,
an ethylene-vinyl acetate copolymer, a polyethylene, a polypropylene, a
polyamidc ;
- the plasticizer as described above;
- at least one compound selected from the group consisting of a
30 thickener, a filler, a cross-linking agent, a cross-linking catalyst and a
tackifier resin, or a mixture thereof.
Preferably, the composition of mastics, plastisols and adhesives
comprises from 1 to 30% by mass of plasticizer, with respect to the mass of
the composition of mastics, plastisols and adhesives, preferably from 2 to
35 20% and more preferably from 5 to 1.5°/o.
According to an embodiment, the composition is a mastic composition
comprising:
- at least one polymcr selected from the group consisting of a polyether
comprising two silanc-type tcrminal functions, a polyurethane
comprising two silane-type tcrminal functions, or a mixture thereof;
- the plasticizer as described above;
5 - and at least one cross-linking agent.
According to an embodiment, the composition is a plastisol composition
comprising:
- at lcast one polymcr selected from the group consisting of a polyvinyl
chloride or an ethylene-vinyl acctate,
10 - the plasticizer as described above,
- a filler.
According to an embodiment, the composition is an adhesive
composition comprising:
- at lcast one polymcr consisting of a polyethylene, a polypropylene, a
15 polyamidc or a polyurcthanc,
- an ethylene-vinyl acctate copolymer ,
- the plasticizcr as described abovc,
- a tackifier resin.
The invention finally relates to the use of the plasticizcr as described
20 above for reducing the phenomenon of blccding in mastics, plastisols or
adhesives.
DETAILED DESCRIPTION OF THE INVENTION
The plasticizcr according to the invention comprises at lcast one
hydrocarbon-containing cut. This hydrocarbon-containing cut has the
2.5 feature of being functionalizcd.
By functionalizcd hydrocarbon-containing cut according to the
invention, is meant a hydrocarbon-containing cut that has been chemically
modified by the introduction of hetcroatoms. The introduction of these
hetcroatoms confers polar properties on the plasticizer according to the
30 invention or generates electronic intcractions capable of creating affinities
wlth the polymcr network present in the mastics, plastisols or adhesives.
Thc polar and/or elcctronlc intcractions make it possible to reduce the
phcnomcna of blccding.
The hetcroatoms arc for example oxygcn, sulphur, nitrogcn and/or
35 phosphorus atoms, preferably the hetcroatoms arc oxygen atoms.
When the heteroatoms are oxygcn atoms, the groups present in the
hydrocarbon-containing cut are, for example, hydroxyl, ketone, carboxylic
acid and/or ester groups. The hydrocarbon-containing cut comprises one
type of group or several types of groups in a mixture.
Preferably, the functionalized hydrocarbon-containing cut comprises
mainly hydroxyl functions; it can be describcd as a hydroxylatcd
5 hydrocarbon-containing cut. Thc functionalizcd hydrocarbon-containing cut
comprises from 1 to 20 mole (X) of hydroxyl groups, preferably from 5 to IO0/o.
According to an embodiment of the invention, these hydroxyl functions
are for example introduced into the hydrocarbon-containing cut by reaction
of an oxidizing agent such as m-CPBA (m-chloro-peroxybenzoic acidl, oxone,
10 hydroperoxide, t-butyl hydroperoxidc, in the presence of a metallic catalyst,
for example based on nickel or iron.
The oxidation preferably leads to the formation of hydroxyl functions
on the hydrocarbon-containing cut, limiting the formation of ketone and/or
acid functions.
IS According to a second embodiment of thc invention, the
functionalization of the hydrocarbon-containing cut can also bc carried out
by oxidation of a specific hydrocarbon-containing cut, i.e. an olcfinic
hydrocarbon-containing cut. A proposed solution is the conversion of
internal or terminal olefins to diols. A possible process is an oxidation in an
20 aqueous medium with hydrogen peroxide in order to form an epoxide, thcn a
diol by hydrolysis.
According to a third embodiment of the invention, the functionalization
of the hydrocarbon-containing cut can also bc carried out by the addition of
hydroxyl functions. A proposed solution is mixing the hydrocarbon-
25 containing cut and a branched alcohol comprising between 14 and 22
carbon atoms such as the Guerbet alcohols comprising 16 to 20 carbon
atoms (for example 2-octyl-1-decanol) and the branched alcohols comprising
from 14 to 15 carbon atoms. The Gucrbct alcohols as describcd in the
literature are branched alcohols obtained by dimerization of aliphatic
30 alcohols with the release of a molecule of water.
