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US010519294B2

(12) United States Patent ( 10 ) Patent No.: US 10,519,294 B2


Bugiolacchio et al. (45 ) Date of Patent: Dec. 31 , 2019
(54 ) SELF -CLEANING COMPOSITE MATERIAL C08K 3/08 (2006.01)
FOR PRODUCING MOLDED KITCHEN AND CO8L 67/06 (2006.01)
BATHROOM INTERIOR DECORATION (52) U.S. CI.
ITEMS CPC C08K 3/22 ( 2013.01 ); C08F 2701
(2013.01); C08K 3/08 ( 2013.01); C08K 5/0025
( 71) Applicant: DELTA SRL , Montecassiano (IT) (2013.01 ); C08K 5/103 (2013.01 ); C08K
5/5415 (2013.01); C08L 67/06 ( 2013.01 );
(72 ) Inventors: Antonio Bugiolacchio , Recanati (IT ); C08K 2003/0812 (2013.01); C08K 2003/2227
Maria Savina Pianesi , Macerata (IT ); ( 2013.01 ); C08K 2003/2241 ( 2013.01) ; C08K
Samuele Rossini, Castelfidardo (IT ) 2201/005 (2013.01)
(58 ) Field of Classification Search
( 73 ) Assignee : DELTA SRL , Montecassiano (MC ) (IT ) CPC CO8K 3/08 ; C08K 3/22 ; CO8K 5/0025 ;
C08K 5/103 ; C08K 5/5415 ; C08F 2/01;
COSL 67/06
( * ) Notice : Subject to any disclaimer, the term of this See application file for complete search history .
patent is extended or adjusted under 35
U.S.C. 154 (b ) by 73 days. (56 ) References Cited
( 21 ) Appl. No.: 15 /570,170 FOREIGN PATENT DOCUMENTS
(22) PCT Filed : May 2, 2016 WO WO2013017651 2/2013
(86 ) PCT No.: PCT/EP2016 /059737 * cited by examiner
$ 371 (c ) ( 1 ), Primary Examiner Edward J Cain
(2 ) Date : Oct. 27 , 2017 (74 ) Attorney , Agent, or Firm — Egbert, McDaniel &
( 87 ) PCT Pub . No.: WO2016 /177662 Swantz , PLLC
PCT Pub . Date : Nov. 10 , 2016 ( 57 ) ABSTRACT

Prior Publication Data


A self -cleaning composite material including the following
(65 ) composition : 50 % -85 % in weight of alumina trihydrate
US 2018/0127563 A1 May 10 , 2018 (ATH ) -based mineral charges; 10 % -30 % of cross - linking
polymer comprising polyester resin ; photocatalytic Titanium
( 30 ) Foreign Application Priority Data Dioxide ( TiO2) dispersed in the cross - linking polymer in a
weight percentage from 0.05 % to 5 % with respect to the
May 6 , 2015 (IT) 102015000014119 weight of the cross- linking polymer; compatibilizing agent
for anchoring between the photocatalytic TiO2 and the
(51) Int . Ci. cross-linking polymer, wherein the anchoring compatibiliz
C08K 3/22 (2006.01) ing agent of the TiO2 is silane; and cross - linking monomers
C08K 5/00 (2006.01) in order to obtain the reticulation of the cross- linking
C08K 5/103 ( 2006.01) polymer by thermal or chemical polymerization .
C08K 5/5415 (2006.01 )
CO8F 2/01 ( 2006.01 ) 13 Claims, 4 Drawing Sheets
U.S. Patent Dec. 31 , 2019 Sheet 1 of 4 US 10,519,294 ?2

??

?
?.

CH3
?.
?

??

CH3
?
?.

I
?
?
?

PERKADOX V

S
!
?
T

I FIG
1
.
H
n

TiO2 IPA+
AMA

Si
OCH3
H3CO ? ?
?.

?.
U.S. Patent Dec. 31 , 2019 Sheet 2 of 4 US 10,519,294 B2

time250min

ATHTiO2+0,3%DPiandMMAoslpyersitoenr time200min
PD+0,3%TiO2ATHoislpyerstieorn
SDi+0,3y%TiO2sQpreUuAsipRonTZ
min150time

FIG
2
.

100min
time

mintime50

min
O

time
30 25 20 15 10 5
U.S. Patent Dec. 31, 2019 Sheet 3 of 4 US 10,519,294 B2

time250min

P
D
TiO2
%
0,3
+ATH
i
o s
l p
y e rs t
i e
o r
n AMMAandPDo+0,3%iTiO2ATH
lsypesrtieorn
QTiO2+0,3%UDSiAsypRerTsZuiopn min200time

150mintime

3
.
FIG

min100time

time50min

tOim en
30 25 20 15 10 5 0
U.S. Patent Dec. 31 , 2019 Sheet 4 of 4 US 10,519,294 B2

minTime-Viscosity
20
TiO2+ATH0,3%DPioslpyerstieorn oMMAandPD+0,3%Ti02oiATHlsyperstieorn
+0,3%TiO2QDSiUyspAreRusTipoZn

+
V–Time60miniscosity FIG
4
.

