PLASTICIZERS, RESIN COMPOSITION, AND METHOD FOR MANUFACTURING
PLASTICIZERS AND RESIN COMPOSITION
5
TECHNICAL FIELD
[0001] The present invention relates to a plasticizer and a
resin composition, and a preparation method thereof, and more
particularly, to a plasticizer and a resin composition which
10 may improve poor physical properties that have been ascribed
to structural limitations although having environmental
friendliness, and a method of preparing the plasticizer and
the resin composition.
BACKGROUND ART
15 [0002] Typically, with respect to a plasticizer, alcohol
reacts with polycarboxylic acid, such as phthalic acid and
adipic acid, to form an ester corresponding thereto. Also,
in consideration of domestic and foreign regulations limiting
phthalate-based plasticizers that are harmful to human body,
20 research into environmentally friendly plasticizers, which
may replace phthalate-based plasticizers such as
terephthalate-based plasticizers, adipate-based plasticizer,
and other polymer-based plasticizers, has continued.
[0003] In order to manufacture flooring materials, wallpaper,
25 sheet products which require light resistance as a physical
PCT/KR2014/009979
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property, an appropriate plasticizer must be used in
consideration of discoloration. With respect to a polyvinyl
chloride (PVC) based compound formulation for a wall paper or
sheet, additives such as plasticizers, fillers, stabilizers,
viscosity reducing agents, dispersants, antifoaming agents5 ,
and a foaming agents are mixed with a PVC resin according to
properties required by the corresponding standards, such as
tensile strength, elongation rate, light resistance, bleeding
phenomenon, and gelling property.
10 [0004] For example, in the case that inexpensive dioctyl
terephthalate is used among environmentally friendly
plasticizers that are applicable to PVC, since its viscosity
is high and the absorption rate of the plasticizer is
relatively low, a bleeding phenomenon, in which the
15 plasticizer comes out from the backside of a sheet, is not
only observed, but gelling property is also not excellent.
[0005] Thus, there is a continuous need to research into
techniques by which a product better than the dioctyl
terephthalate or a novel composition including dioctyl
20 terephthalate is developed and optimally used as a
plasticizer for a vinyl chloride-based resin.
Prior Art Documents
Patent Documents
[0006] (Patent Document 1) Korean Patent Application Laid-
25 Open Publication No. 2006-0087889 (2006.08.03)
PCT/KR2014/009979
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DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0007] As a result of continuous research into plasticizers,
the present inventors found an environmentally friendl5 y
plasticizer which may improve poor physical properties that
have been ascribed to structural limitations although having
environmental friendliness, thereby leading to the completion
of the present invention.
10 [0008] The present invention provides a plasticizer which
may improve physical properties, such as light resistance
required for a compound formulation when used as a
plasticizer of a resin composition, or viscosity, bleeding
phenomenon, and gelling property required for a sheet
15 formulation, a preparation method thereof, and a resin
composition including the plasticizer.
TECHNICAL SOLUTION
[0009] According to an aspect of the present invention,
there is provided a plasticizer including isophthalate and
20 terephthalate. According to another aspect of the present
invention, there is provided a method of preparing a
plasticizer including:
[0010] adding both isophthalic acid and terephthalic acid to
alcohol to obtain a mixture;
25 [0011] adding a catalyst to the mixture to react in a
nitrogen atmosphere;
PCT/KR2014/009979
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[0012] removing unreacted alcohol and neutralizing unreacted
acid; and
[0013] dehydrating and filtering by vacuum distillation to
obtain a plasticizer.
[0014] According to another aspect of the present invention5 ,
there is provided a method of preparing a plasticizer
including: preparing an ester-based mixture including
terephthalate and isophthalate; and
[0015] obtaining a plasticizer by blending the terephthalate
10 and the isophthalate to include the isophthalate in an amount
of 1 wt% to 99 wt% based on a total weight of the ester-based
mixture.