This addition of the hydroxyl functions to the hydrocarbon-containing
cut can for example be carried out by weighing thcn mixing with stirring
from 20 to 70% by weight of branched alcohols and from 30 to 80% by
weight of hydrocarbon-containing cut as described.
35 Preferably, the plasticizer according to the invention comprises at least
one hydrocarbon-containing cut functionalized as described above,
potentially in a mixture with a non-functionalizcd hydrocarbon-containing
cut.
The hydrocarbon-containing cut is constituted by linear, branched
and/or cyclic alkanes, preferably C13 to C23. The hydrocarbon-containing
cut can also be an olefinic hydrocarbon-containing cut, comprising linear,
branched and/or cyclic alkanes, prcfcrably C 14-C22.
By hydrocarbon-containing cut ~vithint he mcaning of the invcntion. is
meant a cut originating from the distillation of crudc oil, prcferably
originating from the atmospheric distillation and/or vacuum distiilation of
crude oil, prcferably originating from atmospheric distillation followed by
vacuum distillation. The hydrocarbon-containing cut according to the
invention is prcferably a gas oil cut.
The hydrocarbon-contain~ng cut according to the invention is also
preferably subjected to stagcs of hydrotreatment, hydrocracklng and/or
catalytic cracking
The hydrocarbon-contalnlng cut accordlng to the invcntlon can also
prcfcrably bc subjected to a stage of hydrodewaxing
The hydrocarbon-containing cut accordlng to the invcntlon 1s also,
preferably, subjected to stages of dc-aromatlzatlon and/or optionally of
desulphurizatlon
The hydrocarbon-containing cut can be a mxture of hydrocarboncontaining
cuts subjected to the stagcs dcscrlbed above
The hydrocarbon-containing cut as dcscrlbcd above has a dlstlllatlon
range DR (in "C) such that 240 5 DR 5 400 and morc prefcrably such that
240 5 DR 5 370 Thc hydrocarbon-containing cut can comprise one or morc
fractions with distillation ranges comprised within that of said cut.
The hydrocarbon-containing cut of gas oil type according to the
invention generally comprises morc than 50% by weight of paraffinic
compounds, preferably more than 60%, even morc prefcrably more than
65%.
The hydrocarbon-containing cut according to the invcntion is generally
constituted by a majority of isoparaffins and a minority of normal paraffins.
Preferably, the hydrocarbon-containing cut contains morc than 50'h by
weight of isoparaffins and less than 20% by wcight of normal paraffins.
The hydrocarbon-containing cut according to the invcntion gcnerally
comprises less than 50% by wcight of naphthcnic compounds, prcferably
less than 45%, even morc prcfcrably less than 40'h.
The hydrocarbon-containing cut according to the invention is
prcfcrably frce of aromatics. By "frce" is meant, a hydrocarbon-containing
cut comprising less than 300 ppm of aromatics, prcferably less than 200
ppm measured by UV spectrometry.
Preferably, the hydrocarbon-containing cut according to the invention
has a sulphur content less than 10 ppm and preferably less than 2 ppm.
.--2-. The hydrocarbon-containing cut according to the invention generally
has a kinematic viscosity at 40°C comprised between 1 and 22 mm2/s,
preferably between 2 and 15 mm2/s and more preferably between 2 and 13
mm2/s according to the standard ASTM D445.
The hydrocarbon-containing cut according to the invcntion has a pour
10 point according to the standard ASTM D97 comprised between -40 and
+1O0C, preferably comprised between -30 and OGC, even more prcferably
comprised between -20 and 0°C.
The hydrocarbon-containing cut according to the invcntion also has
the advantage of being easily available on the market, being relatively
15 economical within the chain of oil distillation products.
The plasticizer according to the invention is free of phthalatc-type
compounds. By "free" according to the invention, is meant a plasticizer
comprising less than 1% by mass of phthalates, with respect to the mass of
plasticizer, preferably less than O.SO/;)m. ore prcferably less than 0. lo/;), even
20 more prcferably less than 0.0 1%.