oTime–Viscosity

10. 0 9.0 0 8.0 0 7.0 0 6.0 0 5.0 4.0 0 3.0 0 2.0 0 1.0 0
0
US 10,519,294 B2
1 2
SELF -CLEANING COMPOSITE MATERIAL Another purpose of the invention is to provide a self
FOR PRODUCING MOLDED KITCHEN AND cleaning composite material that is easily thermoformable
BATHROOM INTERIOR DECORATION and moldable with especially simple molds and a simple
ITEMS molding process.
5 Another purpose of the present invention is to provide a
The present patent application for industrial invention self-cleaning composite material that is intrinsically photo
relates to a self- cleaning composite material for producing catalytic , effective , efficacious, and at the same time envi
molded kitchen and bathroom interior decoration items in ronmental friendly and non -toxic for man and the environ
ment.
general, such as sinks, worktops, washbasins, bathtubs , 10 These purposes are achieved according to the invention
interior decoration articles and the like.
The WO2013 /017651 patent application in the name of with the characteristics of the independent claim 1 .
the same applicant discloses a self -cleaning composite mate In this description percentages are considered as weight
rial having a composition that comprises quartz-based min percentages with respect to the final product, except when
eral charges and photocatalytic nanometric titanium dioxide the percentage ratio is indicated .
hasThethecomposite
followingmaterial according
: to the present invention
15
( TiO2) mixed in a methacrylic syrup containing metylmeth composition
acrylate MMA and polymethyl methacrylate PMMA. Such 50-85 % in weight ofmineral charges with alumina trihy
a composition is mixed with somemineral charges and other drate (ATH ) base with size comprised between 10 and 50
chemicals and the obtained mixture is cast or injected in a micron ,
mold in order to obtain the finished product by means of 20 10-30 % of polyester resin ;
polymerization. photocatalytic Titanium Dioxide ( T10 ,) dispersed in the
The aforementioned patent application WO2013 /017651, methacrylic syrup in a weight percentage of 0.05-5 % with
which uses jartz-based mineral charges and a methacrylic respect to the weight of the polyester resin ;
syrup composed of one monomer and one polymer , dis compatibilizing agent, such as silane, to anchor the pho
closes a material that is used also in kitchen applications that 25 tocatalytic Tio , to the polyester resin ; and
require a high mechanical resistance because the surface cross- linking monomers to obtain the reticulation of the
undergoes high mechanical, chemical and physical stress polyester resin or mixture .
caused by kitchen tools, such as pans, cutting boards, knives polyester resin, a can
Preferably polyester resin is exclusively used . In fact,
be polymerized easily at ambient tem
and cutlery . Nevertheless, the product obtained according to
WO2013/017651 has the typical characteristics of thermo- 30 perature with known
polyester resins is simplecatalysts. The molding
and requires process of
simple inexpensive
hardening materials ; surfaces and shapes are given during molds .
molding when the liquid mixture is polymerized and After making some experimental tests , the applicant
becomes a solid composite . found out that a reticulation of the TiO2 is obtained also with
The surfaces of the product are perfectly homogeneous
and the product is ready for use , without the need of any
35 polyester resin . Moreover, polyester resin is stable and
additional treatment. However, no repairing or polishing remains stable also after adding TiO2.
Advantageously , a polyester resin of POLYLITE 32166
operations are possible after the product is extracted from 16 REICHHOLD type is used . POLYLITE® 32166 is a
the mold . Drilling or cutting operations must be carried outpolyester resin with an isophthalic acid and neopentyl glycol
with machines provided with industrial diamond tools with 40 base , with low viscosity, a high content of solids and a low
MOHS 10 hardness, because they must have a hardness content of styrene . POLYLITE® 32166 polyester resins are
higher than quartz, which has a MOHS hardness of approxi casting resins developed for producing materials that do not
mately 7 need to be covered with gel coat . These resins are rigid , with
Consequently, the quartz mineral charges make the final medium reactivity and low viscosity . They are UV - stabi
product extremely hard , not malleable and with complex 45 lized . POLYLITE® 32166 polyester resin withstands the
moldeability. The term “moldeability ” indicates a transfor deterioration caused by water, has a good resistance to
mation of the resin into composite according to the prior art. stains, a very high temperature at heat deformation , high
Manufacturers of molded products made of hard materials thermal-shock performance, and high resistance to many
use quartz as mineral charge because the surface must organic and inorganic solutions and solvents.
withstand impacts, shocks, and surface scratching . There 50 A mixture of polyester resin and metylmethacrylate
fore, if the final product is damaged or faulty , it cannot be (MMA ) can be used instead of polyester resin .
repaired . Polyester resin has a poor resistance to light, and tends to