[0016] According to another aspect of the present invention,
there is provided a resin composition including the
15 plasticizer in an amount of 5 parts by weight to 150 parts by
weight based on 100 parts by weight of a resin selected from
the group consisting of ethylene vinyl acetate, polyethylene,
polypropylene, polyvinyl chloride, polystyrene, polyurethane,
and a thermoplastic elastomer.
20 ADVANTAGEOUS EFFECTS
[0017] According to the present invention, a plasticizer,
which may improve physical properties, such as light
resistance required for a compound formulation when used as a
plasticizer of a resin composition, or viscosity, bleeding
25 phenomenon, and gelling property required for a sheet
PCT/KR2014/009979
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formulation, by improving poor physical properties that have
been ascribed to structural limitations although having
environmental friendliness, and a resin composition including
the plasticizer may be provided.
MODE FOR CARRYING OUT THE INVENTIO5 N
[0018] Hereinafter, the present invention will be described
in detail.
[0019] First, the present invention has technical features
that provide a plasticizer which may improve poor physical
10 properties that have been ascribed to structural limitations
although having environmental friendliness.
[0020] According to an embodiment of the present invention,
a plasticizer including isophthalate and terephthalate is
provided.
15 [0021] The plasticizer according to the present invention is
an environmentally friendly plasticizer, wherein the
expression “environmentally friendly plasticizer” may denote
an ether-free ester-based plasticizer or ether-free phthaltype
ester-based plasticizer, unless otherwise specified.
20 Herein, the phthalate may include both isophthalate and
terephthalate.
[0022] The expression “ester-free” denotes that an amount of
an ether component included in the plasticizer is in a range
of 1,000 ppm or less, 100 ppm or less, or 10 ppm or less.
25 [0023] In the plasticizer according to the embodiment of the
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present invention, a mixing ratio of the isophthalate to the
terephthalate may be in a range of 1:99 to 99:1 as a weight
ratio.
[0024] In the plasticizer according to the embodiment of the
present invention, the mixing ratio of the isophthalate t5 o
the terephthalate may be in a range of 20:80 to 99:1, 50:50
to 99:1, or 50:50 to 90:10 as a weight ratio.
[0025] Also, in the plasticizer according to the embodiment
of the present invention, the mixing ratio of the
10 isophthalate to the terephthalate may be in a range of 60:40
to 90:10 as a weight ratio.
[0026] In the plasticizer according to the embodiment of the
present invention, the isophthalate may be included in an
amount of 1 wt% to 99 wt%, 20 wt% to 99 wt%, 50 wt% to 99 wt%,
15 50 wt% to 90 wt%, or 60 wt% to 90 wt% based on a total weight
of the plasticizer.
[0027] Specifically, in the plasticizer according to the
embodiment of the present invention, the amount of the
isophthalate may be the same as or greater than an amount of
20 the terephthalate.
[0028] In the plasticizer according to the embodiment of the
present invention, when the amount of the isophthalate used
is the same as or greater than the amount of the
terephthalate, hardness and elongation rate may be
25 significantly improved during the preparation of a compound
PCT/KR2014/009979
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formulation or sheet formulation, and thus, productivity and
workability of the product may be improved and an effect of
increasing plasticizing efficiency may be excellent.
[0029] The isophthalate, for example, may have an end group
independently selected from alkyl groups having 1 to 15 2
carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8
to 10 carbon atoms, 8 and 9 carbon atoms, or 8 carbon atoms.
[0030] In particular, in the plasticizer according to the
embodiment of the present invention, since the isophthalate
10 includes an end group selected from alkyl groups having 8 to
10 carbon atoms, migration resistance and heating loss may be
significantly improved in comparison to a plasticizer using
an ester having an end group selected from alkyl groups
having 7 or less carbon atoms. In the case that migration
15 resistance and heating loss are increased, it may be very
detrimental to processability and long-term stability of the
final product. In particular, an increase in heating loss
may mean a decrease in the amount of the plasticizer present
in the final product.