The plasticizer according to the invention generally has a kinematic
viscosity at 40°C comprised between 5 to 22 mm2/s7 preferably between 5
and 15 mm2/s according to the standard ASTM D445.
The invention also relates to compositions of mastics, plastisols and
25 adhesives comprising the plasticizcr described above.
The invcntion also relates to a mastic composition comprising at least
one polymer selcctcd from the group consisting of a polyether comprising
two silane-type tcrminal functions, a polyurcthanc comprising two silanetype
terminal functions, or a mixture thereof, the plasticizer composition as
30 described above and at least one cross-linking agent.
Preferably, the polymer is a polyether comprising two silanc-type
terminal functions.
Advantageously the: mastic composition comprises from 10 to 50% by
weight of said polymer, preferably from 20 to 30°/0.
35 Advantageously the mastic composition comprises from 10 to 30% by
weight of said plasticizer composition, preferably from 10 to 25%.
In order to satisfy the mechanical and physico-chemical requirements,
the mastic composition also comprises in a standard manner at least one
compound selected from the group consisting of a thickener, a filler, a crosslinking
agent and/or a catalyst.
The invention also relates to a plastisol composition comprising at
least one polymer selected from the group consisting of a polyvinyl chloride
and ethylene-vinyl acetate or EVA, with the plasticizer composition as
described above and a filler.
A subject of the invention is also an adhesive composition, preferably a
thermoplastic adhesive composition, comprising at least one polymer
consisting of a polyethylene, a polypropylene or a polyamide, an ethylenevinyl
acetate copolymer, the plasticizer composition as described above and a
tackifier resin.
The compositions of mastics, plastisols and adhesives according to the
invention comprise from 1 to 30% by mass of plasticizer, with respect to the
mass of the composition, preferably from 2 to 20°/0, more preferably from 5 to
15%.
The compositions of mastics, plastisols and adhesives according to the
invention have the remarkable characteristic of containing less than 0.1 O/O by
weight of phthalatcs with respect to tlie mass of the composition, preferably
less than 0.05O/0, more preferably less than O.OlO/o, even more preferably less
than 0.00 l0/o.
The compositions of thermoplastic mastics, plastisols and adhesives as
described are without phthalates and with a low VOC content in order to
satisfy the current regulatory requircmcnts.
EXAMPLES
In the remainder of the present description, examples of the present
invention are given by way of illustration and are in no case intended to limit
~ tssco pe,
Different hybrid mastic formulations based on silyl modified polymers
(or SMPs) were assessed. These SMP mastics include the ST-PE (,5i ' 1a nc
terminated Polyether) and ST-PU (Silane terminated Polyurethane) product
families.
The following examples describe the SMP mastic compositions
comprising the different plasticizers below:
- di-isodccyl phthalate (or DIDP) as a rcference for the phthalatcs, in
comparative Example 1,
- a functionalized hydrocracked hydrocarbon-containing cut, in
particular a hydroxylated hydrocracked hydrocarbon-containing cut,
in particular a hydroxylatcd cut HYDROSEAL G3H, in Example 2
according to the invention,
- a hydrodewaxed hydrocarbon-containing cut, in particular a
HYDROSEAL G340H cut, in comparativc Example 3,
5 - dl-2-propyl-heptyl phthalatc (DPHP) as a second reference for the
phthalatcs, in comparativc example 3.