The methacrylic syrup that contains MMA requires a turn yellow after a long exposure to UV radiation. The
complex molding know -how ; in fact, special molds and a 55 addition
reduces
of an MMA percentage (0.5-15 % ) to polyester resin
or almost eliminates this phenomenon .
delicate molding process must be used . The use of MMA in polyester makes the structure of the
Moreover, because of the presence of crosslinkers , the composite more performing in terms of mechanical charac
mixture of quartz mineral charges and methacrylic syrup teristics. Moreover, the use of MMA reduces the post- curing
that contains MMA generates high chemical bonds and a time of the polyester product because MMA considerably
high reticulation of the mineral charges of quartz , which is 60 enhances cross-linking during polymerization , more than
highly cross -linked , thus making the final product non styrene that is normally used in polyester resins .
thermoformable or workable . However, the weight percentage of MMA in the mixture
The purpose of the present invention is to eliminate the must be lower than 15 % with respect to the total weight of
drawbacks of the prior art by providing a self-cleaning the mixture . Therefore , the amount of polyester resin must
composite material used to produce kitchen and bathroom 65 be higher than 85 % with respect to the total weight of the
interior decoration products , which is sufficiently soft and mixture. This guarantees the aforementioned advantages,
formable in such manner to be easy to work and repair . which are related to the polyester resin .
US 10,519,294 B2
3 4
Alumina trihydrate (ATH ) has a MOHS hardness that is Being a ductile resin that is very easy to work , the product
lower than 5, thus making the final product sufficiently soft, according to the present invention has unique properties that
malleable , reparable and workable just like wood , that is to allow for making surfaces with no junctions or with almost
say by means of the tools that are ordinarily used by a imperceptible junctions. It is pleasant to see and warm to
carpenter. In view of the above, if the final product is 5 touch , with a velvety surface. Surfaces can be renewed and
damaged , said damage can be repaired with a mechanical restored to their original aspect with an ordinary delicate
operation , such as abrasion and filling with a special glue abrasive detergent and an abrasive sponge . The surfaces can
that can be sandblasted and polished after hardening, thus be sandblasted in matt version or polished with mirrored
perfectly repairing the damaged , cracked or faulty part . polished finish .
Alumina trihydrate (ATH ) must have a size of 10-50 10 This material is easy and fast to maintain . It can be
microns in order to have a homogeneous, compact material cleaned with soapy water or ordinary detergents to remove
with rheology suitable for low pressure casting in a mold , most stains
without sedimentation or sedimentation gradients of the detergents areor recommendeddirt deposited on its surface . Gel or abrasive
, rinsing the surface thoroughly,
mineral charge . using an abrasive sponge; in this way, the original matt
Although TiO2 creates an efficacious reticulation with the 15
polyester resin , it was necessary to check whether, when surface will be maintained . Being a homogeneous material
using ATH , said reticulation does not prevent thermoform in its entire thickness, it can be protected against surface
ability and easy repairness of the final product with suitable aggressions, such as scratches, cigarette burning , and resis
glues or fillers. Experimental tests showed that the final tant stains , restoring the beauty of the original surface by
product obtained after molding is still thermoformable. 20 simply following these instructions; small surface damage
Optionally , mineral charges of siliceous type (SiO2) with can be repaired with an abrasive sponge and an ordinary
size lower than 0.1 mm can be added to the composition in abrasive cleaner. By superficially polishing the damaged
a quantity comprised between 2 % and 15 % with respect to part, if the defect is still visible, the surface can be treated
the composition . For example, cristobalite , calcium silicate, again with very fine sandblasting paper.
wollastonite and/or feldspars , full and hollow (enlightened ) 25 Additional features of the invention will appear clearer
glass microspheres can be used amongstmineral charges of from the following description , which refers to the merely
siliceous type (SiO2). illustrative , not limiting embodiments shown in the
The non -metalliferous mineral charges that can be used examples and in the attached Figures, wherein :
include white talcum , quartz sand , siliceous sand , carbonate FIG . 1 shows the anchoring of TiO2 to polyester resin ;
sand , calcium carbonate , marble granulates, ventilated 30 FIG . 2 is a chart that shows the trend of AE ofmethylene
quartz, barites, kaolins, hydrated alumina, hydrated calcium blue , measured with colorimeter in three samples, after
borate , alumina trihydrate , micas , aluminum oxides, alumi exposure to a Xenon lamp;
num sesquioxyde, magnesium oxides, wollastonite, feld FIG . 3 is a chart that shows the trend of AE of eosin
