Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Unsaturated polyester resin for engineered stone comprising fine and/or porous
particles
[0001] The invention relates to an unsaturated polyester resin of low
molecular weight which is useful
for the preparation of engineered stone. When mixing the unsaturated polyester
resin with a fine
and/or porous inorganic particulate material such as fine quartz and/or
cristobalite, a formable
composition is obtained that can be further processed and cured to finally
yield engineered stone as
composite material. The invention also relates to a method for the preparation
of engineered stone as
well as to the use of the unsaturated polyester resin for the preparation of
engineered stone.
[0002] In the conventional manufacture of engineered stone slabs, a resin
formulation is mixed with
crushed stone, typically quartz fillers and/or quartz aggregates of defined
particle sizes. The resin
formulation is curable upon activation by addition of a metal catalyst and
peroxide. After addition of
said metal catalyst and peroxide, curing of the resin formulation commences
and proceeds until the
resin has been completely cured. During the interim period (pot life) the
curing composition can be
formed into the desired shape of the engineered stone.
[0003] US 8,026,298 relates to a method for the preparation of engineered
stone slab having coated
Jumps of composite stone material. US 8,436,074 relates to artificial marble,
and system and method
of producing artificial marble.
[0004] US 4,032,596 pertains to curing of unsaturated polyester resins in
admixture with ethylenically
unsaturated copolymerizable monomers and is particularly concerned with
promoting or accelerating
the cross linking of such polyester with such vinyl monomers during curing
while retaining
serviceable shelf-life during storage of the permix at ambient or room
temperatures.
100051 WO 2012/104020 relates to a gelcoat composition comprising a reactive
polyester resin and a
particulate inorganic filler and to a method of applying the gelcoat
composition to suitable substrates
such as sanitary basins, e.g. sinks, washbasins, spas, shower basins,
lavatories, and the like. The
solidified gelcoat provides excellent scratch resistance to the surface of the
substrate.
[0006] GB-A 834 286 discloses that the storage life of a copolymerizable
mixture of an unsaturated
alkyd resin and an ethylenic monomer copolymerizable therewith, which mixture
contains an inhibitor
against premature gelation, can be improved by adding thereto, a copper
compound soluble in the
alkyd resin mixture in an amount ranging from 0.25 to 10 parts per million,
based on the weight of the
resinous mixture.
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[0007] US 3,028,360 is concerned with improving the storage life of polyester
resins.
[00081 EP-A 2 610 227 discloses an artificial marble including unsaturated
polyester resin (A),
compound containing silica (B), and luminescent pigment (C).
[0009] W02016/003867 relates to a formable composition for the preparation of
engineered stone
comprising a prepromoted unsaturated polyester resin system, an inorganic
particulate material and a
peroxide component.
[0010] Conventional resin formulations are not satisfactory in every respect
and there is a demand for
methods for the preparation of engineered stone that have advantages compared
to the prior art. The
engineered stone should be easy to manufacture by means of conventional
equipment and should have
excellent optical and mechanical properties.
100111 This object has been achieved by the subject-matter of the patent
claims.
[0012] It has been surprisingly found that engineered stone having excellent
optical and mechanical
properties can be prepared from tine particulate material, especially quartz
and cristobalite, and an
unsaturated polyester resin having a comparatively low molecular weight and
viscosity.
[0013] The unsaturated polyester resin according to the invention is
particularly useful for the
manufacture of engineered stone from cristobalite, which is a silicon dioxide
filler that can be obtained
e.g. by high temperature polymorph transformation of quartz or silica.
Cristobalite has a very white
color and the individual particles are characterized by a plurality of micro
holes (see Figure 1). Fine
quartz also has a very white color.
[0014] Without wishing to be bound to any scientific theory, the unsaturated
polyester resin according
to the invention is capable of penetrating these micro holes thereby filling
them and providing the
cured engineered stone with substantially better mechanical properties
compared to conventional slabs
made from cristobalite with conventional resins.
[0015] The unsaturated polyester resin according to the invention can be used
in comparatively low
amounts relative to the amount of particulate material, e.g. cristobalite.
Conventional resins require
higher amounts, as the wetting properties of such conventional resins are
limited. Stone slabs made
from conventional resins tend to bend upon curing at high temperatures inside
the curing oven. In
consequence, these stone slabs need to be repolished after curing.
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[0016] It has now been surprisingly found that the bending tendency of the
stone slabs that are
manufactured from the unsaturated polyester resin according to the invention
have a substantially less
pronounced bending tendency, if any, as well as substantially improved
mechanical properties. As less
bending occurs, laborious repolishine of the cured material can be reduced
substantially.
[0017] Further, it has been surprisingly found that stone slabs show
substantially less cracks, if any,
when they are manufactured from resins which are derived from fumaric acid
partially or completely
substituting maleic acid or maleic acid anhydride. It is well known that
copolymerization reactivity of
fumarate with styrene is almost 20 times higher than that for maleate. [Osama
M. Musa, Handbook of
Maleic Anhydride Based Materials: Synthesis, Properties and Applications,
Springer, 2017, Vol 1, pp.
251-3101 Unsaturated polyester resins are typically synthesized by using
maleic anhydride that
isomerizes to fumarate during polymer estcrification reaction. The degree of
isomerization is
dependent on type of glycols used and improves by increase of polymer
esterification reaction time
and temperature. Substituting maleic anhydride with fumaric acid can be
therefore advantageous, as it
initially ensures high content of reactive fumarate double bonds, and thus,
results in higher crosslink
density when the resin is cured. Finally, its important to optimize amount of
crosslinking double
bonds in proportion to reactive diluent and to other components in the
unsaturated polymer structure.
Resins with too high content of reactive double bonds, can be too rigid or
brittle to be employed in the
manufacture of engineered stone slabs. It has been found that stone slabs that
are manufactured from
the unsaturated polyester resin according to the invention show substantially
less cracks and
brittleness.
[0018] Furthermore, it has been surprisingly found that stone slabs prepared
from resins comprising
adipic acid or a mixture of adipic acid with phthalic anhydride show
considerably improved
mechanical properties with respect to flexural strength and impact resistance.
It is known that the
aliphatic carbon chain of the adipic acid will enhance flexibility of the
stone slab and reduce cracks.
[0019] Thus, the unsaturated polyester resin according to the invention can be
manufactured and
processed easily and provides better properties at lower consumption.
[0020] Even further, it has been surprisingly found that the unsaturated
polyester resin according to
the invention requires lower amounts of reactive diluents such as styrene. Due
to low styrene content
compared with conventional resins, the residual content of styrene in the
cured stone slabs is reduced,
if any, thereby avoiding styrene-styrene polymers causing poor mechanical
properties and also having
poor UV resistance due to free aromatic conjugated double bonds.
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[0021] A first aspect of the invention related to an unsaturated polyester
resin component for the
preparation of engineered stone, wherein the unsaturated polyester resin
component has a weight
average molecular weight of not more than about 2500 g/mol and is obtained or
is obtainable by
reacting a mixture comprising
(i) a polycarboxylic acid component comprising at least 2 polycarboxylic
acids, wherein a first
carboxylic acid is selected from the group consisting of unsaturated aliphatic
polycarboxylic
acids, anhydrides or esters thereof and a second polycarboxylic acid is
selected from the group
consisting of saturated aliphatic polycarboxylic acids, anhydrides or esters
thereof;
(ii) a polyfunctional alcohol component comprising at least one
polyfunctional alcohol selected
from the group consisting of saturated aliphatic polyfunctional alcohols and
unsaturated
aliphatic polyfunctional alcohols;
(iii) optionally, a monocarboxylic acid component comprising at least one
monocarboxylic acid
selected from aromatic monocarboxylic acids, anhydrides or esters thereof;
saturated aliphatic
monocarboxylic acids, anhydrides or esters thereof; and unsaturated aliphatic
monocarboxylic
acids, anhydrides or esters thereof; and
(iv) optionally, a monofunctional alcohol component comprising at least one
monofunctional
alcohol selected from aromatic rnonofunctional alcohols, saturated aliphatic
monofunctional
alcohols, and unsaturated aliphatic monofunctional alcohols;
wherein the polycarboxylic acid component and/or the polyfunctional alcohol
component and/or the
monocarboxylic acid component and/or the monofunctional alcohol component
comprises ethylenic
unsaturation.
[0022] For the purpose of the invention, "poly" means "at least two. Thus, a
polycarboxylic acid has
at least two carboxylic groups (diacid, triacid, etc.), whereas a
polyfunctional alcohol has at least two
hydroxyl groups (diol, triol, etc.).
[0023] For the purpose of the invention, "component" refers to a constituent
that may be composed of
a single compound or of a plurality (e.g. mixture) of compounds having a
common property. For
example, a polycarboxylic acid component may consist of a single
polycarboxylic acid or of a mixture
of 2, 3 or 4 different polycarboxylie acids. For the purpose of the
specification, unless expressly stated
otherwise, all values referring to a component refer to the total quantity of
said component, i.e. to the
plurality of all compounds having said common property.
[0024] For the purpose of the specification, definitions of weight contents of
monomers that arc
incorporated in the polyester backbone may be related to the total weight of
the resultant polyester
resin after esterification. A skilled person recognizes that depending upon
the starting materials,
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condensation reactions may occur or not. For example, esterification of
ethylene glycol with fumaric
acid releases one equivalent of water, whereas the same reaction with the acid
anhydride does not
release water. For the ease of specification, the water that may be released
in the course of the reaction
is preferably to be disregarded. Accordingly, unless expressly stated
otherwise, any weight
percentages of e.g. a carboxylic acid preferably refer to the residual
equivalent molecular weight of the
carboxylic acid moiety that is finally incorporated in the polymer backbone,
irrespective of whether it
is employed in form of the free acid or e.g. in form of an anhydride thereof.
[0025] Unsaturated polyester resin components are known to a skilled person
and for the purposes of
the invention not particularly limited. Typically, the unsaturated polyester
resin components according
to the invention are characterized by a polymerizable C=C double bond,
optionally in conjugation with
a carbonyl bond.
[0026] These unsaturated polyester resin components arc obtained or arc
obtainable by the
condensation of carboxylic acid monomers with polyfunctional alcohol monomers.
The polyester may
then be dissolved in a reactive monomer, such as styrene, to obtain a solution
that may then be
crosslinkcd. One skilled in the art will appreciate that there are many
different processes and methods
for making unsaturated polyester resin components and other resins having
ethylenic unsaturation that
may be applied within the scope of the invention.
[0027] Preferably,
(i) the polycarboxylic acid component comprises fumaric acid and adipic
acid; and
(ii) the polyfunctional alcohol component comprises propylene glycol and
diethylene glycol.
[0028] Preferably, the molar content of the second polycarboxylic acid which
is selected from the
group consisting of saturated aliphatic polycarboxylic acids, anhydrides or
esters thereof is not more
than 13.5 mole.-%, more preferred not more than 13.0 mole.-%, most preferred
not more than 12.5
mole.-% relative to the molar content of the polycarhoxylic acid component.
[0029] Preferably, the unsaturated polyester resin component according to the
invention is obtained or
is obtainable by reacting a mixture comprising a polycarboxylic acid component
(free acid, salt, ester,
anhydride) and a polyfunctional alcohol component, wherein the polycarboxylic
acid component
and/or the polyfunctional alcohol component comprises ethylenic unsaturation.