The hydrocarbon-containing cut HYDROSEAL G3H is hydroxylatcd in
the following way:
10
Preparation of the catalyst:
417 mg of iron (11) acetate and 697 mg of 2-methyl pyridine arc addcd to
1.25 L of acctonitrile under an inert atmosphere. The mixture is stirred for 1
hour then 821 mg of sodium tctraphenyl borate is added. Aftcr mixing for 1
15 hour, the catalyst solution can bc used for the hydroxylatlon reaction
Hvdroxvlation of the hvdrocarbon-contaming cut HYDROSEAI, G3I-I:
2.5 kg of hydrocarbon-containing cut HYDROSEAI, G3H, the catalyst
solution and 3.75 L of dichloromcthanc arc addcd into a reactor. 'I'hc
mixture is heated to about 37"C, then 1.15 kg of m-chloro-pcroxybcnzoic
20 acid (at 70°/o) dissolved in 2.6 L of dichloromethane and 0.9 L of acctonitrile
are added slowly over a period of 40 minutcs. Mixing is continued for 1 hour
at 40°C and thcn 0.013 equivalent of the catalyst solution of is added diluted
in 200 mL of dichloromcthane and 0.9 L of acetonitrile. 1; 15 kg of m-chloroperoxybcnzoic
acid (at 70%) dissolved in 2.6 L of dichloromcthanc and 0.9 L
25 of acetonitr~le are addcd slowly over a period of 40 minutcs. Mixing is
continued for 4 hours at 40°C, followed by cooling to 25°C and mixing for 24
hours. The mixture is then cooled down to 5°C and neutralized with a 2 M
solution of sodium carbonate. After mixing for 15 minutes, the aqueous
solution is extracted. The organic phase is then washed with 5.5 L of sodium
30 carbonate and mixed for 30 minutcs. Aftcr extraction of the aqueous phase,
the organic phasc is washed 3 tlmcs with 2.5 L of water and conccntratcd
under vacuum. Thcn. 2 washlngs arc carried out with 4 I, of 2 M
hydrochloric acid. Aftcr cxtractlon of thc aqueous phasc. the organic- phasc.
is washed wlth 4 L of sodium hydroxide and 3 L of NaC1, thcn concentrated
35 under vacuum in order to provide 2.2 kg of hydroxylatcd hydrocarboncontaining
cut, with a quantity of alcohol of 24 mole '10 (determination by
silylation of the hydroxylated hydrocarbon-containing cut in the presence of
pyridine and trimethylsilyl chlorldc thcn IN NMR analysis).
Table 1 summarizes the chemical characteristics of the ST-PE mastic
used for thc different evaluations.
The formulation of Examplc 1 contains 17% by weight of a phthalatc
5 plasticizer which is .Jayflex DIDP, with rcspcct to thc mass of thc
formulation. The formulation of Example 2 contains 17% by mass of a
plasticizer which 1s a hydroxylatcd cut Hydroscal G3H, wlth rcspcct to thc
mass of the formulation.
I i 1 Example I according to Example 3 ~
10 Table 1: chemical characteristics
I
I I
' I-'_- the invcntion - -
I
composition composition , composition '
Chemical nature / 1
(in YO by i (in 1 (in 4. by
Properties I
mass, I mass/ mass)
Polymer MS
203H
I
Polyether with silane-type
terminal functions /
Polymer
1 Comparative I
I
I I
I Polymer Polyurethane with silane- 1 I
I I
Example 2 Comparative I
1 ST-PU 1 type term~naflu nctions / i I I 24.5
I I I
, - ST-61 Polymer I - -
' I ~ sterically hundered 1 I
1 0.2
phenolic antl-ox~Ld.a-~Ct I _ II
1 DIDP - - - ---- I - Plasticizer
I Dl 2 p:-opyl licptyl
DPHP 1
I 8
/ phthalate / Plasticize1 ------------ - -LI -
Hydroxylatcd Hydroseal
I
2 1 G3H / Plasticizer
Hydroseal I Hydroseal G340H
I
HDW 1 1
-- hydrodewaxed 1
1
I 1
I I Amorphous silica / I
I
1
Rheologic Agent I
I
I Carbital 1 I
Chalk / filler 4 9 9 I 1 4 9 9 , 110s I +- --
1
I
Calcium carbonate / Filler ]
-- 56
I Dynasilan 1 Vinyltrimethoxysilan/ 1
0.8
I VTMO I 1 drying agent I - -
I 1 Silane derivative / drying
I
I ' 1.8
agent
I
3 I
I Dynasilan
Aminopropylmcthoxysilanc , I
AMMO 1 1 1 I
cross-linking agent
r
I
1 . . - - - - - 1 Organosilane / cross- I I -
, Te2g2o3k at ~ i o c t y l t i n ~ ~ ~ o/ l a1 t e 0.3
I 1 0.3 I
I I
I
I
1 I
1 1 linking agent
I
- 1 Organic tln / catalyst I I .- C - - -
0.2
1
! 'TOTAL I 1 100 100 ----- 100
. _ _ _ _ _ .
I i--- I
Table 2 summarizcs the results obtained for the different formulations.
Table 2: - Mec-h-a - nical-- p-ro perties- - . -- -. -- - - -- . -- -. - - .