20 [0031] Thus, the plasticizer according to the embodiment of
the present invention may include the isophthalate which
includes an ester having an end group selected from alkyl
groups having 8 to 10 carbon atoms in order to improve
migration resistance and heating loss.
25 [0032] In the plasticizer according to the embodiment of the
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present invention, the isophthalate may be
dialkylisophthalate, and the alkyl may be an alkyl having 1
to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon
atoms, 8 to 10 carbon atoms, 8 and 9 carbon atoms, or 8
carbon atoms5 .
[0033] As a specific example, the isophthalate may have a
structure represented by Chemical Formula 1 below.
[0034] [Chemical Formula 1]
10 [0035] Also, according to the plasticizer according to the
embodiment of the present invention, the terephthalate may be
included in an amount of 1 wt% to 99 wt%, 1 wt% to 80 wt%, 1
wt% to 50 wt%, 10 wt% to 50 wt%, or 10 wt% to 40 wt% based on
the total weight of the plasticizer.
15 [0036] The terephthalate may have an end group independently
selected from alkyl groups having 1 to 12 carbon atoms, 3 to
11 carbon atoms, 4 to 10 carbon atoms, 8 to 10 carbon atoms,
8 and 9 carbon atoms, or 8 carbon atoms.
[0037] As a specific example, the terephthalate may include
20 an alkyl group having the same number of carbon atoms as the
end group of the above-described isophthalate.
[0038] According to an embodiment of the present invention,
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since the terephthalate particularly includes an end group
selected from alkyl groups having 8 to 10 carbon atoms,
migration resistance and heating loss may be significantly
improved in comparison to a plasticizer using an ester having
an end group selected from alkyl groups having 7 or les5 s
carbon atoms. In the case that migration resistance and
heating loss are increased, it may be very detrimental to
processability and long-term stability of the final product.
In particular, an increase in heating loss may mean a
10 decrease in the amount of the plasticizer present in the
final product.
[0039] Thus, the plasticizer according to the embodiment of
the present invention may include the terephthalate which
includes an ester having an end group selected from alkyl
15 groups having 8 to 10 carbon atoms in order to improve
migration resistance and heating loss.
[0040] In the plasticizer according to the embodiment of the
present invention, the terephthalate may be
dialkylterephthalate, and the alkyl may be an alkyl having 1
20 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon
atoms, 8 to 10 carbon atoms, 8 and 9 carbon atoms, or 8
carbon atoms.
[0041] As another example, the terephthalate may have a
structure represented by Chemical Formula 2 below.
25 [0042] [Chemical Formula 2]
PCT/KR2014/009979
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[0043] A one-pot preparation method or a blending method may
be used as a method of preparing the plasticizer according to
the embodiment of the present invention. For example, the
one-pot preparation method is as follows5 :
[0044] That is, isophthalic acid is added to alcohol
(hereinafter, referred to as “first step”).
[0045] A catalyst is added to the mixture and reacted in a
nitrogen atmosphere.
10 [0046] Thereafter, unreacted alcohol is removed and
unreacted acid is neutralized.
[0047] Subsequently, dehydration and filtration may be
performed by vacuum distillation to prepare the plasticizer.
[0048] As a specific example, the isophthalic acid and the
15 terephthalic acid may be added in a weight ratio of 20:80 to
99:1, 50:50 to 99:1, or 50:50 to 90:10.
[0049] Also, as another example, the isophthalic acid and
the terephthalic acid may be added in a weight ratio of 60:40
to 90:10.
20 [0050] Also, for example, the blending method is as follows:
[0051] Terephthalate and isophthalate are prepared.
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[0052] The plasticizer may be prepared by blending the
terephthalate and the isophthalate so as to include the
isophthalate in an amount of 1 wt% to 99 wt%, 20 wt% to 99
wt%, 50 wt% to 99 wt%, 50 wt% to 90 wt%, or 60 wt% to 90 wt%.
