EP2578552A1
EP2578552A1
EP2578552A1
(19)
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in the sheet or block to provide different appearances epoxy resin that may be used in the present invention.
exhibit equivalent or superior natural aesthetic effects to For example, a bifunctional or multifunctional epoxy resin
those of natural marble. Further, the resin sheet or block may be used. Here, an example of the bifunctional or
is directly subjected to pressing into artificial marble, multifunctional epoxy resin may be at least one selected
thereby preventing formation of impurities including bub- 5 from the group consisting of a bisphenol A epoxy resin,
bles in the artificial marble upon molding, and finally im- a bisphenol S epoxy resin, a tetraphenyl ethane epoxy
parting excellent gloss and strength to the artificial mar- resin, and a phenol novolac epoxy resin, without being
ble. limited thereto.
[0015] Also, the artificial marble may include two types [0021] The artificial marble of the present invention in-
of resin regions, that is, the first region and the second 10 cludes a coloring component added together with the
region, which are distinguished from each other as de- base resin and exhibiting different appearances in re-
scribed above, or may include more than two regions of gions of the artificial marble. The coloring component is
different resins as needed, thereby exhibiting colorful pat- not limited to a particular kind but may include any one
terns. which is mixed with the resin and imparts natural aes-
[0016] There is no restriction as to the kind of base 15 thetic effects. Examples of the coloring component may
resin that may be used in the present invention, and any include pigments, dyes, chips, or mixtures thereof.
typical base resin in the art may be used without limita- [0022] The pigment or dye may include any organic or
tion. Examples of the base resin may include an acrylic inorganic pigment or dye used in the art depending on a
resin, an unsaturated polyester resin, and an epoxy resin, desired appearance without being limited to particular
which may be used alone or in combinations thereof. 20 kinds. Also, the chips are not limited to a particular kind
[0017] Examples of the acrylic resin may include mon- but may include any chip used in the art, for example,
omers including methyl (meth)acrylate, ethyl (meth)acr- resin chips or natural ingredient chips. Here, the resin
ylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, chips may be prepared by manufacturing a flat substrate
benzyl (meth)acrylate, and glycidyl (meth)acrylate, or using an acrylic resin, an unsaturated polyester resin, an
mixtures thereof, , without being limited thereto. 25 epoxy resin, or a melamine resin and cutting the substrate
[0018] There is no restriction as to the kind of unsatu- into pieces having a suitable size. In this process, various
rated polyester that may be used in the present invention. pigments or dyes may be added to the resin, thereby
For example, the unsaturated polyester resin may be a producing color chips. Further, examples of the natural
resin obtained prepared by condensation of α,β-unsatu- ingredient chips may include shell, stone, stone powder,
rated dibasic acid or a mixture of the dibasic acid and a 30 quartz, charcoal powder, red clay, magnet powder,
saturated dibasic acid with polyvalent alcohol. Here, the herbs, pearl, mirror powder, or mixtures thereof. Howev-
resin may have an acid value of 5 to 50 and a molecular er, the coloring component including the chips used in
weight of 1,000 to 5,000, without being limited thereto. the present invention may be selected depending on de-
The polyester resin may be prepared by any method, sired appearances without being limited to the above ex-
without being limited thereto, for example, by mixing a 35 amples.
dibasic acid with polyvalent alcohol in a certain ratio (for [0023] The coloring component may be present in an
example., a mole ratio of alcoholic hydroxyl groups to amount of 0.1 to 500 parts by weight based on 100 parts
carboxyl groups is 0.8 to 1.2), performing condensation by weight of the base resin in the artificial marble. How-
of the mixture at 140 to 250°C under an inert gas atmos- ever, this amount is just an illustrative example, and the
phere, such as carbon dioxide gas and/or nitrogen gas 40 amount of the coloring component may be adjusted op-
while removing produced water, and gently raising tem- tionally depending on a desired appearance.