Said mixture may also
comprise saturated or unsaturated, aliphatic or aromatic monocarboxylic acids
and/or saturated or
unsaturated, aliphatic or aromatic monofunctional alcohols in order to adjust
the average molecular
weight of the polyester molecules.
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[0030] Preferably, the unsaturated polyester resin component is obtained or is
obtainable by reacting a
mixture comprising a polyfunctional alcohol and a carboxylic acid, a
carboxylic acid ester and/or a
carboxylic acid anhydride, i.e. the unsaturated polyester resin component is
derived from a monomer
composition (in the following also referred to as "mixture") comprising a
polyfunctional alcohol and a
carboxylic acid, a carboxylic acid ester and/or a carboxylic acid anhydride.
[0031] In a preferred embodiment, the mixture comprises a polyfunctional
alcohol and a
polycarboxylic acid, a polycarboxylic acid ester and/or a polycarboxylic acid
anhydride, i.e. the
unsaturated polyester resin component is the condensation product of one or
more polycarboxylic
acids, polycarboxylic acid esters and/or polycarboxylic acid anhydrides with
one or more
polyfunctional alcohols. More preferably, the mixture comprises a
polyfunctional alcohol and a
polycarboxylic acid and/or a polycarboxylic acid anhydride, i.e. the
unsaturated polyester resin
component is the condensation product of one or more polycarboxylic acids
and/or polycarboxylic
acid anhydrides with one or more polyfunctional alcohols.
[0032] The unsaturated polyester resin component according to the invention
has a weight average
molecular weight of not more than about 2500 g/mol, preferably not more than
about 2200 g/mol;
more preferably not more than about 2100 g/mol, still more preferably not more
than about 2000
g/mol, yet more preferably not more than about 1900 (limo', even more
preferably not more than about
1800 g/mol or not more than about 1700 g/mol, and in particular not more than
about 1500 g/mol.
[0033] Suitable methods for measuring the weight average molecular weight of
unsaturated polyester
resins are known to the skilled person and include size exclusion
chromatography.
[0034] Suitable methods for altering the weight average molecular weight of
unsaturated polyester
resins are known to the skilled person. The average molecular weight can be
influenced by the content
of polyfunctional monomers thereby influencing the degree of cross-linking, as
well as by the content
of monofunctional monomers thereby influencing the degree of end-capping.
[0035] Preferably, the unsaturated polyester resin component according to the
invention has a
viscosity (prior to curing) in the range of about 150 to about 400 mPas. More
preferred, the
unsaturated polyester resin component according to the invention has a
viscosity in the range of about
200 to about 350 mPas, even more preferred in the range of about 200 to about
300 mPas. Preferably,
the viscosity is measured according to ISO 2555 in a Brookfield viscometer at
25 C.
[0036] Preferably, the unsaturated polyester resin component according to the
invention has a
viscosity (prior to mixing with additives) in the range of about 400 to about
500 mPas at 100 C, more
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preferably in the range of about 400 to about 450 mPas at 100 C. Preferably,
the viscosity is
measured according to ISO 2555 in a Brookfield viscometer. The aforementioned
viscosity relates to
the viscosity of the unsaturated polyester resin component as such without any
additives, solvents,
diluents and the like, i.e. the unsaturated polyester resin component only
consisting of
(i) a polycarboxylic acid component as defined above;
(ii) a polyfunctional alcohol component as defined above;
(iii) optionally, a rnonocarboxylic acid component as defined above; and
(iv) optionally, a monofunctional alcohol component as defined above;
wherein the polycarboxylic acid component and/or the polyfunctional alcohol
component and/or the
monocarboxylic acid component and/or the naonofunctional alcohol component
comprises ethylenic
unsaturation.
[0037] The unsaturated polyester resin component according to the invention is
obtained or is
obtainable from a monomer mixture comprising a polycarboxylic acid component
comprising at least
two polycarboxylic acids independently of one another selected from the group
consisting of aromatic
polycarboxylic acids, anhydrides or esters thereof; saturated aliphatic
polycarboxylic acids, anhydrides
or esters thereof; and unsaturated aliphatic polycarboxylic acids, anhydrides
or esters thereof.
[0038] In a preferred embodiment, the polycarboxylic acid component comprises
a carboxylic acid, a
carboxylic acid ester and/or a carboxylic acid anhydride, wherein the
carboxylic acid, the carboxylic
acid ester and/or the carboxylic acid anhydride are/is selected from aliphatic
and aromatic
polycarboxylic acids and/or the esters and anhydrides thereof, wherein the
term "aliphatic" covers
acyclic and cyclic, saturated and unsaturated polycarboxylic acids and the
esters and anhydrides
thereof. Preferably, the carboxylic acid, the carboxylic acid ester and/or the
carboxylic acid anhydride
are/is selected from unsaturated and aromatic polycarboxylic acids and/or the
esters and anhydrides
thereof. More preferably, the carboxylic acid, the carboxylic acid ester
and/or the carboxylic acid
anhydride are/is selected from unsaturated polycarboxylic acids and/or the
esters and anhydrides
thereof.
[00391 In another preferred embodiment, the polycarboxylic acid component
comprises a carboxylic
acid, a carboxylic acid ester and/or a carboxylic acid anhydride, wherein the
carboxylic acid, the
carboxylic acid ester and/or the carboxylic acid anhydride are/is selected
from unsaturated
polycarboxylic acids and/or the esters and anhydrides thereof, and used in
combination with a second
carboxylic acid, carboxylic acid ester and/or carboxylic acid anhydride, which
are/is selected from
aliphatic and/or aromatic polycarboxylic acids and/or the esters and
anhydrides thereof. Preferably, the
carboxylic acid, the carboxylic acid ester and/or the carboxylic acid
anhydride are/is selected from
unsaturated polycarboxylic acids and/or the esters and anhydrides thereof, and
used in combination
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with a second carboxylic acid, carboxylic acid ester and/or carboxylic acid
anhydride, which are/is
selected from saturated and/or aromatic polycarboxylic acids and/or the esters
and anhydrides thereof.
More preferably, the carboxylic acid, the carboxylic acid ester and/or the
carboxylic acid anhydride
arc/is selected from unsaturated polycarboxylic acids and/or the esters and
anhydrides thereof, and
used in combination with a second carboxylic acid, carboxylic acid ester
and/or carboxylic acid
anhydride, which are/is selected from aromatic polycarboxylic acids and/or the
esters and anhydrides
thereof. Even more preferably, the carboxylic acid, the carboxylic acid ester
and/or the carboxylic acid
anhydride are/is selected from unsaturated polycarboxylic acids and/or the
esters and anhydrides
thereof, and used in combination with a second carboxylic acid, carboxylic
acid ester and/or
carboxylic acid anhydride, which are/is selected from aromatic polycarboxylic
acids and/or the esters
and anhydrides thereof, wherein the second carboxylic acid, carboxylic acid
ester and/or carboxylic
acid anhydride have/has a limited weight proportion in the reactive
unsaturated polyester resin system
compared to the carboxylic acid, the carboxylic acid ester and/or the
carboxylic acid anhydride
selected from unsaturated polycarboxylic acids and/or the esters and
anhydrides thereof, the weight
ratios (second carboxylic acid, carboxylic acid ester and/or carboxylic acid
anhydride : carboxylic
acid, the carboxylic acid ester and/or the carboxylic acid anhydride selected
from unsaturated
polycarboxylic acids and/or the esters and anhydrides thereof) being less than
about 0.8:1, preferably
less than about 0.5:1, more preferably about less than 0.2:1, even more
preferably less than about
0.1:1, and most preferably less than about 0.05:1.
[0040] The use of the saturated and/or aromatic polycarboxylic acids,
polycarboxylic acid esters
and/or polycarboxylic acid anhydrides in combination with unsaturated
polycarboxylic acids,
polycarboxylic acid esters and/or polycarboxylic acid anhydrides may serve to
decrease the crosslink
density after curing of the unsaturated polyester resin component, and
consequently the unsaturated
polyester resin component will typically be more flexible, shock resistant,
unbrittic, and the like.
[0041] In another preferred embodiment, the polycarboxylic acid component
comprises a blend of a
carboxylic acid, a carboxylic acid ester and/or a carboxylic acid anhydride,
wherein the carboxylic
acid, the carboxylic acid ester and/or the carboxylic acid anhydride are/is
selected from aliphatic and
aromatic dicarboxylic acids and/or the esters and anhydrides thereof, wherein
the term "aliphatic"
covers acyclic and cyclic, saturated and unsaturated dicarboxylic acids and
the esters and anhydrides
thereof. Preferably, a first carboxylic acid, the carboxylic acid ester and/or
carboxylic acid anhydride
are/is selected from unsaturated dicarboxylic acids and/or esters and
anhydrides thereof, and is used in
combination with a second carboxylic acid, carboxylic acid ester and/or
carboxylic acid anhydride,
which arc/is selected from saturated and/or aromatic polycarboxylic acids
and/or the esters and
anhydrides thereof. More preferably, a first carboxylic acid and/or a
carboxylic acid anhydride
selected from fumaric acid, maleic acid, and maleic acid anhydride is used in
combination with a
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second carboxylic acid and/or carboxylic acid anhydride selected from
isophthalic acid, phthalic acid,
terephthalic acid, and phthalic anhydride. More preferably, fumaric acid is
used in combination with
isophthalic acid or phthalic acid.
[0042] In a preferred embodiment, the polycarboxylic acid component comprises
a binary mixture of
- an aromatic polycarboxylic acid, anhydride or ester thereof with
- a saturated aliphatic polycarboxylic acid, anhydride or ester thereof.
[0043] In a preferred embodiment, the polycarboxylic acid component comprises
a binary mixture of
- an aromatic polycarboxylic acid, anhydride or ester thereof with
- an unsaturated aliphatic polycarboxylic acid, anhydride or ester thereof.
[0044] In a preferred embodiment, the polycarboxylic acid component comprises
a binary mixture of
- a saturated aliphatic polycarboxylic acid, anhydride or ester thereof
with
- an unsaturated aliphatic polycarboxylic acid, anhydride or ester thereof.
[0045] In a preferred embodiment, the polycarboxylic acid component according
to the invention
comprises a ternary mixture of
- an aromatic polycarboxylic acid, anhydride or ester thereof; with
- a saturated aliphatic polycarboxylic acid, anhydride or ester thereof;
and with
- an unsaturated aliphatic polycarboxylic acid, anhydride or ester thereof.
[0046] Preferred aromatic polycarboxylic acids are selected from aromatic
dicarboxylaic acids,
aromatic tricarboxylic acids, aromatic tetracarboxylic acids, and their
corresponding acid anhydrides.
A skilled person recognizes that the aromatic polycarboxylic acids may also be
employed in form of
esters, e.g. methyl esters or ethyl esters, in the corresponding
transesterification reactions.
[0047] Exemplary aromatic polycarboxylic acids include isophthalic acid,
phthalic acid, terephthalic
acid, tetrachlorophthalic acid, trimellitic acid, 1,2,4,5-
benzenetetracarboxylic acid, and 1,2,4-
benzenetricarboxylic acid. Preferred aromatic polycarboxylic acids are
isophthalic acid, phthalic acid,
terephthalic acid, and tetrachlorophthalic acid. More preferred aromatic
polycarboxylic acids are
isophthalic acid, and phthalic acid. The most preferred aromatic
polycarboxylic acid is isophthalic
acid.