I - -,
i r t i ' !:xsmp!c 2 Cornpara:;vc I Cxamph: i I acconiing to i x a m p l 3 1 1 the inucntion ! i
Characteristic
Bleeding 1 No ! No Ycs
1 Viscosity after 0 day / 56 days ( ~1n3 a.s) 1 6150 / 4800 1I 4650 / 3450
(Internal mcthodl I
I
Shear strength (application of thc mastic 1 I I
Skin-formation time (smoothing time) 1 I 1
to a \vooden substrate) EN 28 1 after 3
days
(In N/mmL) ([>IN !SN 14293) --
after 0 daq / 56 days (in mln)
I
(Internal method)
Shear strength (applicatlon of thc mastlc I I
8 / 10 1 49/55 I
1
I
.-
I
I to a wooden substrate) ICN 281 after 3
2.0 0.9
days 1
I (in mm) (DIN EN 1a293) I
I
Elastic~tym odulus at 1009'0 (2 mm fllrn) I1 I
I
I Shore A hardness after 28 days at I dmbicnt temprraturc 2 8
1
3 days / 28 days (ln N/mm7) 1 0.44 / 0 46 0.23 / 0 31 I
1
2 4 I
'i'enslle strength (2 rnm film)
(DIN IS0 7419) I
- L - - I-- 1-
3 days / 28 days ( ~Nn/ mm2) / 1.13 / 1.16 0.73 / 0.98 1
I
(DIN 53504, S2)
Elongat~on at brcak at 3 days / 28 da) s I
I
(in %I)
cycle 11) at ambic'nt tcmpcraturc ( ~ n 1 0.,536 I 0.390 I
I
- - - - I
Elasticity modulus at 1 00'i/i2 (aluminiunl
I
I cqclc A) at ambient tcmperaturc ( ~ n 0.518
I I 0.398 1
I
N/mm2) (DIN 5245.5- 1) - _--I I+ -4
Elasticity modulus at 100% (cement 1
rycle f3) at ambient t?mpcraturc (IP 1 0 461 I 0.624 1 1
I I 1
I 1 Elasticity modulus at 100'Yo (cement I
I I
I (in N!mmL) (DIN 52455-1)
I
-1
I
Elasticity modulus at 100'!4 (aluminium ;
I
cycle B) at ambicnt trmprraturc (,n i 0.51 1 1 0.522 1
N/mmL) (DIN 524.55 1) I
t
Elastic rrcovrrq at ambicn: tcmprraturr
(in '%J) 6 4 1 I
I 68 I
Thcsc results show that ~t 1s ~mposslblc to rcplacc 1000/o of thc
phthalates by a hydrodewaxcd hydrocarbon-containing cut. Indccd, blccding
is observed with comparative example 3 which incorporates 7% of Hydroseal
5 G340H, the hydroseal G340H being in mixture wlth phthalatcs of the DPHP
type. The mcchanical properties of ST-PU mastics have thus not been
assessed.
I t should be noted that the mcchanical propcrtics of the S'T-PE mastic
containing the functionallzed composition I-Iydroscal G3H as plasticizer arc
1? at lcast just as good as or even bcttcr than those of a mastlc containing
DIDP as plasticizer In particular for bleeding and elastic recover?- (according
to the standard DIN EN IS0 7389-B).
5 hydrocarbon-containing cut characterized in that the hydrocarboncontaining
cut is functionalizcd.
2. Plasticizcr for mastics, plastisols, and adhesives according to claim 1
characterizcd in that the hydrocarbon-containing cut is functionalizcd by
at least one group comprising a hcteroatom, such as oxygcn, sulphur,
10 phosphorus and/or nitrogen atoms.
3. Plasticizer for mastics, plastisols, and adhcsivcs according to claim 1 or 2
charactcrized in that the hydrocarbon-containing cut is functionalizcd by
at lcast one group comprising an oxygcn atom.
4. Plasticizcr for mastics, plastisois, and adhcsivcs according to claim 1 , 2
1 ,5 or 3 charactcrizcd in that thc hydrocarbon-containing cut is
functionalized by at lcast onc group sclcctcd from the hydroxyl, ester,
carboxylic acid and/or ketone groups.