perature according to the degree of reaction. [0024] Each of the first region and the second region
[0019] Here, examples of the α,β-unsaturated dibasic may further include 200 to 500 parts by weight of inor-
acid or saturated dibasic acid may include maleic anhy- ganic fillers based on 100 parts by weight of the base
dride, citraconic acid, fumaric acid, itaconic acid, phthalic 45 resin forming each region. The inorganic fillers may in-
acid, phthalic anhydride, isophthalic acid, terephthalic clude any compound used in the art, for example, alumi-
acid, succinic acid, adipic acid, sebacic acid, and/or tet- num hydroxide, magnesium hydroxide, calcium carbon-
rahydrophthalic acid. Examples of the polyvalent alcohol ate, silica, alumina, calcium aluminate, and mixtures
may include ethylene glycol, diethylene glycol, triethyl- thereof, without being limited thereto. Particularly, inor-
ene glycol, propylene glycol, dipropylene glycol, tripro- 50 ganic fillers having a particle size of 3 to 200 mm may be
pylene glycol, polypropylene glycol, 1,3-butylene glycol, used, but are not limited thereto. In the present invention,
hydrogenated bisphenol A, trimethylolpropane monoaryl the inorganic fillers may be treated with a silane coupling
ether, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol agent, a titanate coupling agent or stearic acid on the
and/or glycerin. As needed, the polyester resin may fur- surface thereof in order to guarantee dispersibility and
ther include monobasic acids, such as acrylic acid, pro- 55 mechanical strength while preventing precipitation there-
pionic acid and/or benzoic acid; or polybasic acids, such of.
as trimellitic acid and/or benzol tetracarbonic acid. [0025] The inorganic filler may be present in an amount
[0020] Further, there is no restriction as to the kind of of 200 to 500 parts by weight based on 100 parts by
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weight of the base resin in each region. If the amount of captan, trimethylbenzyl mercaptan, and mixtures there-
the inorganic filler is less than 200 parts by weight, it is of. The radical carrier may be present in an amount of
difficult to obtain suitable viscosity in the manufacturing 0.1 to 5 parts by weight based on 100 parts by weight of
process. If the amount of the inorganic filler exceeds 500 the base resin in each region, without being limited there-
parts by weight, the resin can have an excessively high 5 to.
viscosity, thereby exhibiting low formability. [0032] Furthermore, the artificial marble of the present
[0026] The artificial marble of the present invention invention may further include at least one kind of additives
may further include 0.2 to 5 parts by weight of a crosslink- selected from the group consisting of silicon or non-sili-
er based on 100 parts by weight of the base resin of each con antifoaming agents; silane including trimethoxysi-
of the first region and the second region. Here, the 10 lane, acid coupling agent, or titanate coupling agents;
crosslinker is not limited to a particular kind but may in- phenyl salicylate, benzophenone, benzotriazole, nickel
clude any crosslinker which may form a cross-link with derivative, or radical scavenger-type UV absorbers; hal-
the base resin constituting the artificial marble. Examples ogen, phosphorus or inorganic metal flame retardants;
of the crosslinker may include at least one selected from stearic acid or silicone releasing agents; catechol or hy-
the group consisting of ethylene glycol di(meth)acrylate, 15 droquinone polymerization inhibitors; and phenol, amine,
diethylene glycol di(meth)acrylate, triethylene glycol di quinone, sulfur or phosphorus antioxidants.
(meth)acrylate, tetraethylene glycol di(meth)acrylate, tri- [0033] The present invention also relates to a method
methylolpropane tri(meth)acrylate, 1,6-hexanediol di of manufacturing artificial marble, which includes prepar-
(meth)acrylate, polybutylene glycol di(meth)acrylate, ne- ing uncured resin sheets or blocks using at least two dif-
opentyl glycol di(meth)acrylate, and mixtures thereof. 20 ferent types of resin compositions providing different aes-
[0027] The crosslinker may be present in an amount thetic effects, respectively; kneading the resin sheets or
of 0.2 to 5 parts by weight based on 100 parts by weight blocks of the at least two different types of resin compo-
of the base resin in each region. If the amount of the sitions and forming the kneaded product into an uncured
crosslinker is less than 0.2 parts by weight, bonding marble resin sheet or resin block; and pressing the mar-
strength of materials can be deteriorated due to formation 25 ble resin sheet or resin block.