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[0048] Exemplary aromatic polycarboxylic acid esters can be derived from
isophthalic acid, phthalic
acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid, 1,2,4,5-
benzenetetra-carboxylic acid,
and 1,2,4-benzenctricarboxylic acid.
[0049] Exemplary aromatic polycarboxylic acid anhydrides can be derived from
isophthalic acid,
phthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid,
1,2,4,5-
benzenetetracarboxylic acid, and 1,2,4-benzenetricarboxylic acid. Preferred
aromatic polycarboxylic
acid anhydrides arc the aromatic polycarboxylic acid anhydrides of phthalic
acid and
tetrachlorophthalic acid. The most preferred aromatic polycarboxylic acid
anhydride is phthalic
anhydride.
[0050] Preferred saturated aliphatic polycarboxylic acids are selected from
the group consisting of
saturated aliphatic dicarboxylic acids, saturated aliphatic tricarboxylic
acids, saturated aliphatic
tctracarboxylic acids, and their corresponding acid anhydrides. A skilled
person recognizes that the
saturated aliphatic polycarboxylic acids may also be employed in form of
esters, c.a. methyl esters or
ethyl esters, in the corresponding transesterification reactions.
[0051] Exemplary saturated aliphatic polycarboxylic acids include adipic acid,
chlorendic acid,
dihydrophthalic acid, dimethy1-2,6-naphthenic dicarboxylic acid, d-methyl
glutaric acid,
dodecanedicarboxylic acid, glutaric acid, hexahydrophthalic acid, oxalic acid,
malonic acid, suberic
acid, azelaic acid, nadic acid, pimelic acid, sebacic acid, succinic acid,
tetrahydrophthalic acid, 1,2-
cyclohexane dicarboxylic acid, 1,3-cyclohcxane dicarboxylic acid, 1,4-
cyclohexane dicarboxylic acid,
and Diels-Aldcr adducts made from malcic acid anhydride and cyclopentadiene.
Preferred saturated
polycarboxylic acids are succinic acid, glutaric acid, d-methyl glutaric acid,
adipic acid, sebacic acid,
and pimelic acid. More preferred saturated polycarboxylic acids arc adipic
acid, succinic acid, and
glutaric acid.
[0052] Exemplary saturated polycarboxylic acid esters can be derived from
adipic acid, chlorendic
acid, dihydrophthalic acid, dimethy1-2,6-naphthenic dicarboxylic acid, d-
methyl glutaric acid,
dodccanedicarboxylic acid, glutaric acid, hexahydrophthalic acid, nadic acid,
pimelic acid, sebacic
acid, succinic acid, tctrahydrophthalic acid, 1,2-cyclohexane dicarboxylic
acid, 1,3-cyclohexane
dicarboxylic acid, 1,4-cyclohexanc dicarboxylic acid, and DicIs-Alder adducts
made from maleic acid
anhydride and cyclopentadiene.
[0053] Exemplary saturated polycarboxylic acid anhydrides can be derived from
adipic acid,
chlorendic acid, dihydrophthalic acid, dimethy1-2,6-naphthenic dicarboxylic
acid, dimethylglutaric
acid, dodecanedicarboxylic acid, glutaric acid, hexahydrophthalic acid, nadic
acid, pimelic acid,
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sebacic acid, succinic acid, tetrahydrophthalic acid, 1,2-cyclohexanc
dicarboxylic acid, 1,3-
cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and Diels-
Alder adducts made from
maleic acid anhydride and cyclopentadicne. Prefcrred saturatcd polycarboxylic
acid anhydrides are the
saturated polycarboxylic acid anhydrides of chlorcndic acid, dihydrophthalic
acid, dimethylglutaric
acid, elutaric acid, hexahydrophthalic acid, nadic acid, succinic acid,
tetrahydrophthalic acid. More
preferred saturated polycarboxylic acid anhydrides are dihydrophthalic
anhydride, hexahydrophthalic
anhydride, tetrahydrophthalic anhydride, and succinic anhydride.
[0054] Preferred unsaturated aliphatic polycarboxylic acids are selected from
the group consisting of
unsaturated aliphatic dicarboxylic acids, unsaturated aliphatic tricarboxylic
acids, unsaturated aliphatic
tetracarboxylic acids, and their corresponding acid anhydrides. A skilled
person recognizes that the
unsaturated aliphatic polycarboxylic acids may also be employed in form of
esters, e.g. methyl esters
or ethyl esters, in the corresponding transesterification reactions.
[0055] Exemplary unsaturated polycarboxylic acids include chloromaleic acid,
citraconic acid,
fumaric acid, itaconic acid, maleic acid, mesaconic acid, and
methyleneelutaric acid. Preferred
unsaturated polycarboxylic acids are fumaric acid, itaconic acid, maleic acid
and mesaconic acid,
glutaconic acid, traumatic acid, muconic acid, nadic acid, methylnadic acid,
tetrahydrophthalic acid,
hexahydrophthalic acid. More preferred unsaturated polycarboxylic acids are
fumaric acid and maleic
acid. The most preferred unsaturated polycarboxylic acid is fumaric acid.
[0056] Exemplary unsaturated polycarboxylic acid esters can be derived from
chloromaleic acid,
citraconic acid, fumaric acid, itaconic acid, maleic acid, mesaconic acid, and
methylencelutaric acid.
Preferred unsaturated polycarboxylic acids are fumaric acid, itaconic acid,
maleic acid and mesaconic
acid.
[0057] Exemplary unsaturated polycarboxylic acid anhydrides can be derived
from chloromaleic acid,
citraconic acid, fumaric acid, itaconic acid, maleic acid, mesaconic acid, and
methyleneelutaric acid.
Preferred unsaturated polycarboxylic acid anhydrides are the unsaturated
polycarboxylic acid
anhydrides of chloromaleic acid, malcic acid, citraconic acid, and itaconic
acid. More preferred
unsaturated polycarboxylic acid anhydrides are maleic acid anhydride,
citraconic anhydride, and
itaconic anhydride. The most preferred unsaturated polycarboxylic acid
anhydride is maleic acid
anhydride.
[0058] Preferably, the polycarboxylic acid component comprises a ternary
mixture of
- at least one aromatic dicarboxylic acid, anhydride or ester thereof; which
is preferably selected
from isophthalic acid, phthalic acid, and the anhydrides thereof; with
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- at least one saturated aliphatic dicarboxylic acid, anhydride or ester
thereof, which is preferably
adipic acid or adipic acid anhydride; and with
- at least one unsaturated aliphatic dicarboxylic acid, anhydride or ester
thereof; which is preferably
selected from maleic acid, fumaric acid and the anhydrides thereof.
[0059] Preferably, the polycarboxylic acid component comprises at least one
saturated aliphatic
polycarboxylic acid, anhydride or ester thereof. Preferably, the at least one
saturated aliphatic
polycarboxylic acid, anhydride or ester thereof has at least 12 carbon atoms,
more preferred at least 10
carbon atoms, even more preferred at least 9 carbon atoms and most preferred
at least 8 carbon atoms.
Preferably the at least one saturated aliphatic polycarboxylic acid, anhydride
or ester thereof is adipic
acid or adipic acid anhydride.
[0060] Preferably, the polycarboxylic acid component, more preferably the
unsaturated polyester
resin component, does not comprise maleic acid or maleic acid anhydride. For
the purpose of the
invention, the above means that the system contains substantially no maleic
acid or maleic acid
anhydride, preferably at most 10 ppm, more preferably at most 5 ppm, most
preferably at most I ppm
maleic acid or maleic acid anhydride, and in particular no detectable maleic
acid or maleic acid
anhydride at all. Suitable methods for determining the content of maleic acid
or maleic acid anhydride
in a system are known to the skilled person.
[0061] A skilled person will recognize that when maleic acid or maleic acid
anhydride is employed in
polyester synthesis, some maleic functionalities remain in the resin. Without
wishing to be bound to
any scientific theory, resins comprising a high content of maleic have a lot
of reactive double bonds
and can be too rigid or brittle to be employed in the manufacture of
engineered stone slabs. Slabs
prepared from such resins typically show cracks.
[0062] Preferably, the weight content of the polycarboxylic acid component is
within the range of
about 55 31 wt.-%, more preferably about 55 30 wt.-%, still more preferably
about 55 25 wt.-%, yet
more preferably about 55 20 wt.-%, even more preferably about 55 15 wt.-%,
most preferably about
55 10 wt.-%, and in particular about 55 5 wt.-%; in each case relative to the
total weight of the
polycarboxylic acid component, the polyfunctional alcohol component, the
optionally present
monocarboxylic acid component, and the optionally present monofunctional
alcohol component.
[0063] In preferred embodiments of the polycarboxylic acid component according
to the invention,
- the molar
content of the at least one aromatic dicarboxylic acid, anhydride or ester
thereof is within
the range of about 25 23 mole.-%, more preferably about 25 18 mole.-%, still
more preferably
about 25 15 mole.-%, yet more preferably about 25 12 mole.-%, even more
preferably about 25+9
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mole.-%, most preferably about 25 6 mole.-% and in particular about 25 3 mole.-
%, in each case
based on all aromatic dicarboxylic acids, anhydrides or esters thereof; and/or
- the molar
content of the at least one saturated aliphatic dicarboxylic acid, anhydride
or ester thereof
is within the range of; and about 12.5 10.5 mole.-%, more preferably about
12.5 9.0 mole.-%, still
more preferably about 12.5 7.5 mole.-%, yet more preferably about 12.5 6.0
mole.-%, even more
preferably about 12.5 4.5 mole.-%, most preferably about 12.5 3.0 mole.-% and
in particular
about 12.5 1.5 mole.-%, in each case based on all saturated aliphatic
dicarboxylic acids,
anhydrides or esters thereof; and/or
- the molar content of the at least one unsaturated aliphatic dicarboxylic
acid, anhydride or ester
thereof is within the range of about 65 31 mole.-%, more preferably about 65
30 mole.-%, still
more preferably about 65 25 mole.-%, yet more preferably about 65 20 mole.-%,
even more
preferably about 65 15 mole.-%, most preferably about 65 10 mole.-%and in
particular about
65 5 mole.-%, in each case based on all saturated aliphatic dicarboxylic
acids, anhydrides or esters
thereof;
in each case relative to the total molar content of (i) the polycarboxylic
acid component.
[0064] Preferably, the unsaturated polyester resin component comprises a
polycarboxylic acid
component, wherein the molar ratio of (adipic acid or adipic acid anhydride)
to (phthalic acid or
phthalic acid anhydride) in the unsaturated polyester resin component is in
the range of (0.5 to 3) : (1.5
to 3), more preferably in a range of (0.7 to 1.5) : (2 to 3), most preferred
in a range of about (1) : (3).
Without wishing to be bound to any scientific theory it is believed that the
aliphatic carbon chain of
the adipic acid will enhance flexibility of the stone slab.
[0065] Preferably, the unsaturated polyester resin component comprises a
polycarboxylic acid
component, wherein the molar ratio of (saturated aliphatic polycarboxylic
acids, anhydrides or esters
thereof) to (unsaturated aliphatic polycarboxylic acids, anhydrides or esters
thereof) in the polyester
resin component is in a range of (0.5 to 1.5) : (6.5 to 8.5), more preferably
in a range of (0.8 to 1.2) :
(6.8-7.8), most preferred in a range of about (1) : (7.5).