spar, virgin ground glass, and full and hollow ( enlightened ) measured with colorimeter, in three samples after exposure
glass microspheres. 35 to a Xenon lamp ; and
Moreover, virgin or recovered mineral charges can be FIG . 4 is a chart that shows the viscosity trend in three
added . The recovery of mineral charges derives from samples over time.
charges coming either from processing ATH materials , The production process of the self-cleaning material pro
quartz ceramic and recovery glass or from ground sinks vides for a first step in which the TiO2 active principle is
scrap . 40 added to polyester resin . This step provides for an exclusive
A dispersion is obtained from mixing the materials of the anchoring process, by means of covalent bond , of the TiO2
composition , which contains photocatalytic nanometric active principle to the composite structure of the polyester
TiO2 that is chemically and intimately bond to the compo resin , by means of a compatibilizing anchoring agent com
sition structure , thusmaking the entire dispersion photocata posed of the anchoring silanizing agent that determines the
lytic both superficially and inside. 45 formation of the covalent bond between the photocatalytic
The product obtained by polymerizing said dispersion is TiO2 and the polyester resin .
a composite of polyester resin charged with a soft mineral Silane is the cause of a silanization reaction that produces
charge (MOHS hardness lower than 5). Such product is a a covalent bond between TiO2 and the polyester substrate.
highly innovative product with no precedents on the market Such a bond guarantees the anchoring of the TiO2 to the
until now , because it is a soft product that can be easily 50 structure by means of a strong irreversible bond .
worked, repaired and thermoformed , in addition to having Silane is perfectly dispersed in the polyester resin by
exceptional intrinsic photocatalytic properties . means of agitation at 900 rpm for 10 minutes. Successively,
It must be considered that polyester resin does not require the photocatalytic TiO2 is added to the polyester resin in
any special molding know -how or skills because this tech order to obtain the best dispersion possible . Such a formu
nology has been studied and used for many years. Polyester 55 lation is kept in dispersion with a screw agitator at a speed
resin molding makes use of simple systems and known of 900 rpm for 2.5 hours . Then the speed is increased to 1800
catalysts. The molds used to process said polyester disper rpm for 30 minutes, in such manner to guarantee a complete
sions are very simple to make (using epoxy resin , or dispersion of the Tio , in the polyester resin .
polyester resin or polyethylene with fiberglass reinforce The time necessary for the functionalization , that is to say
ments ), not structured and advantageously inexpensive. 60 for the silanization of the photocatalytic titanium , is approxi
Using alumina trihydrate (ATH ) as mineral charge , the mately 3 hours. After such a reaction time the remaining
final product is a composite that can be easily worked with components can be added .
ordinary carpenter's tools, such as saws; moreover, surfaces FIG . 1 shows the anchoring of Tio , to the polyester resin .
can be sandblasted or polished with ordinary sand -blasting All the other components are added after anchoring the
and polishing papers . The surfaces can be cut, rounded , 65 TiO2 to the silossanic function of the silane , starting from
filled , polished , thermoformed , perforated , sandblasted and alumina trihydrate (ATH ) mineral charges, followed by
glued . crosslinkers.
US 10,519,294 B2
5 6
Such a charged dispersion is kept homogeneously in The peculiarity of the invention is represented by the
agitation with a screw agitator at a speed of 900 rpm for 2.5 dispersion of photocatalytic titanium dioxide ( T10 , ) inside
hours and at a speed of 1800 rpm for 30 minutes. the polyester resin and polyester with methylmethacrylate
The final dispersion is placed in a mold and polymeriza and mineral charge that is successively polymerized . For this
tion is carried out either thermally or chemically at ambient 5 reason , the following comparative studies and tests were
temperature . made both on cross -linked resins and on resins containing
Thermally , the material is heated starting from an ambient the photocatalytic Tioz, both after adding inorganic mate
temperature of 25-30 ° C. for a time comprised between 30 rial, such as alumina trihydrate (ATH ) mineral charges that
and 40 minutes , then the temperature is increased with 10 represent the majority of the final product .
heating ramps up to 100 ° C. and cooled according to the type The photocatalytic degradation is exclusively carried out
of dispersion and to the thermostatation system of the mold . by the TiO2 that is found on the surface of the polymeric
Table 1 shows an example of a typical heating cycle for material. TiO2 is a heterogeneous catalyst that, when acti
a strongly charged polyester dispersion . vated by light, can generate a series of oxigenated active
15 species, such as O2. , . OH , and H2O2, which are suitable for
TABLE 1 degrading most organic agents . Therefore, TiO2 only acts as