of uneven parts on the surface of the artificial marble or [0034] Fig. 1 is a flowchart of a method of manufactur-
generation of bubbles in upper or lower parts thereof and ing artificial marble according to an embodiment of the
heat resistance or discoloration resistance can be re- present invention.
duced. If the amount of the crosslinker exceeds 5 parts [0035] First, uncured resin sheets or blocks are pre-
by weight, phase change of chips can occur or an aes- 30 pared using at least two different types of resin compo-
thetic pattern of the artificial marble can be deteriorated. sitions prepared to exhibit different aesthetic effects after
[0028] Each of the first region and the second region curing, respectively.
of the artificial marble may further include a crosslinking [0036] This process may include, for example, (1) pre-
accelerator. paring a raw material composition by kneading resin syr-
[0029] The crosslinking accelerator is not limited to a 35 up and inorganic fillers; and (2) forming the raw material
particular kind but may include organic peroxides, for ex- composition into an uncured resin sheet or block by cal-
ample, diacyl peroxides, such as benzoyl peroxide and endering, extruding, pressing, or casting.
dicumyl peroxide; hydroperoxides, such as butyl hy- [0037] In preparation (1) of the raw material composi-
droperoxide and cumyl hydroperoxide; t-butyl peroxy tion, the resin syrup is not particularly limited but may
maleic acid; t-butyl hydroperoxide; t-butyl hydroperoxy- 40 include any resin syrup generally used in the field of ar-
butyrate; acetyl peroxide; lauroyl peroxide; azobisisobu- tificial marble. The resin syrup generally corresponds to
tyronitrile; azobisdimethylvaleronitrile; t-butyl peroxyne- the base resin and may be prepared by dissolving a
odecanoate; and t-amyl peroxy-2-ethylhexanoate, which high-molecular weight compound (e.g., polymer or oli-
may be used alone or in combinations thereof. The gomer) in a monomer. For example, in manufacturing
crosslinking accelerator may be used together with a po- 45 artificial marble using an acrylic resin according to the
lymerization initiator. present invention, a polymer of one of the aforemen-
[0030] In addition to the above components, a mixture tioned acrylic monomers (e.g., polymethyl methacrylate)
of amine peroxide and sulfonic acid or a mixture of per- is used as the high molecular weight compound and one
oxide and a cobalt compound is used such that polym- of the aforementioned acrylic monomers (e.g., methyl
erization and curing may be performed at room temper- 50 methacrylate) is used as the monomer, without being lim-
ature. The crosslinking accelerator may be present in an ited thereto.
amount of 0.2 to 3 parts by weight based on 100 parts [0038] In preparing the resin syrup, the content of each
by weight of the base resin, without being limited thereto. component is not particularly limited but may be adjusted
[0031] The first or second region of the artificial marble suitably depending on a desired viscosity. For example,
of the present invention may further include a radical car- 55 the resin syrup may include about 10 to 50 wt% of a
rier. Here, the radical carrier is not limited to a particular monomer.
kind but may include mercaptan compounds, such as [0039] In addition to the high molecular weight com-
n-dodecyl mercaptan, t-dodecyl mercaptan, benzyl mer- pound and the monomer, the resin syrup may further
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include additives, such as a crosslinker and a crosslink- on purposes, thereby producing artificial marble having
ing accelerator, as described above, and may suitably a substantially similar pattern to that of natural marble.
contain a coloring component capable of providing aes- [0049] Next, the marble resin sheet or block is subject-
thetic effects. ed to pressing. Pressing may include, for example, (a)
[0040] In preparation (1) of the raw material composi- 5 placing the marble resin sheet or block in a mold; and (b)
tion, the resin syrup (liquid raw material) is kneaded with pressing the resin sheet or block at 30 to 150°C and 5 to
the inorganic filler, thereby adjusting viscosity. Here, 50 Kg/cm2.