[0066] The unsaturated polyester resin component according to the invention is
obtained or is
obtainable from a monomer mixture comprising a polyfunctional alcohol
component comprising at
least one polyfunctional alcohol selected from the group consisting of
aromatic polyfunctional
alcohols, saturated aliphatic polyfunctional alcohols, and unsaturated
aliphatic polyfunctional alcohols.
[0067] Preferably, the polyfunctional alcohol is a saturated aliphatic
polyfunctional alcohol selected
from the croup consisting of saturated aliphatic diols, saturated aliphatic
triols, saturated aliphatic
tetraols.
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[0068] Examples of saturated aliphatic polyfunctional alcohols include but are
not limited to ethylene
glycol, propylene glycol, 1,3-propanediol, 1,4-propanedio1, 1,4-butancdiol,
2,2-dimethy1-1,3-propane-
diol, 2-methy1-1,3-propanediol, glycerol, trimethylol propane and oxyalkylatcd
adducts thereof such as
glycol ethers, e.g. diethylene glycol, dipropylcne glycol, and polyoxyalkylcne
glycol.
[0069] Preferably, the polyfunctional alcohol is an unsaturated aliphatic
polyfunctional alcohol
selected from the group consisting of unsaturated aliphatic diols, unsaturated
aliphatic triols,
unsaturated aliphatic tetraols.
[0070] Preferably, the polyfunctional alcohol is an aromatic polyfunctional
alcohol selected from the
group consisting of aromatic diols, aromatic triols and aromatic tetraols
[0071] Examples of aromatic polyfunctional alcohols include but are not
limited to bisphenol A,
bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol
E, bisphenol F,
bisphenol FL, bisphenol G, bisphenol M, bisphenol P, bisphenol P1-1, bisphenol
S, bisphenol TMC,
and bisphenol Z.
[0072] In a preferred embodiment, the polyfunctional alcohol is selected from
aliphatic and aromatic
polyfunctional alcohols, wherein the term "aliphatic" covers acyclic and
cyclic, saturated and
unsaturated polyfunctional alcohols. Preferably, the polyfunctional alcohol is
selected from aliphatic
polyfunctional alcohols. More preferably, the polyfunctional alcohols are
selected from aliphatic
polyfunctional alcohols having from 2 to 12 carbon atoms. Still more
preferably, the polyfunctional
alcohols are selected from diols having from 2 to 10 carbon atoms, most
preferably from diols having
3, 4, 6, 7, 8, 9 or 10 carbon atoms. It is particularly preferred that the
polyfunctional alcohol is a diol
having 3 carbon atoms.
[0073] Exemplary diols include alkanediols, butane-1,4-diol, 2-buty1-2-ethy1-
1,3-propanediol
(BEPD), 1,3-butylene glycol, butane-1,4-diol, cyclohexane-1,2-diol,
cyclohexane dimethanol,
diethyleneelycol, 2,2-dimethy1-1,4-butancdiol, 2,2-dimethylheptanediol, 2,2-
dimethyloctanediol, 2,2-
dimethylpropanc-1,3-diol, dipentacrythritol, dipropylcne glycol, di-
trimethylolpropanc, ethylene-
glycol, hexanc-1,6-diol, 2-methyl-1,3-propanediol, ncopcntyl glycol, 5-
norbornenc-2,2-dimethylol,
2,3-norbornene diol, oxa-alkanediols, pentaerythritol, polyethylenepropane-3-
diol, 1,2-propanediol,
triethyleneglycol, trimethylolpropane, tripentaerythirol, 2,2,4-trimethy1-1,3-
pentanediol, and 2,2-bis(p-
hydroxycyclohexyl)-propanc.
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[0074] In a preferred embodiment, the polyfanctional alcohol is a diol
selected from the group
consisting of butane-1,4-diol, 2-butyl-2-ethyl-1,3-propanediol (BEPID), E3-
butylene glycol,
cyclohexane-1,2-diol, cyclohexanc dimethanol, diethylenglycol, 2,2-dinaethy1-
1,4-butanediol, 2,2-
dimethylhept anediol, 2,2-dimethy loctancdiol, 2,2-
dimethylpropane-1,3-diol, dipentaerythritol,
dipropylene glycol, di-trimethylolpropane, hexane-1,6-diol, 2-methy1-1,3-
propanediol, 5-norbornene-
2,2-dimethylol, 2,3-norbornene diol, oxa-alkanediols, pentaerythritol,
polyethylene glycol, propane-3-
diol, 1,2-propanediol (also called 1,2-propyleneglycol), triethyleneglycol,
trimethylolpropane,
tripentaerythritol, 2,2,4-trimethy1-1,3-pentancoliol, and 2,2-bis(p-
hydroxycyclohexyl)-propane. More
preferably, the polyfunctional alcohol is selected from the group consisting
of 1,2-propanediol (1,2-
propylene glycol), dipropylene glycol, and cyclohexanc-E2-diol. Still more
preferably, the
polyfunctional alcohol is selected from 1,2-propanediol (1,2-propylene glycol)
and dipropylene glycol.
It is particularly preferred that the polyfunctional alcohol is 1,2-
propanediol (1,2-propylene glycol),
dipropylene glycol or a combination thereof. Most preferably, the
polyfunctional alcohol is 1,2-
propanediol (1,2-propylene glycol).
[0075] Preferably, the polyfunctional alcohol component comprises a mixture of
at least two saturated
aliphatic polyfunctional alcohols; preferably selected from the group
consisting of propylene glycol,
dipropylene glycol, ethylene glycol, and diethylene glycol.
[0076] Preferably, the weight content of the polyfunctional alcohol component
is within the range of
about 35 21 wt.-%, more preferably about 35 18 wt.-%, still more preferably
about 35 15 wt.-%, yet
more preferably about 35 12 wt.-%, even more preferably about 35 9 wt.-%, most
preferably about
35 6 wt.-% and in particular about 35 3 wt.-%, in each case relative to the
total weight of the
polycarboxylic acid component, the polyfunctional alcohol component, the
optionally present
monocarboxylic acid component, and the optionally present monofunctional
alcohol component.
[0077] The unsaturated polyester resin component according to the invention
may he obtained or is
obtainable from a monomer mixture optionally comprising a monocarboxylic acid
component.
[0078] The monocarboxylic acid component preferably comprises a monocarboxylic
acid selected
from saturated aliphatic monocarboxylic acids, unsaturated aliphatic
carboxylic acids, aromatic
carboxylic acids, the salts, esters and anhydrides thereof.
[0079] Exemplary monocarboxylic acids include acrylic acid, benzoic acid,
ethylhexanoic acid, and
methacrylic acid. Preferred monofunctional carboxylic acids are acrylic acid
and methacrylic acid.
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[0080] The weight content of the monocarboxylic acid component may be within
the range of from
about 0.01 wt.-% to about 10 wt.-%, more preferably from about 0.01 wt.-% to
about 2 wt.-%, relative
to the unsaturated polyester resin system.
[0081] In a preferred embodiment, the unsaturated polyester resin component
according to the
invention is obtained or is obtainable from a monomer mixture comprising a
monocarboxylic acid
component, wherein the weight content of the monocarboxylic acid component,
relative to the total
weight of the unsaturated polyester resin component is not more than about 7.0
wt.-%, more preferably
not more than about 6.0 wt.-%, still more preferably not more than about 5.0
wt.-%, yet more
preferably not more than about 4.0 wt.-%, even more preferably not more than
about 3.0 wt.-%, most
preferably not more than about 2.0 wt.-% and in particular not more than about
1.0 wt.-%.
[00821 In another preferred embodiment, the unsaturated polyester resin
component according to the
invention is obtained or is obtainable from a monomer mixture not comprising
any monocarboxylic
acid component.
[0083] The unsaturated polyester resin component according to the invention
may be obtained or is
obtainable from a monomer mixture optionally comprising a monofunctional
alcohol component.
Preferably, the unsaturated polyester resin component according to the
invention comprises at least
one monofunctional alcohol selected from aromatic monofunctional alcohols,
saturated aliphatic
monofunctional alcohols, and unsaturated aliphatic monofunctional alcohols.
[0084] Exemplary monofunctional alcohols include benzyl alcohol, cyclohexanol,
2-ethyhexyl
alcohol, 2-cyclohexyl ethanol, and lauryl alcohol.
[0085] Preferably, the unsaturated polyester resin component according to the
invention comprises at
least one aromatic monofunctional alcohols, preferably benzyl alcohol.
[0086] Preferably, the weight content of the monofunctional alcohol component
is within the range of
about 7.0 6.5 wt.-%, more preferably about 7.0 6.0 wt.-%, still more
preferably about 7.0 5.0 wt.-%,
yet more preferably about 7.0 4.0 wt.-%, even more preferably about 7.0 3.0
wt.-%, most preferably
about 7.0 2.0 wt.-% and in particular about 7.0 1.0 wt.-%, in each case
relative to the total weight of
the polycarboxylic acid component, the polyfunctional alcohol component, the
optionally present
monocarboxylic acid component, and the optionally present monofunctional
alcohol component.
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[0087] Preferably, the unsaturated polyester resin component according to the
invention comprises
both, a polyfunctional alcohol component comprising at least two saturated
aliphatic diols as well as a
monofunctional alcohol component.
)0088] Preferably,
- the molar content of the at least two saturated aliphatic diols is within
the range of about 88 11
mole.-%, more preferably about 88 10 mole.-%, still more preferably about 88 9
mole.-%, yet
more preferably about 88 8 mole.-%, even more preferably about 88 6 mole.-%,
most preferably
about 88 4 mole.-%, and in particular about 88 2 mole.-%, based on all
saturated aliphatic diols;
and/or
- the molar content of the at least one monofunctional alcohol is within the
range of about 12 11
mole.-%, more preferably about 12 10 mole.-%, still more preferably about 12 9
mole.-%, yet
more preferably about 12 8 mole.-%, even more preferably about 12 6 mole.-%,
most preferably
about 12 4 mole.-%, and in particular about 12 2 mole.-%, based on all
monofunctional alcohols;
in each case relative to the total molar content of (ii) the polyfunctional
alcohol component and (iv) the
monofunctional alcohol component.
[0089] In a preferred embodiment, the unsaturated polyester resin component
comprises
- at least one aromatic dicarboxylic acid, anhydride or ester thereof selected
from isophthalic acid,
phthalic acid, and the anhydrides thereof; and/or
- at least one saturated aliphatic dicarboxylic acid, anhydride or ester
thereof which is adipic acid or
adipic acid anhydride; and/or
- at least one unsaturated aliphatic dicarboxylic acid, anhydride or ester
thereof which is fumaric acid
and the anhydrides thereof; and/or
- at least two saturated aliphatic diols selected from the group consisting of
propylene glycol, and
diethylene glycol.
[0090] Without wishing to be bound to any scientific theory, a high content of
fumaric double bonds
in the polyester resin will give high crosslink density when the resin is
cured and the adipic acid, due
to its alkyl chain, will give flexibility to the cured polyester resin. A
skilled person will recognize that
another flexibilizing constituent is diethylene glycol.