TIME (min ) Temperature catalyst and does not participate in the degradation process
directly
0
0-60
30 ° C.
65 ° C.
Based on the above considerations , the preparation of the
For 8 hours 100 ° C. 20 material functionalized with TiO2was carried out by mixing
various organic components as indicated below :
Organic Part
Chemically , using the same formulation /chemical com methacrylic syrup : metylmethacrylate (MMA )/polyme
position , polymerization occurs by means of a series of tylmethacrylate (PMMA ) or
suitable catalysts that start the reaction at ambient tempera- 25 polyester resin of POLYLITE 32166-16 REICHHOLD
ture . type or
TBPM terbutyl peroxymaleate produced by Pergan PER polyester resin of POLYLITE 32166-16 REICHHOLD
OXAN PM - 25 type and methyl methacrylate MMA
Ca(OH )2 Cross -Linking Agents :
THIOCURE® PETMP Pentaerythritol tetra (3 -mercapto- 30 dietylenglicoledimethacrilate (EGDM );
propionate ) produced by BRUNO BOCK . tetraetylenglicoledimethacrilate (TEGDM );
The same aesthetic , mechanical and chemical results are trimetylolpropane trimethacrylate (TMPTMA);
achieved in the two different chemical and thermal polym 3Anchoring Molecule
-metacriloxipropyltrimetoxisilane (SILANE );
erizations .
The polyester resins functionalized with photocatalytic 35 Silanization Catalysts
TiO2 showed excellent results in terms of degradation of isopropylamine ( IPA );
various organic molecules , such as oleic acid and coloring methacrylic acid (AMA);
agents , like eosin Y, methylene blue and red methyl. It was Releasing agents:
possible to obtain a charged polymeric material with self stearic acid ;
cleaning surface by means of TiO2 mass dispersion in
40 Zn -stearate ;
presence of the 3- ( trimethoxysilyl)propyl methacrylate Families of Mineral Charges
silossanic function . Silicates (quartz , cristobalites, silicons, glass , glass full
and /or empty enlightened glass microspheres) ,of either
The silossanic group allows for anchoring TiO2 to the virgin or recovered type
polyester resin structure and at the same time acts as 45 Aluminas (alumina trihydrate ATH , aluminum oxides ) of
disgregating agent; in this way, TiO2 is completely dispersed either virgin or recovered type .
in the material both on the surface and in the mass. Recovery can be of both internal and external type . It is
The alumina trihydrate ( ATH ) mineral charge particles of internal type by re -using ground sinks as GREEN recov
with size lower than 0.1 mm provide a suitable homogeneity ery mineral charge or of external type by using mineral
to the dispersion composition and favor a homogeneous 50 charges recovered from other industries, such as ceramic and
surface upon molding. mine industries instead of quartz , or ATH or other virgin
Advantageously , TiO2 is in anatase form and in powder, mineral charges.
with a nanometric grain size lower than 300 nm . Following are three examples of the samples used for
Advantageously , the polymeric part is only composed of various comparative tests with the prior art . The sample
polyester resin . 55 compositions are characterized by a different content of
A methacrylic monomer, such as methyl methacrylate organic part, mineral charges and TiO2, but with the same
(MMA ), can be added to the polyester resin , in weight amount of cross - linking agents and silane.
percentage lower than 15 % compared to the weight of the
polyester resin and MMA mixture . EXAMPLE 1 ( PMMA /MMA (Syrup ) +0.3 %
Preferably, the compatibilizing anchoring agent is silane, 60 TiO2 + Quartz ) (Composition Described in
which is added to the mixture in a quantity equal to TiO2; WO2013 /017651)
silane can be added up to a double quantity compared to
TiO2 in order to guarantee a complete disgregation of the The following components are mixed in a 1000 cc high
photocatalyist ( TiO2) . density polyethylene container using a screw agitator ( speed
If the compatibilizing agent is trimetoxisilane , silaniza- 65 from 900 to 1800 rpm ):
tion catalysts, isopropilamine (IPA ) and methacrylic acid 305.00 grams of high -purity methyl methacrylate ;
(AMA ) are used in equal quantity . 45 grams ofmethyl methacrylate polymer.
US 10,519,294 B2
7 8
The mixture was agitated until the complete dissolution of Then the following components are added :
the PMMA polymetylmethacrylate polymer was obtained . 3 grams of TiO2 P -25 produced by DEGUSSA ;
Then the following components were added : Minimum mixing time is 2.5 hours and then the following
6 grams of silane DYNASYLAN MEMO 3 ( Trimethox components are added :
ysilyl)propyl methacrylate ; 5 559.2 grams of ATH (alumina trihydrate ) mineral charge
with size lower than 50 micron
3 grams of TiO2 P - 25 produced by DEGUSSA ; 4.00, 3.00 , 12.00 grams of cross - linking agents, respec
Minimum mixing time is 2.5 hours and then the following tively of EGDM - TEGDM - TMPTM ;
components are added : 1.5 g of zinc stearate.
620.36 grams of quartz-type mineral charge with 0.1-0.6 10 Variable quantities ofmethacrylic acid and isopropylam
mm size and white color ine mixtures of approximately 0.06 and 0.07 grams respec
4.00 , 3.00 , 12.00 grams of cross-linking agents, respec tively are used as silanization catalysts.