kneading may be carried out using a tool generally used [0050] As such, according to the present invention, an
in the art, e.g., a kneader. In this process, the viscosity uncured sheet or block is placed in a mold and subjected
of the mixture may be adjusted to 5,000 to 100,000 Ps. 10 to pressing, thereby producing artificial marble having
If the viscosity is less than 5,000 Ps, pressing cannot be excellent gloss and mechanical strength without bubbles
suitably performed. If the viscosity is greater than even after pressing at a low temperature and a low pres-
100,000 Ps, the viscosity of the mixture can increase sure.
excessively high, thereby making it difficult to mold the [0051] The method of the present invention may further
kneaded product into a sheet or block. 15 include post-processes, for example, cooling the cured
[0041] In formation (2) of the uncured resin sheet or product after ejecting from the mold, cutting the cured
block, the kneaded product is formed into an uncured product into pieces having a desired size, and/or suitably
resin sheet or block. Here, the sheet or block may be sanding the surface of artificial marble.
formed by any method, for example, suitably using cal-
endering, extruding, pressing, or casting, without being 20 Examples
limited thereto, so long as the high molecular weight com-
pound, the monomer, or the crosslinker included in the [0052] Next, the present invention will be explained in
kneaded product does not react with each other. more detail with reference to the following examples.
[0042] Further, the dimensions of the resin sheets or These examples are provided for illustrative purposes
blocks, e.g., thickness or area, are not particularly limited, 25 only and are not to be in any way construed as limiting
but may be suitably adjusted depending on desired pur- the present invention.
poses.
[0043] Then, the uncured resin sheets or blocks are Example 1
kneaded and formed into an uncured marble resin sheet
or resin block. 30 Preparation of uncured resin sheet
[0044] Kneading the resin sheets or blocks may be car-
ried out by any method, for example, a typical kneader, [0053] 100 parts by weight of acrylic resin syrup con-
in consideration of desired aesthetic patterns. taining 30 wt% of polymethyl methacrylate and 70 wt%
[0045] Further, forming the mixture into the uncured of methyl methacrylate, 400 parts by weight of aluminum
marble resin sheet of block may be carried out by any 35 hydroxide, 0.2 parts by weight of t-butyl peroxyneo-
method known in the art, for example, calendering, ex- decanoate, 0.3 parts by weight of t-amyl peroxy-2-ethyl-
truding, pressing, or casting, under conditions that pre- hexanoate, 3 parts by weight of ethylene glycol dimeth-
vent the components included in the sheet or block from acrylate, 0.2 parts by weight of normal dodecyl mer-
causing a curing reaction. captan, 0.2 parts by weight of an antifoaming agent (BYK
[0046] Further, the dimensions of the marble resin 40 555, BYK-Chemie, Germany), 0.75 parts by weight of a
sheet or block, e.g., thickness or area, are not particularly coupling agent (BYK 900, BYK-Chemie, Germany), and
limited but may be suitably adjusted depending on de- 0.2 parts by weight of a UV stabilizer (Hisorp-P, LG
sired purposes. Chem, Korea) were mixed into a raw material slurry. 0.3
[0047] As described above, at least two types of sheets parts by weight of a pigment as a coloring component
or blocks providing different aesthetic effects are knead- 45 was added to the slurry, thereby preparing a resin com-
ed and formed into an uncured marble resin sheet or position.
resin block, which is then effectively placed in a mold in [0054] Then, the resin composition was added to a
the pressing process, thereby improving molding effi- kneader including 400 parts by weight of aluminum hy-
ciency while preventing generation of bubbles therein droxide and 200 parts by weight of chips through an inlet
during molding. 50 pipe and kneaded for about 20 minutes to have a viscosity
[0048] Further, at least two types of uncured resin of about 1,000 cps. Then, the kneaded product was re-
sheets or blocks providing different aesthetic effects are moved and molded from a bulk state into a sheet using
kneaded and formed into a marble resin sheet or resin slab rollers.
block, thereby imparting a natural pattern such as a wa- [0055] Meanwhile, another resin sheet was prepared
ter-flowing pattern to final artificial marble, which is dis- 55 by the same process as above except that a combination
tinguished from conventional artificial marble of solid- of a pigment and chips providing a different appearance
color chips. Further, a plurality of sheets or blocks may from that of the pigment and the chips used as above
be used to form a marble resin sheet or block depending was used as a coloring component.