[0091] Particularly preferred embodiments A' to A8, B' to B5, and CI to C7 of
the unsaturated
polyester resin component according to the invention are compiled in the
tables here below. All values
are provided in wt.-%, relative to the total weight of all monomers
(polycarboxylic acid component,
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polyfunctional alcohol component, optionally present monocarboxylic acid
component, and optionally
present monofunctional alcohol component) from which the unsaturated polyester
resin component is
obtained (or obtainable):
[wt.-%1 A' A' A' A4 A' A6 A7 A'
poly-functional alcohol component 36 30 36 26 36 22
36 18 36 14 36 10 36 7 36 3
monofunctional alcohol component 7 6.5 7 6 7 5.5 7 5 7 4.5 7
4 7 3 7 2
polycarboxylic acid component 57 50 57 45 57 40
57 35 57 30 57 25 57 20 57 15
[wt.-%] B1 B2 B3 B4 B'
saturated aliphatic difunctional alcohol(s) 36 30 36 25 36
20 36 I5 36 10
aromatic monofunctional alcohol(s) 7 6.5 7 6 7 5 7 4 7 3
saturated aliphatic dicarboxylic(s) acid or anhydride(s) thereof 8 7 8 6
8 5 8 4 8 3
aromatic dicarboxylic acid(s) or anhydride(s) thereof 17 15 17 13 17 11
17 9 17 7
unsaturated aliphatic dicarboxylic acid(s) or anhydride(s) thereof 32 30 32 25
32 20 32 15 32 10
[wt.-%] C' C2 C3 c4 C5 c6 C7 C7
monopropylene glycol 32 30 32 26 32
22 32+18 32 14 32 10 32 7 32 3
diethylene glycol 4 3.6 4 3.2 4 2.8 4 2.4 4 2 4 I.6 4
1.2 4 0.8
benzyl alcohol 7 6.5 7 6 7 5.5 7 5 7 4.5 7 4
7 3.5 7 3
adipic acid or adipic acid anhydride 8 7.5 8 7 8 6 8 5 8 4 8
3 8 2 8 1
phthalic acid or phthalic acid anhydride 17 16 17 14 17 12 17 10 17 8 17
6 17 4 17 2
funiaric acid or fumaric acid anhydride 32 30 32 26 32 22 32 I8 32 14 32 10 32
6 32 2
[0092] In a preferred embodiment, the unsaturated polyester resin component
according to the
invention is obtained or is obtainable from a monomer mixture not comprising
maleic acid, a salt,
anhydride or ester thereof.
[00931 In another preferred embodiment, the unsaturated polyester resin
component according to the
invention is obtained or is obtainable from a monomer mixture comprising
maleic acid, a salt,
anhydride or ester thereof, wherein the weight content of maleic acid, a salt,
anhydride or ester thereof,
relative to the total weight of the unsaturated polyester resin component is
not more than about 7.0
more preferably not more than about 6.0 wt.-%, still more preferably not more
than about 5.0
wt.-%, yet more preferably not more than about 4.0 wt.-%, even more preferably
not more than about
3.0 wt.-%, most preferably not more than about 2.0 wt.-% and in particular not
more than about 1.0
wt.-%.
[00941 Another aspect of the invention relates to a prepromoted unsaturated
polyester resin system for
the preparation of engineered stone, which system comprises
(i) a unsaturated polyester resin component according to the invention as
described above;
(ii) a metal catalyst capable of catalyzing curing of said unsaturated
polyester resin component;
preferably a zinc salt of a carboxylic acid, more preferably a zinc salt of a
C -70 carboxylic acid,
still more preferably a zinc salt of a C6-17 carboxylic acid, most preferably
zinc octanoate;
(iii) a quaternary ammonium salt; preferably a benzyl-N,N,N-trialkylammonium
salt or a N,N,N,N-
tetraalkylammonium salt; and
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(iv) optionally, one or more additives selected from the group consisting of
reactive diluents,
accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers,
inhibitors and rheoloey
modifiers.
[0095] All preferred embodiments of the unsaturated polyester component
according to the invention
that have been defined above analogously also apply to the prepromoted
unsaturated polyester resin
system according to the invention and thus, are not repeated hereinafter.
[0096] For the purpose of the invention, a "prepromoted" resin already
contains the metal catalyst as
promoter, but not yet the initiator (peroxide) for the radical reaction that
causes curing. The
prepromoted resin has long shelf-life and may be marketed as precursor. The
initiator (peroxide) is
then shortly added before the prepromoted resin is employed in the production
of the final product, i.e.
of the engineered stone.
[0097] Preferably, the prepromoted unsaturated polyester resin system
according to the invention is
cobalt free. For the purpose of the invention, ''cobalt free" means that the
system contains substantially
no cobalt, preferably at most 10 ppm, more preferably at most 5 ppm, most
preferably at most 1 ppm
cobalt, and in particular no detectable cobalt at all. Suitable methods for
determining the cobalt content
of a system are known to the skilled person such as ESCA or high resolution
inductively coupled
plasma mass spectrometry.
[0098] In a preferred embodiment, not only the prepromoted unsaturated
polyester resin system, but
the entire formable composition according to the invention is cobalt free,
i.e. the inorganic particulate
material as well as the peroxide component are cobalt free as well, such that
no cobalt is entrained.
[00991 It has been found that when employing zinc salts or copper salts
instead of cobalt salts as
metal catalysts (promoters), the cobalt free unsaturated polyester resin
system has a long shelf life.
Thus, the marketed cobalt free unsaturated polyester resin system may already
initially contain the
zinc salts or copper salts, thus rendering the unsaturated polyester resin
system a "prepromoted"
unsaturated polyester resin system. Thus, when preparing engineered stone from
the prepromoted
unsaturated polyester resin system according to the invention, only the
initiator (peroxide) needs to be
added, but not the metal catalyst (promoter), which is already contained. This
makes the cobalt free
unsaturated polyester resin system safer and easier to handle compared to
conventional systems that
require separate addition of initiator and cobalt promoter.
[0100] The prepromoted unsaturated polyester resin system according to the
invention is preferably
cobalt free. Thus, cobalt salts such as cobalt naphthenate or cobalt octoate,
which are contained in
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conventional prepromoted unsaturated polyester resin systems for the
preparation of engineered stone,
are preferably not contained in the prepromoted unsaturated polyester resin
system according to the
invention.
[0101] The same applies to additives that arc contained in conventional
prepromoted unsaturated
polyester resin system for the preparation of engineered stone in order to
support the effect of the
cobalt catalysts, such as dirnethylaniline (DMA) or diethylaniline (DEA).
Preferably, the prepromoted
unsaturated polyester resin system according to the invention contains neither
DMA nor DEA.
[0102] The prepromoted unsaturated polyester resin system according to the
invention comprises a
metal catalyst capable of catalyzing curing of said unsaturated polyester
resin component.
[0103] Preferably, the metal catalyst that is contained in the prepromoted
unsaturated polyester resin
system according to the invention comprises zinc or copper, preferably in form
of a zinc salt or a
copper salt.
[0104] In a preferred embodiment, the metal catalyst is a zinc salt. The zinc
salts of carboxylic acids
are preferred. Non-limiting examples of typical zinc salts include the zinc
salts of C1-70 carboxylic
acids and polyctu-boxylic acids, preferably zinc salts of C6-12 carboxylic
acid and polycarboxylic acids,
including zinc acetate, zinc propionate, zinc butyrate, zinc pentanoate, zinc
hexanoate, zinc
heptanoate, zinc 2-ethyl hexanoate, zinc octanoate, zinc nonanoate, zinc
decanoate, zinc neodecanoate,
zinc undecanoate, zinc undecenylate, zinc dodecanoate, zinc palmitate, zinc
stearate, zinc oxalate, and
zinc naphthenate. Other zinc salts useful herein include the zinc salts of
amino acids such as zinc
alanine, zinc methionine, zinc glycine, zinc asparagine, zinc aspartine, zinc
serine, and the like. Other
zinc salts include zinc citrate, zinc maleate, zinc benzoate, zinc
acetylacetonate, and the like. Other
zinc salts include zinc chloride, zinc sulfate, zinc phosphate, and zinc
bromide. The zinc chalcogens
and zinc oxide can also be used. Zinc octoanate (zinc octoate) is particularly
preferred.
[0105] In another preferred embodiment, the metal catalyst is a copper salt.
Preferred copper salts are
copper (I) salts or copper (II) salts. Preferred copper salts include but are
not limited to copper acetate,
copper octanoate, copper naphthenate, copper acetylacetonate, copper chloride
or copper oxide.
[0106] The content of the metal catalyst, preferably zinc octanoate, relative
to the total weight of the
prepromoted unsaturated polyester resin system according to the invention, is
preferably within the
range of from about 0.001 wt.-% to about 1 wt.-%, more preferably about 0.001
wt.-% to about 0.02
wt.-%. Preferably, the content of the metal catalyst, preferably zinc
octanoate, relative to the total
weight of the prepromoted unsaturated polyester resin system according to the
invention, is within the
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range of about 0.020+0.015 wt.-%, more preferably about 0.020 0.010 wt.-%,
even more preferably
about 0.020 0.004 wt.-9C, still more preferably about 0.020 0.005 wt.-%, most
preferably about
0.020 0.006 wt.-%.
[01071 The content of the metal catalyst, preferably zinc octanoate, relative
to the total weight of the
formable composition according to the invention, is preferably within the
range of from about 0.0001
wt.-% to about 0.01 wt.-%, more preferably about 0.0001 wt.-% to about 0.002
wt.-%. Preferably, the
content of the metal catalyst, preferably zinc octanoate, relative to the
total weight of the formable
composition according to the invention, is within the range of about 0.0020
0.0015 wt.-%, more
preferably about 0.0020 0.0010 wt.-%, even more preferably about 0.0020 0.0005
wt.-%, still more
preferably about 0.0020 0.0003 wt.-%, most preferably about 0.0020 0.0002 wt.-
%.
[0108] The prepromoted unsaturated polyester resin system according to the
invention comprises a
quaternary ammonium salt, preferably a benzyl-N,N,N-trialkylammonium salt or a
N,N,N,N-
tetraalkylmmoni um salt.
[0109] Preferably, the quaternary ammonium salt that is contained in the
prepromoted unsaturated
polyester resin system according to the invention is a benzyl-N,N,N-
trialkylammonium salt or a
N,N,N,N-tetraalkylammonium salt. Preferred representatives include but are not
limited to benzyl-
N,N,N-trimethylammonium salts such as bcrizyl-N,N,N-trimethylammonium
chloride; and benz-
alkonium chlorides such as benzyl-N,N,N-00-alkyl-dimethyl-ammonium salts, e.g.
benzyl-N,N,N-
C,o-alkyl-dimethyl-ammonium chloride. N,N-00-dialkyl-N,N-dimethyl ammonium
salts, and the
mixtures thereof.
[0110] The content of the quaternary ammonium salt, relative to the total
weight of the prepromoted
unsaturated polyester resin system according to the invention, is preferably
within the range of from
about 0.001 wt.-% to about 5 wt.-%, more preferably about 0.01 wt.-% to about
0.5 wt.-%. Preferably,
the content of the quaternary ammonium salt, relative to the total weight of
the prepromoted
unsaturated polyester resin system according to the invention, is within the
range of about 0.20+0.15
wt.-%, more preferably about 0.20 0.10 wt.-%, most preferably about 0.20 0.05
wt.-%.