tively of EGDM - TEGDM -TMPTM ; Then , the mineral charge and the Zn -stearate are added
0.60 grams of zinc stearate . and the dispersion is agitated or rolled for at least 6 hours,
which is the time needed by the mineral charge for bonding
Variable quantities
propylamine of methacrylic
( IPA ) mixtures acidrespectively
of 0.22 grams (AMA) andwere
iso- 15 with the silossanic functions that are still free.
used as silanization catalysts . Then , 0.5 % of Luperox MEKP (Methyl Ethyl Ketone
peroxide) polymerization catalyst at 1.5 % and 0.15 % of
Preparation is made by mixing the aforementioned com stearic acid as releasing agent are added and the solution is
ponents in the following order ; firstly , methyl methacrylate agitated at 1800 rpm for 15 minutes. The material is cast in
is mixed with polymetylmethacrylate (PMMA ). Then cross- 20 the molds and polymerization is carried out at constant
linking agents ( EGDM , TEGDM , TMPTM ) and Zn -stearate temperature with water at 65 ° C. for 1 hour, successively,
are added and the dispersion is agitated for at least 2.5 hours . post -curing is made at 90 ° C. for 8 hours with polymeriza
In this way, the organic part is mixed , then DYNASY tion according to Table 1.
LAN MEMO (3-( Trimethoxysilyl)propyl methacrylate ) is EXAMPLE 3 (Polyester and MMA Solution + 0.3 %
added , followed by the addition of P - 25 TiO2, AMA and 25 TiO2 + ATH ) (Invention )
IPA ; in such way, it is guaranteed that the Tio , interacts with
the silossanic function before adding the mineral charge The following components are mixed in a 1000 cc high
which is provided in excess with respect to TiO2; the density polyethylene container using a screw agitator ( 900
Ti – O – Si bond is sufficiently strong and this excludes 1800 rpm ):
competition phenomena between quartz and the silossanic 30 370.00 grams of POLYLITE 32166-16 REICHHOLD
function Si(OCH3)3 ), thus guaranteeing the anchoring of polyester;
the photocatalytic TiO , to the polymeric structure . 60 grams of high - purity methyl methacrylate;
Then , the mineral charge and the Zn - stearate are added 6 grams of silane DYNASYLAN MEMO 3 ( Trimethox
and the dispersion is agitated or rolled for at least 6 hours, 35 ysilyl)propyl methacrylate ;
which is the time needed by the recovery mineral charge for 3 grams of TiO2 P -25 produced by DEGUSSA ;
bonding with the silossanic functions that are still free . Minimum mixing time is 2.5 hours and then the following
components are added :
Then , 0.5 % of Perkadox 16 polymerization catalyst and 549.92 gramsofATH (alumina trihydrate ) mineral charge
0.15 % of stearic acid as releasing agent are added and the with size lower than 50 micron
solution is agitated at 1800 rpm for 30 minutes. 40 2.25 , 1.5 , 6 grams of cross-linking agents, respectively of
The final dispersion is placed in a mold and polymeriza EGDM - TEGDM - TMPTM ;
tion is made thermally : the material is heated starting from 1.20 grams of zinc stearate .
an ambient temperature of 25-30 ° C., which is gradually Variable quantities of methacrylic acid and isopropylam
increased with heating ramps up to 100° C. and cooled , for ine mixtures of approximately 0.06 and 0.07 grams respec
an average time comprised between 20 and 40 minutes 45 tively are used as silanization catalysts .
according to the type of dispersion and to the thermostata Then , the mineral charge and the Zn-stearate are added
tion time of the mold . and the dispersion is agitated or rolled for at least 6 hours ,
Then , the mineral charge and the Zn -stearate are added which is the time needed by the mineral charge for bonding
and the dispersion is agitated or rolled for at least 6 hours , with the silossanic functions that are still free .
which is the timeneeded by the mineral charge for bonding 50 Then , 0.5 % of Luperox MEKP (Methyl Ethyl Ketone
with the silossanic functions that are still free . Peroxide) polymerization catalyst at 1.5 % and 0.15 % of
Then , 0.5 % of Perkadox 16 polymerization catalyst and stearic acid as releasing agent are added and the solution is
0.15 % of stearic acid as releasing agent are added and the agitated at 1800 rpm for 15 minutes. The material is then
solution is agitated at 1800 rpm for 30 minutes . Then the cast in the molds and polymerization is carried out at
material is cast in the molds and polymerization is carried 55 constant temperature with water at 65 ° C. for 1 hour;
out according to the prior art . successively , post -curing is made at 90 ° C. for 8 hours with
polymerization according to Table 1.
EXAMPLE 2 (Polyester + 0.3 % TiO2 + ATH ) As it can be seen , in all samples of examples 1, 2 and 3 ,
(Invention ) Silane was added in double percentage than TiO2. The TiO2
60 dispersion and the catalyst disgregation is guaranteed both
The following components are mixed in a 1000 cc high by the nanometric size of the TiO2 P - 25 (average diameter
density polyethylene container using a screw agitator (900 is approx . 21 nm ) and by the presence of the silossanic group
1800 rpm ): provided in excess compared to the Ti02.
420.00 grams of polyester POLYLITE 32166-16 REICH It was possible to obtain a polymeric material with
HOLD ; 65 self -cleaning surface by means of mass dispersion of the