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Preparation of uncured marble resin sheet consisting of aluminum hydroxide, magnesium hy-
droxide, calcium carbonate, silica, alumina, and cal-
[0056] The prepared two resin sheets were placed in cium aluminate.
a kneader and kneaded for about 10 seconds to provide
a marble pattern having two mixed patterns. Then, the 5 8. The artificial marble of claim 1, wherein the first re-
bulk composition having the marble pattern was removed gion or the second region further comprises 0.2 to 5
and formed into an uncured marble resin sheet. parts by weight of a crosslinker based on 100 parts
by weight of the base resin.
Preparation of artificial marble
10 9. The artificial marble of claim 8, wherein the crosslink-
[0057] The prepared marble resin sheet was placed in er comprises at least one selected from the group
a mold preheated to about 120°C and subjected to press- consisting of ethylene glycol di(meth)acrylate, dieth-
ing at about 15 Kg/cm2, followed by removing the mold ylene glycol di(meth)acrylate, triethylene glycol di
and cooling and sanding the resin sheet, thereby produc- (meth)acrylate, tetraethylene glycol di(meth)acr-
ing artificial marble. Fig. 2 illustrates the artificial marble 15 ylate, trimethylolpropane tri(meth)acrylate, 1,6-hex-
prepared in this manner. anediol di(meth)acrylate, polybutylene glycol di
(meth)acrylate, and neopentyl glycol di(meth)acr-
Example 2 ylate.
[0058] Artificial marble was prepared in the same man- 20 10. The artificial marble of claim 1, further comprising:
ner as in Example 1 except that a coloring component at least one selected from the group consisting of
was suitably changed to provide a different aesthetic pat- crosslinking accelerators, radical carriers, coupling
tern from that of the artificial marble of Example 1. Fig. agents, UV absorbers, flame retardants, releasing
3 illustrates the artificial marble prepared in this manner. agents, polymerization inhibitors, and antioxidants.
25
11. A method of manufacturing artificial marble, com-
Claims prising:
1. Artificial marble comprising a pressed product of an preparing uncured resin sheets or blocks using
uncured marble resin sheet or resin block, the artifi- 30 at least two different types of resin compositions
cial marble comprising: a first region comprising a providing different aesthetic effects, respective-
base resin and a coloring component; and a second ly;
region comprising a base resin and a coloring com- kneading the resin sheets or blocks and forming
ponent providing an appearance different from that the kneaded product into an uncured marble res-
of the coloring component of the first region. 35 in sheet or resin block; and
pressing the marble resin sheet or resin block.
2. The artificial marble of claim 1, wherein the base
resin comprises an acrylic resin, an unsaturated pol- 12. The method of claim 11, wherein the preparing un-
yester resin, or an epoxy resin. cured resin sheets or blocks comprises (1) preparing
40 a raw material composition by kneading resin syrup
3. The artificial marble of claim 1, wherein the coloring and inorganic fillers; and (2) forming the raw material
component comprises a pigment, a dye, or a chip. composition into an uncured resin sheet or block us-
ing calendering, extruding, pressing, or casting.
4. The artificial marble of claim 3, wherein the chip com-
prises a resin chip or a natural ingredient chip. 45 13. The method of claim 12, wherein the raw material
composition has a viscosity of 5,000 to 100,000 Ps.
5. The artificial marble of claim 1, wherein the coloring
component is present in an amount of 0.1 to 500 14. The method of claim 11, wherein the marble resin
parts by weight based on 100 parts by weight of the sheet or block is formed by calendering, extruding,
base resin. 50 pressing, or casting.
6. The artificial marble of claim 1, wherein the first re- 15. The method of claim 11, wherein the pressing the
gion or the second region further comprises 200 to marble resin sheet or resin block comprises: (a) plac-
500 parts by weight of inorganic fillers based on 100 ing the marble resin sheet or block in a mold; and
parts by weight of the base resin. 55 (b) pressing the resin sheet or block at 30 to 150°C
and 5 to 50 Kg/cm2.
7. The artificial marble of claim 6, wherein the inorganic
fillers comprise at least one selected from the group
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