[0111] The prepromoted unsaturated polyester resin system according to the
invention may comprise
one or more additives selected from the group consisting of reactive diluents,
accelerators, co-
promoters, dispersing agents, UV absorbers, stabilizers, inhibitors and
rheology modifiers. Suitable
additives are known to the skilled person. In this regard it can be referred
to e.g. Ernest W. Flick,
Plastics Additives, An Industrial Guide, 3rd ed. 2002, William Andrew
Publishing.
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[01121 The total content of optional additives, relative to the total weight
of the prepromoted
unsaturated polyester resin system according to the invention, is preferably
within the ranee of from
about 0.001 wt.-% to about 45 wt.-%, or about I wt.-91 to about 45 wt.-%, more
preferably about 10
wt.-% to about 45 wt.-%, even more preferably about 20 wt.-% to about 40 wt.-
%, most preferably
about 30 wt.-% to about 40 wt.-% or about 33 wt.-% to about 38 wt.-%.
[0113] Preferably, the prepromoted unsaturated polyester resin system
comprises a reactive diluent
selected from the group consisting of styrene, substituted styrene, mono-, di-
and polyfunctional esters
of monofunctional acids with alcohols or polyfunctional alcohols, mono-, di-
and polyfunctional esters
of unsaturated rnonofunctional alcohols with carboxylic acids or their
derivatives.
[0114] Preferably, the reactive diluent comprises styrene and/or 1,4
butanediol methacrylate
(BDDMA) and/or butyl methacrylatc.
[0115] Preferably, the content of reactive diluent, preferably styrene, is
within the ranee of about
30 8 wt.-%, more preferably about 30 7 wt.-%, still more preferably about 30 6
wt.-%, yet more
preferably about 30 5 wt.-%, even more preferably about 30 4 wt.-%, most
preferably about 30 3
wt.-% and in particular about 30 2 wt.-%, in each case relative to the total
weight of the prepromoted
unsaturated polyester resin system.
[0116] Inhibitors may be contained in the prepromoted unsaturated polyester
resin system to lengthen
the gel time (pot life). Inhibitors are useful when very lone gel times are
required or when resin is
curing quickly due to high temperatures. Some common inhibitors include
tertiary butyl catechol,
hydroquinone, and toluhydroquinone.
[0117] Preferably, an inhibitor and a reactive diluent are mixed with the
unsaturated polyester resin
component simultaneously. Preferably, an inhibitor and a reactive diluent are
mixed with the
unsaturated polyester resin component before other additives are added.
[0118] Fillers may be contained in the prepromoted unsaturated polyester resin
system. Alumina
trihydrate may be contained e.g. to improve flame retardancy and reduce smoke
emissions. Calcium
carbonate, talc and kaolin clays may be contained e.g. to increase the
stiffness. Silicon carbide and/or
aluminum oxide may be contained in the prepromoted unsaturated polyester resin
system e.g. to
reduce liner deterioration caused by abrasion.
[0119] The prepromoted unsaturated polyester resin system may further comprise
dispersing agents,
which are chemicals that aid in the dispersion of solid components in the
resin composition, i.e.
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enhance the dispersion of solid components in the unsaturated resin. Useful
dispersing agents include
but are not limited to copolymers comprising acidic functional groups like BYK
- W 996 available
for Byk USA, Inc., Wallingford, Connecticut, U.S.A. ("Byk"), unsaturated
polycarboxylic acid
polymer comprising polysiloxanc copolymer, like BYKO - W 995 available from
Byk, copolymer
comprising acidic functional groups, like BYKC) - W 9011 available from Byk,
copolymer comprising
acidic functional groups, like BYKO - W 969 available from Byk and alkylol
ammonium salt of an
acidic polyester. Combinations of dispersing agents may be used.
[0120] The prepromoted unsaturated polyester resin system can comprise a co-
promoter to enhance
cure. Co-promoters useful in the invention include 2,4-petendione ("2,4-PD") ,
2-acetylbutyrolactone,
ethyl acetoacetonate, n,n-diethyl acetoacetarnide and the like, and
combinations thereof.
10121] The prepromoted unsaturated polyester resin system may comprise a
coupling agent. Coupling
agents useful in the invention include but are not limited to silanes, e.g. 3-
trimethoxy-silyl-propyl-
methacrylate, and silane modified polyethylene glycol.
[0122] The prepromoted unsaturated polyester resin system may also comprise
theology modifiers.
Typical theology modifiers include fumed silica, organic clay and combinations
thereof.
[0123] In addition, the prepromoted unsaturated polyester resin system may
comprise other
conventional additives such as synergist agents. These synergist agents
include polysorbate 20 (Tween
20), polyhydroxycarboxylic acid esters, such as BYKC) - R605 and R606
available from Byk and the
like, and combinations thereof.
[0124] Another aspect of the invention relates to a formable composition for
the preparation of
engineered stone comprising
(A) a prepromoted unsaturated polyester resin system according to the
invention as described above;
(B) an inorganic particulate material; and
(C) a peroxide component.
[0125] All preferred embodiments of the unsaturated polyester component
according to the invention
and of the prepromoted unsaturated polyester resin system according to the
invention that have been
defined above analogously also apply to the formable composition according to
the invention and thus,
are not repeated hereinafter.
[01261 The formable composition according to the invention has the advantage
that it can be
processed on conventional plants for the manufacture of engineered stone
without any adaptations.
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Furthermore, as the unsaturated polyester resin system contained in the
formable composition is
prepromoted already, the final manufacturing process merely requires the
mixing of (A), (B) and (C)
with one another and thus, facilitates the process compared to conventional
processes requiring
separate addition of metal catalyst (promoter).
[0127] The formable composition according to the invention comprises an
inorganic particulate
material, preferably silicon dioxide, more preferably quartz and/or
cristobalite. Typically, the
inorganic particulate material is the main constituent of the formable
composition and provides the
engineered stone with the desired appearance.
[0128] Preferably, the inorganic particulate material is made from stone, e.g.
crushed stone.
[0129] Preferably, the inorganic particulate material that is contained in the
formable composition
according to the invention comprises quartz and/or cristobalitc.
10130] In a preferred embodiment, the inorganic particulate material,
preferably the silicon dioxide,
more preferably fine quartz has an average particle size of not more than
about 0.25 pm, more
preferably not more than about 0.20 pm, still more preferably not more than
about 0.18 pm, yet more
preferably not more than about 0.16 pm, even more preferably not more than
about 0.14 pm, most
preferably not more than about 0.12 pm, and in particular not more than about
0.10 pm.
[0131] In another preferred embodiment, the inorganic particulate material,
preferably the silicon
dioxide, more preferably cristobalitc has an average particle size within the
range of about 45 35 pm,
more preferably 45 30 pm, still more preferably 45 25 pm, yet more preferably
45 20 pm, even
more preferably 45 15 pm, most preferably 45 10 pm and in particular 45 5 pm.
[0132] Suitable methods for determining the average particle size and particle
size distribution of an
inorganic particulate material are known to the skilled person such as laser
light scattering according
to ASTM C1070-01(2014) or electric sensing zone technique according to ASTM
C690-09.
[0133] Preferably, the weight content of the inorganic particulate material is
about 70 wt.-% to about
99.9 wt.-%, more preferably about 80 wt.-% to about 95 wt.-%, relative to the
total weight of the
formable composition. Preferably, the content of the inorganic particulate
material is within the ranee
of about 90 7 wt.-%, more preferably about 90 6 wt.-%, still more preferably
about 90 5 wt.-%, yet
more preferably about 90 4 wt.-%, even more preferably about 90 3 wt.-%, most
preferably about
90 2 wt.-%, and in particular about 90 1 wt.-%, relative to the total weight
of the formable
composition.
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[0114] In order to induce curing of the formable composition according to the
invention, a radical
initiator is needed. The initiator generates free radicals reacting with the
ethylenic unsaturations of the
unsaturated polyester resin component, thereby causing cross-linking of the
polymer network.
Preferred peroxides are organic peroxides that work together with the metal
catalyst (promoters) to
initiate the chemical reaction that causes a resin to gel and harden. The
amount of time from which the
peroxide is added until the resin begins to eel is referred to as the "gel
time" or "pot life". Peroxide and
metal catalyst levels can be adjusted, to a certain extent, to shorten or
lengthen the gel time and
accommodate both high and low temperatures. If a longer eel time is required,
inhibitors can be added.
[0135] Preferably, the peroxide component is a hydroperoxide and/or an organic
peroxide, more
preferably an organic hydroperoxide.
[0136] Preferably, the peroxide component is selected from the group
consisting of methyl ethyl
ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIKE)), benzoyl
peroxide (BP0), tert-
butyl peroxibenzoate (TBPB), cumene hydroperoxide (CHP), and mixtures thereof.
[0137] Curnene hydroperoxide and/or methyl isobutyl ketone peroxide are
particularly preferred. It
has been surprisingly found that cumene hydroperoxide and/or methyl isobutyl
ketone peroxide as
peroxide component, preferably in combination with zinc salts or copper salts
as metal catalysts
(promoters), has particular advantages with respect to pot life, appearance
and mechanical properties
of the engineered stone, allowing for the complete omission of cobalt salts.
[0138] Preferably, the content of the peroxide component, preferably cumene
hydroperoxide and/or
methyl isobutyl ketone peroxide, is about 0.001 wt.-1 to about 0.1 wt.-%, more
preferably about
0.005 wt.-% to about 0.05wt.-%, relative to the total weight of the formable
composition. Preferably,
the content of the peroxide component, preferably cumene hydroperoxide and/or
methyl isobutyl
ketone peroxide, relative to the total weight of the formable composition
according to the invention, is
within the range of about 0.20 0.15 wt.-%, more preferably about 0.20 0.10 wt.-
%, most preferably
about 0.20 0.05 wt.-%.
[0139] Preferably, the formable composition according to the invention is
cobalt free.
[0140] Preferably, the content of the prepromoted unsaturated polyester resin
system (total content of
(i), (ii), (iii) and (iv)) is about 0.1 wt.-% to about 30 wt.-%, more
preferably about 5 wt.-% to about 20
wt.-%, relative to the total weight of the formable composition. Preferably,
the content of the
prepromoted unsaturated polyester resin system (total content of (i), (ii),
(iii) and (iv)) is within the
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range of about 10 7 wt.-%, more preferably about 10 6 wt.-%, still more
preferably about 10 5 wt.-
%, yet more preferably about 10 4 wt.-%, even more preferably about 10 3 wt.-
%, most preferably
about 10 2 wt.-%, and in particular about 10 1 wt.-%, relative to the total
weight of the formable
composition.
[0141] In preferred embodiments, the weight content of the prepromoted
unsaturated polyester resin
system is not more than about 15 wt.-%, more preferably not more than about 14
wt.-%, still more
preferably not more than about 13 wt.-%, yet more preferably not more than
about 12.5 wt.-%, even
more preferably not more than about 12 wt.-%, most preferably not more than
about 11.5 wt.-% and in
particular not more than about 11 wt.-%, in each case relative to the total
weight of the formable
composition.