6 grams of silane DYNASYLAN MEMO 3 ( Trimethox TiO2 in the presence of the 3( Trimethoxysilyl)propyl meth
ysilyl)propyl methacrylate ; acrylate silossanic function . The silossanic group allows for
US 10,519,294 B2
9 10
anchoring the TiO2 to the structure of the polymeric mate TABLE 2 -continued
rial, and at the same time acts as disgregating agent. ?? AE AE ?? ?? ??
METHYLENE time time time time time time
EXAMPLE 4 (PMMA/MMA (Syrup) + 0.3 % BLUE 0 50 100 150 200 250
TiO2+ Quartz ) (Composition Described in 5 DEGRADATION min min min min min min
WO2013/017651) with Chemical Catalysis ) EXAMPLE Polyester 0 11 13 14 15 16
2 composite + 0.3 %
The same formulation of EXAMPLE 1 is chemically TiO2 + ATH
polymerized with a series of suitable catalysts that start the EXAMPLE Polyester-MMA 0 12 13 15 16 17
3 and 5 composite + 0.3 %
reaction at ambient temperature . They are: 10
0.3 % TiO2 + ATH
TBPM terbutyl peroximaleate produced by Pergan PER
OXAN PM -25 in percentage from 0.5 % to 2.0 % ,
namely 1 % Table 2 and FIG . 2 show the degradation of methylene
Ca(OH ) 2 in percentage from 0.5 % -1.0 % , namely 0.6 %
THIOCURE® PETMP Pentaerythritol tetra ( 3-mercapto- 15 sampleoffrom
blue a composite sample from example 1 and 4 , of a
example 2 and of a sample from example 3 and
propionate ) produced by BRUNO BOCK in percentage 5 (0.3 % of photocatalytic TiO , and mineral charges ).
from 0.1 % to 1.0 % , namely 0.2 %
EXAMPLE 5 (Polyester and MMA Solution + 0.3 % TABLE 3
TiO2+ ATH ) ( Invention ) with Chemical Catalysis) 20 ?? ?? ?? ?? ?? ??
time time time time time time
The same formulation of EXAMPLE 3 is chemically DEGRADATION 0 50 100 150 200 250
polymerized with a series of suitable catalysts that start the WITH EOSINE min min min min min min
reaction at ambient temperature . The catalysts can be: EXAMPLE Syrup composite + 0 15 20 22 25 28
TBPM terbutyl peroximaleate produced by Pergan PER 1 and 4 0.3 % TiO2 +
OXAN PM -25 in percentage from 0.5 % to 2.0 % , 25 QUARTZ
namely 1 % EXAMPLE Polyester 0 13 15 20 22 25
Ca (OH )2 in percentage from 0.5-1.0 % , precisely 0.6 % 2 composite + 0.3 %
THIOCURE® PETMP Pentaerythritol tetra ( 3 -mercapto TiO2 + ATH
EXAMPLE Polyester-MMA
propionate ) produced by BRUNO BOCK in percentage 3 and 5 composite + 0.3 %
0 11 16 20 21 24
from 0.1 % to 1.0 % , namely 0.2 % 30 TiO2 + ATH
Comparative Tests on Polymerized - Composite Samples
1. TiO , Photocatalytic Activity
The photocatalytic activity was checked by assessing the Table 3 and FIG . 3 show the eosin degradation ofa sample
decoloration of the following organic coloring agents, such from example 1 and 4 , of a sample from example 2 and of
as eosin and methylene blue , which simulate the natural 35 a sample from example 3 and 5 (0.3 % of photocatalytic TiO2
coloring agents that are mostly used in cooking , such as and mineral charges ).
wine, vinegar, strawberries, and other staining agents, which Based on the test results , coloring agents are degraded by
are placed on the composite surface . TiO2 ; this is a very important result because it allows for
a ) Self -cleaning of surfaces stained with eosin ; defining the surface of material from examples 1 and 4 , 2
bThe) Selfself-cleaning
-cleaningof surfaces stainedstained
of surfaces with methylene
with eosin blue
and; 40 and 3bonded
and 5 as self-cleaning ;moreover, itconfirmsthat TiO2
methylene blue allows for assessing the degradation capac had to the structure of the polyester resin of
ity of TiO2 against some coloring agents, such as eosin and TiO2 emerges to 3the
examples 2 and and 5 , according to the invention , because
surface as in example 1 on methacrylic
methylene blue. syrup , according to the prior art.
The photocatalytic activity of the composite of examples 45
1 and 4 , 2 and 3 and 5 (0.3 % of photocatalytic TiO2 and In all tests the materials that contained TiO2 showed a
mineral charges) was checked . The photocatalytic activity high dispersion and homogeneity of TiO2, without decanta
was checked by immersing the composite of examples 1 and tion phenomena , as shown by the chromatic coordinates ,
4 , 2 and 3 and 5 (0.3 % of photocatalytic TiO2) in a 0.0025 that is to say the color variation of the dispersion to assess
M solution of methylene blue and eosin Y and measuring the 50 the dispersion homogeneity in the tests of Table 4 below .
time needed to degrade said coloring agents . Degradation
was made using a Xenon lamp (SolarBox 1500 and 25 TABLE 4
mW /cm², 2 = 280-400 nm , outdoor filter ) and coloring was ??
monitored with colorimetric measurements (Color 17
X -Rite ). Measurements were made after 60 , 90 , 150, 210 , 55 EXAMPLE 1 Syrup composite + 0.3 % TiO2 +
WO2013 /017651 QUARTZ
0.50
and 270 minutes of exposure and the colorimetric variation EXAMPLE 2 Polyester composite + 0.3 % TiO2 + 0.60
was expressed in function of AE . Invention ATH
EXAMPLE 3 Polyester-MMA composite + 0.3 % 0.40
TABLE 2 Invention TiO2 + ATH
60
EXAMPLE 4 Syrup composite + 0.3 % TiO2 + 0.50
?? ?? ?? ?? ?? ?? WO2013/017651 QUARTZ chemical catalysis
METHYLENE time time time time time time EXAMPLE 5 Polyester-MMA composite + 0.3 % 0.40
BLUE 0 50 100 150 200 250 Invention TiO2 + ATH chemical catalysis
DEGRADATION min min min min min min