5. Plasticizer for mastics, plastisols, and adhesives according to any one of
claims 1 to 4 characterized in that the functionalized hydrocarbon-
2 (> containing cut mainly comprises hydroxyl groups.
6. Plasticizer for mastics, plastisols, and adhesives according to any one of
claims 1 to 5 charactcrized in that the functionalizcd hydrocarboncontaining
cut comprises from I to 20 mole '/; of hydroxyl groups,
preferably from 5 to 1 0%.
25 7. Plasticizcr for mastics! plastisols, and adhesives according to any one of
claims 1 to 6 charactcrizcd in that the hydrocarbon-containing cut is a
hydrotreatcd, hydrocracked or catalytically cracked hydrocarboncontaining
cut or an olcfinic hydrocarbon-containing cut.
8. Plasticizcr for mastics, plastisols, and adhcsivcs according to any one of
3 0 claims 1 to 7 characterized in that the hydrocarbon-containing cut is a
dc-aromatizcd and/or dcsulphurizcd hydrocarbon-containing cut or an
olefinic hydrocarbon-containing cut.
9. Plasticizcr for mastics, plastisols, and adhcsivcs according to any one of
claims 1 to 8, characterized in that the hydrocarbon-containing cut has a
35 boiling point comprised between 240 and 400°C.
10. Plasticizer for mastics: plastisols, and adhesives according to any onc
of claims i to 9: charactcrizcd in that the hyt-frocarbon-containingc ut has
.4-?
\;
a kinematic viscosity at 40°C compriscd bct~veen 1 and 22 mm2/s
according to the standard ASTM D445.
i 1, Plasticizer for mastics, plastisols, and adhesives according to any one
of claims 1 to 10, characterized in that the hydrocarbon-containing cut
-
3 has a pour point ranging from -40 to +I0 "C according to the standard
ASTM D97.
12. Plasticizer for mastics, plastisols, and adhesivcs according to anq- one
of claims 1 to 1 1, characterized in that the hydrocarbon-containing ~ Lt I
has a content of aromatic compounds measured by UV spectroscopy of
10 less than 300 ppm: preferably less than 200 ppm.
13. Plasticizer for mastics, plastisols, and adhesives according to one of
claims 1 to 12, characterized in that it comprises less than 1°/o by weight
of phthalates, with respect to the wcight of plasticizcr,
14. Composition of mastics, plastisols, or adhcsivcs comprising
15 - at least one polymer selected from the group consisting of a polycthcr
comprising two silane-type terminal functions) a polyurethane comprising
two silane-type terminal functions, a polyvinyl chloride, an ethylene-vinyl
acetate copolymer, a polyethylcnc, a polypropylene, a polyamide, or a
mixture thereof;
20 - the plasticizer according to any one of claims I to 13;
- at least onc compound sclectcd from thc group consisting of a
thickener, a filler, a cross-linking agent, a cross-linking catalyst and a
tackificr resin, or a mixture thereof.
15. Composition of mastics, plastisols, or adhesivcs according to claim 14
25 characterized in that it comprises from 1 to 30°h by mass of plasticizer,
with respect to the mass of the composition of mastics, plastisols, or
adhesives, preferably from 2 to 20Y0, more preferably from 5 to 15O/0.
16. Composition according to claim 14 or 15, which is a mastic
composition comprising:
30 - at least one polymer sclcctcd from the group consisting of a polyethcr
comprising t~vo silane-type terminal functions, a poly~lrcthanc
comprising two silanc-typc terminal functions or a mixture thcreofl
- the plasticizcr according to any one of claims 1 to 13;
- and at least one cross-linking agent.
35 17. Composition according to claim 14 or 15, which is a compositioli of
plastisols comprising:
- at least one polymer selected from the group consisting of a polyvinyl
chloride or an ethylene-vinyl acetate copolymer;
o - the plasticizer according to any onc of claims I to 13;
- a filler.
18. Composition according to claim 14 or 15, which is a composition of
'3
c', adhesive comprising:
7
3 - at least one polymer consisting of a polyethylene, a polypropylene, a
polyamide or a polyurethane;
- an ethylene-vinyl acetate copolymer;
- the plasticizer according to any one of claims 1 to 13;
- a tackifier resin.
10 19. Use of the plasticizer according to any one of claims I to 13 for
reducing the phcnomenon of blccding in mastics, plastisols or adhesivcs.