101421 Preferably, the formable composition according to the invention has a
pot life of at least about
30 minutes, more preferably at least about I hour, still more preferably at
least about 1.5 hours and
most preferably at least about 2 hours. Preferably, at 40 C the pot life of
the formable composition
according to the invention, measured after mixing components (A) and (C) and
optionally (B), is
within the range of about 4.3 3.5 hours, more preferably about 4.3 3.0 hours,
still more preferably
about 4.3 2.5 hours, yet more preferably about 4.3 2.0 hours, even more
preferably about 4.3 1.5
hours, most preferably about 4.3 1.0 hours, and in particular about 4.3 0.5
hours.
[0143] Preferably, the formable composition according to the invention has a
polymerization time at
110 C of at least about 30 minutes, more preferably at least about 1 hour.
Preferably, at 110 C the
polymerization time of the formable composition according to the invention, is
within the range of
about 60 35 minutes, more preferably about 60 30 minutes, still more
preferably about 60 25
minutes, yet more preferably about 60 20 minutes, even more preferably about
60 15 minutes, most
preferably about 60 10 minutes, and in particular about 60 5 minutes.
[0144] Another aspect of the invention relates to a method for the preparation
of a unsaturated
polyester resin component according to the invention as described above
comprising the step of
reacting a mixture comprising
(i) a polycarboxylic acid component;
(ii) a polyfunctional alcohol component;
(iii) optionally, a monocarboxylic acid component; and
(iv) optionally, a monofunctional alcohol component;
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wherein the polycarboxylic acid component and/or the polyfunctional alcohol
component and/or the
monocarboxylic acid component and/or the monofunctional alcohol component
comprises ethylenic
unsaturation.
[0145] Preferably, the unsaturated polyester resin component is prepared in a
process comprising the
steps of
(a) mixing and heating the (i) polycarboxylic acid component, the (ii)
polyfunctional alcohol
component, and potassium acetate; and
(b) adding the optionally present (iv) monofunctional alcohol, a (i)
polycarboxylic acid component
differing from the (i) polycarboxylic acid component of step (a) and an
inhibitor to the mixture
obtained in step (a).
[0146] Still another aspect of the invention relates to an unsaturated
polyester resin component that is
obtainable by the above method.
[0147] Another aspect of the invention relates to a method for the preparation
of a prepromoted
unsaturated polyester resin system according to the invention as described
above comprising the step
of mixing
(i) a unsaturated polyester resin component according to the invention as
described above;
(ii) a metal catalyst capable of catalyzing curing of said unsaturated
polyester resin component;
(iii) a quaternary ammonium salt; and
(iv) optionally, one or more additives selected from the group consisting of
reactive diluents,
accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers,
inhibitors and rheology
modifiers.
[0148] Preferably, in step (iv) of the method for the preparation of a
prepromoted unsaturated
polyester resin system an inhibitor and a reactive diluent are mixed with the
unsaturated polyester
resin component simultaneously. Preferably, in step (iv) of the method for the
preparation of a
prepromoted unsaturated polyester resin system an inhibitor and a reactive
diluent are mixed with the
unsaturated polyester resin component before other additives are added.
[0149] Still another aspect of the invention relates to an unsaturated
polyester resin system that is
obtainable by the above method.
[0150] Still another aspect of the invention relates to a method for the
preparation of a formable
composition according to the invention as described above comprising the step
of mixing
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(A) a prepromoted unsaturated polyester resin system according to the
invention as described above;
(B) an inorganic particulate material; and
(C) a peroxide component.
[01511 Still another aspect of the invention relates to formable composition
that is obtainable by the
above method.
[0152] Another aspect of the invention relates to a method for the preparation
of engineered stone
comprising the steps of
(a) providing a formable composition according to the invention as
described above ;
(b) forming the composition prepared in step (a) into a desired shape; and
(c) allowing the composition formed in step (13) to cure.
[0153] Another aspect of the invention relates to engineered stone obtainable
by the method
according to the invention as described above.
[0154] All preferred embodiments of the unsaturated polyester component
according to the invention,
of the prepromoted unsaturated polyester resin system according to the
invention, and of the formable
composition according to the invention that have been defined above
analogously also apply to the
methods according to the invention as well as to the products obtainable by
said methods and thus, are
not repeated hereinafter.
[0155] Preferably, the engineered stone according to the invention has a
flexural strength of at least
about 70 MPa, more preferably at least about 80 MPa, still more preferably at
least about 90 MPa, and
most preferably at least about 100 MPa. Preferably, the flexural strength is
within the range of about
105 35 MPa, more preferably about 105 30 MPa, still more preferably about 105
25 MPa, yet more
preferably about 105 20 MPa, even more preferably about 105 15 MPa, most
preferably about
105 10 MPa, and in particular about 105 5 MPa. Methods for determining the
flexural strength of
engineered stone are known to the skilled person, e.g. ASTM C880.
[0156] Preferably, the engineered stone according to the invention has an
impact resistance of at least
about 4 J/m, more preferably at least about 6 J/m, still more preferably at
least about 8 J/m, and most
preferably at least about 10 J/nt. Preferably, the impact resistance is within
the range of about 11+7.0
J/m, more preferably about 11 6.0 J/m, still more preferably about 11 5.0 J/m,
yet more preferably
about 11 4.0 J/m, even more preferably about 11 3.0 J/m, most preferably about
11 2.0 J/m, and in
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particular about 11 1.0 J/m. Methods for determining the impact resistance of
engineered stone are
known to the skilled person, e.g. standard EN 41617-9.
[0157] Another aspect of the invention relates to the use of
- a unsaturated polyester resin component according to the invention as
described above;
- a prepromoted unsaturated polyester resin system according to the invention
as described above; or
- a formable composition according to the invention as described above
for the preparation of engineered stone.
[0158] All preferred embodiments of the unsaturated polyester component
according to the invention,
of the prepromoted unsaturated polyester resin system according to the
invention, of the formable
composition according to the invention, of the methods according to the
invention as well as of the
products obtainable by said methods that have been defined above analogously
also apply to the uses
according to the invention and thus, are not repeated hereinafter.
[0159] The following examples further illustrate the invention hut are not to
be construed as limiting
its scope.
Example I:
[0160] An unsaturated polyester resin was prepared from the following monomers
and subsequently
mixed with styrene (reactive diluent):
parts per weight comparative inventive
monopropylcnc glycol 26 28
diethylene glycol 0 3
benzyl alcohol 0 6
adipic acid 0 6.7
phthalic acid anhydride 31 15
maleic acid 11 0
fumaric acid 0 28
styrene 37 22
weight average Mw [e/mole] 2000
[0161] The preparation of the unsaturated polyester resin component comprised
the steps of
(a) mixing and heating the monopropylene glycol (PG), diethylene glycol
(DEG), adipic acid (AA),
phthalic anhydride (PAN), and potassium acetate; and
(b) adding benzyl alcohol, fumaric acid and an inhibitor to the mixture
obtained in step (a).
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[0162] Stone slabs (thickness 2 cm) having the following composition were
manufactured from the
comparative and the inventive unsaturated polyester resin:
comparative inventive
Resin % 14 12
Cristobalite filler 45 micron % 28 .. 30
Cristobalite filler 45 micron % 58 .. 58
[0163] The mechanical properties of the obtained stone slabs were investigated
and the results are
summarized in the table here below:
comparative inventive
Flexural strength [MPa] 60 .. 105
Bending yes no
Impact resistance [J/ml 6 .. I I
[0164] It becomes clear from the above comparative data that the unsaturated
polyester resin
according to the invention provides engineered stone having superior
properties compared to
engineered stone manufactured from conventional unsaturated polyester resins.
Example 2 (comparative) and example 3 (comparative):
[0165] Two unsaturated polyester resin were prepared from the following
monomers:
example 2 (comparative) example 3 (comparative)
component lgl [moll [mol]
propylene glycol 400.00 5.26 390.10 5.13
diethylene glycol 39.00 0.37 40.28 0.38
inhibitor solution 25% HQ 0.06
phosphoric acid 0.05
phthalic anhydride 474.00 3.20 229.64 1.55
benzyl alcohol 81.47 0.75
maleic acid anhydride 177.00 1.81 350.74 3.58
inhibitor solution 25% HQ 0.06 0.132
Total 1090.17 10.64 1092.35 11.40
Distillate -90.17 -92.35
Plastic 1000.00 1092.35
[0166] Synthesis of resin example 2 (comparative): propylene glycol,
diethylene glycol,
hydroquinone solution, phosphoric acid, phthalic anhydride and maleic
anhydride were charged to a
reactor equipped with a thermocouple, a mechanical stirrer, a fractionating
column, a distillation head,
a condenser and nitrogen sparge. Agitation was started as soon as a sufficient
quantity of material was
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in the reactor. The reactor was sparged with nitrogen and heated to a
temperature of 205 5 C, while
maintaining the column top temperature at 100 2 C. Sampling for acid number
and Brookfield CAP
viscosity (first at 125 C and later at 150 C, cone#3) was started as soon as
a reactor temperature of
greater than 200 5 C was reached. When the acid number was 85-100 vacuum was
applied and
increased gradually. The reaction mixture was heated at 205 5 C under vacuum
until Brookfield CAP
viscosity (at 150 C, cone#3) of 2.2-2.6 P and an acid number of 30-40 mgKOH/g
(100% solids) were
reached. Then the vacuum was released and the reaction mixture was cooled to a
temperature of 190-
200 C and the rest of hydroquinone solution added.
[0167] Synthesis of resin example 3 (comparative): propylene glycol,
diethylene glycol, phthalic
anhydride, benzyl alcohol, maleic anhydride and hydroquinone solution were
charged to a reactor
equipped with a thermocouple, a mechanical stirrer, a fractionating column, a
distillation head, a
condenser and nitrogen sparge. Agitation was started as soon as a sufficient
quantity of material was in
the reactor. The reactor was sparged with nitrogen and heated to a temperature
of 205-210 C, while
maintaining the column top temperature at 100 2 C. Sampling for acid number
and Brookfield CAP
viscosity (at 100 C, cone#3) was started as soon as reactor reached top
temperature. When the acid
number was 60-65 vacuum was applied and increased gradually. The reaction
mixture was heated at
205-210 C under vacuum until Brookfield CAP viscosity (at 100 C, cone#3) of
4.5-5.0 P and an acid
number of 41-45 mgKOH/g (100% solids) were reached. Then the vacuum was
released and the
reaction mixture was cooled to a temperature of 185 5 C.
[01681 The thus obtained comparative resins had the following properties:
Molecular weight and viscosity example 2 example 3
data: (comparative) (comparative)
Mn [g/mol] 1563 1023
Mw [g/moll 2726 1705
Mp [g/mol] 2306 1278
Pdi 1,74 1.67
Viscosity (mPas) 220-260 @150 C 450-500 @100 C
AV 30-40 41-45
[0169] After synthesis the comparative resins were mixed with styrene
(reactive diluent) and other
additives:
example 2 example 3
(comparative) (comparative)
component [g] wt.-% [g] wt.-%
styrene 519.92 34 450.00 29
copper naphthenate 8%
0.05
in styrene
hydroquinone 25% 0.18 0.30
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in PGMME solution
further additives 2.30
sum additives 522,45 450.30
[0170] Dilution of resin example 2 (comparative): resin was dropped slowly to
a thin tank, which was
charged beforehand with styrene (519.92 g), copper naphthenate 8% in styrene
solution (0.05 g), and
hydroquinone 25% in propylene glycol monomethyl ether (PGMME) solution (0.18
g). During drop,
thin tank temperature was maintained at maximum 85 5 C. Mixing and cooling of
the thin tank was
continued until temperature was decreased below 40 C. The final resin was
adjusted with additional
additives.