EXAMPLE Syrup composite + 0 10 12 13 14 15


65 2. Viscosity Variation with Silane Addition
1 and 4 0.3 % TiO2 +
QUARTZ The viscosity of samples from examples 1, 2 and 3 with
Silane and TiO2 in 1 : 2 ratio , at 0 time, at 60 minutes and at
US 10,519,294 B2
11 12
120 minutes was measured in order to assess the chemical TABLE 7
bond of Silane with the polyester resin .
An evident variation of the resin viscosity is found after Bending
adding silane to a polyester resin or to a polyester resin and THERMOFORMABILITY degree
MMA with the addition of TiO2. Such a variation confirms 5 EXAMPLE 1 and 4 Syrup composite + 0.3 % 0°
the presence of direct interaction phenomena between TiO2 TiO2 + QUARTZ
and silane . The measurement of TiO2 silanization time EXAMPLE 2 Polyester composite + 250
through the viscosity value of dispersions with different 0.3 % TiO2 + ATH
addition of silane gave the results shown in Table 5 and in 10 EXAMPLE 3 and 5 Polyester-MMA 24 °
FIG . 4 below . composite + 0.3 % TiO2 +
ATH
TABLE 5
Cps Cps
Cps Viscosity Viscosity 15
As shown in Table 7, the samples of examples 2 and 3 and
Viscosity time time 5 according to the invention have a bending degree higher
VISCOSITY time 0 60 min 120 min than 20 °, whereas the sample of example 1-4 has no bending
EXAMPLE Syrup dispersion + 8,000 7,100 6,400 degree . The bending degree is the angle that can be formed
1 0.3 % TiO2 + QUARTZ from a flat surface that is considered as angle 0 ° .
EXAMPLE Polyester dispersion + 4,000 3,500 3,300 20 Therefore , samples 2a and 3 and 5 are thermoformable ,
2 0.3 % TiO2 + ATH
EXAMPLE Polyester dispersion 9,000 7,800 6,800 whereas samples 1 and 4 are not thermoformable .
3 MMA + 0.3 % TiO2 +
ATH Numerous variations and modifications can be made to
the present embodiments of the invention , which are within
the reach of an expert of the field , falling in any case within
The viscosity values were measured at a temperature of 25 claims
the scope
approximately 20 ° C.As shown in Table 5 and FIG . 4 , all the .
of the invention as disclosed by the attached
examples show a clear variation of viscosity when silane is
added , this being an evident sign that a chemical bond is The invention claimed is :
established. Data shows that the higher viscosity reduction
is more evident after the first 60 minutes, this being a clear 30
1. A self-cleaning composite material comprising:
sign that the chemical bond is established within such a 50-85 % by weight of mineral charges,
period of time. 10-30 % by weight of polymer ;
3. Visible Cross -Linking on the Surface of the Finished photocatalytic titanium dioxide ( TiO2);
Product 35
In this test the finished products are sinks obtained from a compatibilizing agent for anchoring between the pho
the dispersions of examples 1, 2 and 3. Cross -linking is tocatalytic TiO2 and the polymer, wherein said anchor
visible with the naked eye in the three finished products ing compatibilizing agent of the photocatalytic TiO2 is
because the sink surfaces show a very reticulated and very silane; and
matt surface with a very high aesthetic appeal. Such a 40 cross- linking monomers that cross -link the polymer ,
surface is very different from the surfaces that do not contain wherein said mineral charges comprise alumina trihy
titanium dioxide bonded with silence, which are on the drate (ATH ), and said cross- linking polymer comprises
contrary very polished , with non -homogeneous opacity and polyester resin , wherein the photocatalytic titanium
poor cross-linking. dioxide is dispersed in the cross- linked polymer in a
4. Hardness and Thermoformability 45 weight percentage of 0.05 % -5 % with respect to a
Hardness and thermoformability tests were carried out on weight of the cross -linked polymer .
the samples of examples 1, 2, 3, 4 and 5 , as respectively 2. The self-cleaning composite material of claim 1,
shown in Table 6 and 7 below . Hardness was measured in wherein said alumina trihydrate (ATH ) has a grain size of
HRM . 50 10-50 microns.
TABLE 6 3. The self-cleaning composite material of claim 1 ,
wherein methylmethacrylate (MMA ) is added to said poly
HARDNESS HRM ester resin in a weight percentage lower than 15 % of the
EXAMPLE 1 Syrup composite + 0.3 % TiO2 + QUARTZ 105.00 55
weight of the polyester resin and a methyl methacrylate
EXAMPLE 2 Polyester composite + 0.3 % TiO2 + ATH 90.00 (MMA) mixture.
EXAMPLE 3 Polyester -MMA composite + 0.3 % TiO2 + 92.00
ATH 4. The self-cleaning composite material of claim 1,
EXAMPLE 4 Syrup composite + 0.3 % TiO2 + QUARTZ 104.00 wherein said silane is 3-(trimethoxysilyl) propyl methyl
EXAMPLE 5
chemical catalysis
Polyester-MMA composite + 0.3 % TiO2 + 93.00
methacrylate and said silane is in a double quantity with
ATH chemical catalysis 60 respect to the photocatalytic TiO2.
5. The self-cleaning composite material of claim 1, further
comprising :
Asshown in Table 6 , the samples of examples 2 and 3 and silanization catalysts .
5 according to the invention have low hardness features
compared to the sample of example 1 according to the prior 65 6. The self-cleaning composite material of claim 1,
art . For this reason , samples 2 and 3 and 5 are easy to work , wherein said photocatalytic titanium dioxide is in an anatase
whereas samples 1 and 4 are difficult to work . form and in a powder with a grain size lower than 300 nm .
US 10,519,294 B2
13 14
7. The self-cleaning composite material of claim 1, the polyester resin , the silane and the photocatylitic
wherein said crosslinking monomers comprise ethylene gly titanium dioxide in order to obtain a reticulation of the
col dimethacrylate (EGDM ), tetraethylene glycolmethacry polyester resin ;
late (TEGDM ) and trimethylolpropane trimethacrylate agitating the final mixture ; and
( TMPTMA ). 5 polymerizing the mixture in a mold .
8. The self-cleaning compositematerial of claim 1, further 10. The process of claim 9 , wherein said silane is added
comprising: in a double quantity with respect to the photocatalytic TiO2.
11. The process of claim 9, wherein the agitating of the
fine particles of a silicate with a grain size lower than 0.1 polyester resin and the silane the agitating of the polyester
mm , in a weight percentage between 2 % and 15 % with 10 resin , silane and titanium dioxide ( TiO2) mixture are made
respect to the weight of the total composite material. with a screw agitator at a speed of between 900 rpm and
9. A production process for a self-cleaning composite 1800 rpm respectively for a time of 30 minutes and 2.5 hours
material , the production process comprising : before the step of adding.
preparing a polyester resin in a quantity corresponding to 12. The process of claim 9 , wherein step of polymerizing
10 % -30 % of a final product weight; 15 in the mold is made at an initial temperature of 50° C. that
dispersing silane in the polyester resin ; increases gradually to 100 ° C. for a time of 8 hours .
agitating the polyester resin and the silane ; 13. The process of claim 9 , wherein step of polymerizing
dispersing photocatalytic titanium dioxide ( TiO2) in the is performed chemically , at room temperature , by one or
polyester resin and the silane, in a weightpercentage of more of TBPM ( Tert- Butyl Peroxymaleate ) in a percentage
0.05 % -5 % with respect to a weight of the polyester 20 Ca (OH%) 2to(calcium
from 0.5 2.0 % ,
hydroxide ) in a percentage from 0.5 %
resin ; to 1.0 % ,
agitating the polyester resin , the silane and the titanium PETMP Pentaerythritol Tetra( 3 -mercaptopropionate ) in a
dioxide (TiO2 ); percentage from 0.1 % to 1.0 % .
adding 50 % -85 % in weight of alumina trihydrate ( ATH )
based mineral charges and cross - linking monomers to

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