[0171] Dilution of resin example 3 (comparative): resin was dropped slowly to
a thin tank, which was
charged beforehand with styrene (450 g), and hydroquinone 25% in propylene
glycol monomethyl
ether (PGMME) solution (0.3 g). During drop, thin tank temperature was
maintained at maximum
80 5 C. Mixing and cooling of the thin tank was continued until temperature
was decreased below
40 C. The final resin was adjusted with additional additives.
Example 4 (inventive):
[01721 An unsaturated polyester resin was prepared from the following
monomers:
inventive example 4
mol.-
component g mol wt.-%
propylene glycol 384.59 5.06 33.10 44.75
diethylene glycol 38.24 0.36 3.29 3.19
phthalic anhydride 198.66 1.34 17.10 11.87
adipic acid 90.03 0.62 7.75 5.45
potassium acetate 0.05
bcnzyl alcohol 77.94 0.72 6.71 6.38
maleic acid
anhydride
fumaric acid 371.87 3.21 32.01 28.35
inhibitor solution
25% HQ 0.39
Total 1161.77 11.31
Distillate -161.77
Plastic 1000.00
[01731 The unsaturated polyester resin of example 4 was prepared in two steps.
The first step
comprised the reaction of the following monomers:
component lgi [moll
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propylene glycol 384.59 5.06
diethylene glycol 38.24 0.36
phthalic anhydride 198.66 1.14
adipic acid 90.03 0.62
potassium acetate 0.05
[0174] Propylene glycol, diethylene glycol, phthalic anhydride, adipic acid
and potassium acetate
were charged to a reactor equipped with a thermocouple, a mechanical stirrer,
a fractionating column,
a distillation head, a condenser and nitrogen sparge. Agitation was started as
soon as a sufficient
quantity of material was in the reactor. The reactor was sparged with nitrogen
and slowly heated to a
temperature of 205-2I0 C. First water distillate/exotherm was observed at a
reaction temperature of
165-175 C and the temperature of the water distillate at the column top was
maintained at 100 2 C.
As soon as exotherm was subsided the reaction temperature was further
increased until the acid
number of the product was about 75-85 (100% solids) and the reactor
temperature was greater than
I80 C. The reaction mixture was cooled to I50-170 C.
[0175] The second step comprised the reaction of the following components:
component [g] [moll
benzyl alcohol 77.94 0.72
fumaric acid 371.87 3.21
hydroquinone 25% in PGMME solution 0.39
[0176] Benzyl alcohol, fumaric acid and hydroquinone 25% in propylene glycol
monomethyl ether
(PGMME) solution were added to the reactor containing the reaction product of
step 1. The reaction
mixture was heated to a temperature of 205-210 C as fast as possible, while
maintaining the column
top temperature at 100 2 C. Sampling for acid number and Brookfield CAP
viscosity (at I00 C,
cone#3 or #4) was started as soon as a reactor temperature of greater than 180
C was reached. When
the acid number was smaller 70 and/or the column top temperature dropped below
80 C, vacuum was
applied and increased gradually. The reaction mixture was heated at 205-210 C
under vacuum until
Brookfield CAP viscosity (at I00 C, cone#3 or #4) of 4,0 - 4,5 P and an acid
number of 27-37
mgKOH/e (100% solids) were reached. Then the vacuum was released and the
reaction mixture was
cooled to a temperature of 180 5 C.
[0177] The thus obtained inventive polyester resins had the following
properties:
Molecular weight and viscosity inventive
data example 4
Mn [g/moll 1047
Mw [g/moll 2000
Mp [g/mol] 1663
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Pdi 1.91
Viscosity (mPas) @100 C 400-450
AV 27-17
[0178] After synthesis the inventive polyester resins were mixed with styrene
(reactive diluent) and
other additives:
inventive example 5
component Egl wt.-%
styrene 423.00 29
hydroquinone 25% in PGMME solution 0.10
further additives 15.22
sum additives 438,32
[0179] The thus obtained resin was diluted in styrene. The resin was dropped
slowly to a thin tank,
which was charged beforehand with styrene (423 g, 10,46 mol) and hydroquinone
25% in propylene
glycol monomethyl ether (PGMME) solution (0,098 g). During drop, thin tank
temperature was
maintained at maximum 80 5 C. Mixing and cooling of the thin tank was
continued until temperature
was decreased below 35 C. The final resin was adjusted with additional
additives.
Examples 5 to 9 (comparative), and examples 10 to 13 (inventive):
[0180] Stone slabs were manufactured from the comparative polyester resins of
examples 2 and 3 and
the inventive unsaturated polyester resin of example 4. The mechanical
properties of the obtained
stone slabs were investigated. The compositions of the stone slabs and the
mechanical properties of the
stone slabs are summarized in the table here below:
Example comp. 5 comp. 6 comp. 7 comp. 8
comp. 9 ¨ inv. 10 inv. 11 inv. 12 inv. 13
_..._ 0
Resin of example 2 (comp.) of example 3 (comp-) of
example 4 (inv.) t=.1
o
Molecular weight 2726 g/mol 1705 g/mol ¨
2000 g/rnol ot)
"ca7
co
Resin [wt.-W] 10 12 14 10 _ 12 10
12 14 12 ,J1
¨ I.+
Cristobalite Filler
cc
- 30 30 - 30 -
30 30 30 00
45 microns [wt.-%1_ _
0.1-0.4 Cristobalite
- 58 56 - 58 -
- 56 58
Iwt.-%1 _
Quartz Filler
30 - - 30 - 30
- - -
45 Microns Iwt.-%1
0.1-0.3 Quartz [wt.-%] 35 - - 35 - _ 35
. 58 - -
_.,
0.3-0.6 Quartz [wt.-WI 25 - 25
25 - - -
_
SUM 100 100 100 100 100 100
100 100 100
P TiO2 on resin [wt.-%] I 0 10 10 10 10 10
_ 10 10 10 0
,..
-, _ .
Cobalt (6%) on resin
.
0.20 0.20 0.20 0.20 0.20 0.20
0.20 0.20 0.20
[wt.-%1,JI
al.
al. TBPB on Resin [wt.-Vc] 2 2 2 2 2
2 2 2 2 "
- . Memo 1-
silane on resin
.
2 2 2 2 2 2
2 2 2 ,I,
Iwt.-%]
.
Slab prepared from comp. 5 comp. 6 comp. 7 inv. 8 inv. 9
inv. 10 inv. 11 inv. 12 inv. 13 .
-
Slab thicknes [cm] 2 2 2 2 2 2
2 2 2
Flexural Strength [MPa] 65 60 75 55 65
70 95 100 105
dry /mass mass bad, bad,
Wetting good good good
good good good
not uniform too wet too wet
Bending no no yes yes no _ no
no some no
Cracks no no . no yes _ yes _ yes
, no some no - .0
n
Impact Resistance 1.1/ml 5 5 5 3 4 _
6 9.5 9 11 1-3
,
UV after 1000 h QUV A
(7)
7.9 8 8.2 - 7
6.8 7 6.8 IV
db
-1
o
0./1
cie
o
o
c.,
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[0181] The following table shows the common industrial standard for mechanical
properties of
engineered stone slabs:
industrial
standard
slab thickness [cnil 2
Flexural Strength [MPal > 45
wetting good
Bending no
cracks no
Impact Resistance [Jim] >4
UV after 1000 h QUV A db < 10
slab thickness [cm]
[0182] Accelerated weathering (QUV) simulates damaging effects of long term
outdoor exposure of
materials. The test was carried out according to ASTM method G 154 (QUV A),
Stone slabs were
exposed to varying conditions: ultraviolet radiation, moisture and heat. In
the test, UV radiation (UV
cycle: 8 h 60 C) and water vapor (condensation cycle: 4 h 50 C) conditions
are alternated. Overall
exposure time was 1000 h. The degree of color change due to weathering and UV-
exposure is
measured with the value "c/h". The value "db" is related to yellowing of the
stone slabs, wherein an
increase of the db-value or a positive db-valtie indicates that the change is
to a more (darker) yellow
color of the artificial stone slabs and a decrease of the db-value or a
negative db-value indicates a
change to a more blue color of the artificial stone slabs.
[0183] The experimental data shows that the unsaturated polyester resin
according to the invention
provides engineered stone having superior properties compared to engineered
stone manufactured
from conventional unsaturated polyester resins with respect to changes in
color. Whereas the stone
slabs manufactured from conventional unsaturated polyester resins had db-
values around 8 the slabs
prepared from the inventive polyester resin had db-values around 7, i.e.
showed less yellowing.
[0184] The above comparative data illustrates that the unsaturated polyester
resin according to the
invention provides engineered stone having superior properties compared to
engineered stone
manufactured from conventional unsaturated polyester resins. The engineered
stone slabs prepared
from the inventive unsaturated polyester resins showed improved mechanical
properties compared to
stone slabs prepared from unsaturated polyester resin having a molecular
weight of more than about
2500 g/mol.
[0185] The experimental data illustrates that resins comprising fumaric acid
and a saturated
polycarboxylic acid such as adipic acid show improved mechanical properties.
The resins employed in
the manufacture of the stone slabs of comparative examples 5 to 9 did not
comprise fumaric acid or a
saturated polycarboxylic acid. The stone slabs prepared therefrom showed a
flexural strength of up to
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75 MPa and an impact resistance of up to 5 J/m. The resins employed in
inventive examples 10 to 13
comprised fumaric acid and a saturated polycarboxylic acid. In contrast
thereto, the stone slabs
prepared from the inventive resins showed a flexural strength of up to 105 MPa
and an impact
resistance of up to 11 Jim.
[0186] Further, the stone slabs of comparative examples 8 and 9 had cracks.
Said stone slabs were
prepared from resins comprising a rather high content of maleic acid anhydride
and a rather low
content of diethylene glycol. Without wishing to be bound to any scientific
theory, the cracks in the
engineered stone slabs may be caused by the reactivity of the reactive double
bonds of the maleic acid
anhydride and also by the low content of diethylene glycol.
[0187] Further, the experimental data illustrates that the inventive
unsaturated polyester resins show
improved properties when employed with cristobalite fillers in the manufacture
of engineered stone
slabs compared to conventional resins which show poor properties when employed
with cristobalite
fillers.
[0188] The engineered stone slabs of comparative examples 6 and 9 and of
inventive example 13
have the same content of resin and cristobalite fillers. Whereas the slabs of
comparative examples 6
and 9 showed poor wetting properties or cracks in the stone slabs, the slabs
prepared from the
inventive resin in example 13 showed good wetting properties, did not bend and
had no cracks.
[0189] Further, the stone slabs prepared from the inventive resin with
cristobalite had considerably
better mechanical properties. The flexural strength of the stone slab of
example 13 was 105 MPa
compared to only 60 MPa and 65 Mpa, respectively, of the stone slabs of
comparative examples 6 and
9. FUrthermore, the impact resistance was higher (inventive: 11 Jim vs.
comparative: 5 J/m).