[0053] In the blending method, the terephthalate may b5 e
prepared by the steps of: adding terephthalic acid to alcohol
and then adding a catalyst to react in a nitrogen atmosphere;
removing unreacted alcohol and neutralizing unreacted acid;
and dehydrating and filtering by vacuum distillation.
10 [0054] Also, in the blending method, the isophthalate may be
prepared by the steps of: adding isophthalic acid to alcohol
and then adding a catalyst to react in a nitrogen atmosphere;
removing unreacted alcohol and neutralizing unreacted acid;
and dehydrating and filtering by vacuum distillation.
15 [0055] The alcohol used in the one-pot preparation method or
blending method, for example, may be an aliphatic or aromatic
compound having an alkyl group having 1 to 20 carbon atoms.
Specific examples of the alcohol may be at least one selected
from the group consisting of aliphatic alcohols having an
20 alkyl group having 1 to 20 carbon atoms and isomers thereof,
such as methanol, ethanol, propanol, n-butanol, iso-butanol,
tert-butanol, pentanol and isomers thereof, hexanol and
isomers thereof, heptanol and isomers thereof, octanol and
isomers thereof such as 2-ethylhexyl alcohol and n-octyl
25 alcohol, , nonanol and isomers thereof such as isononyl
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alcohol, decanol and isomers thereof such as 2-propylheptyl
alcohol, 4-methyl-2-propyl hexyl alcohol, 5-methyl-2-propylhexyl
alcohol, n-decyl alcohol, undecanol and isomers thereof,
and dodecanol and isomers thereof, and aromatic alcohols
having an alkyl group having 1 to 20 carbon atoms or not5 ,
such as phenol and benzyl alcohol.
[0056] As another example, the alcohol may be a branchedchain
aliphatic alcohol having an alkyl group having 1 to 20
carbon atoms, 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4
10 to 10 carbon atoms, 8 to 10 carbon atoms, 8 and 9 carbon
atoms, or 8 carbon atoms.
[0057] The alcohol used in the one-pot preparation method
may be used in an amount of 150 mol% to 500 mol%, 200 mol% to
400 mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270
15 mol% to 330 mol% based on total 100 mol% of a mixture of the
terephthalic acid and the isophthalic acid.
[0058] Also, the alcohol used in the blending method may be
used in an amount of 150 mol% to 500 mol%, 200 mol% to 400
mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270 mol%
20 to 330 mol% based on 100 mol% of the terephthalic acid.
[0059] Furthermore, the alcohol used in the blending method
may be used in an amount of 150 mol% to 500 mol%, 200 mol% to
400 mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270
mol% to 330 mol% based on 100 mol% of the isophthalic acid.
25 [0060] Examples of the catalyst used in the one-pot
PCT/KR2014/009979
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preparation method or the blending method may include at
least one selected from the group consisting of acid
catalysts such as sulfuric acid, hydrochloric acid, nitric
acid, para-toluenesulfonic acid, methanesulfonic acid,
ethanesulfonic acid, propanesulfonic acid, butanesulfoni5 c
acid, and alkyl sulfuric acid; metal salts such as aluminum
lactate, lithium fluoride, potassium chloride, cesium
chloride, calcium chloride, ferric chloride, and aluminum
phosphate; metal oxide such as heteropolyacid;
10 natural/synthetic zeolite; cation and anion exchange resins;
and organic metals such as tetra alkyl titanate and polymers
thereof. As a specific example, tetra alkyl titanate may be
used.
[0061] An amount of the catalyst used may vary depending on
15 the type thereof, and for example, with respect to a uniform
catalyst, the amount of the catalyst used may be in a range
of 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 1 wt% to 5 wt%, or 2
wt% to 4 wt% based on total 100 wt% of a reactant. With
respect to a non-uniform catalyst, the amount of the catalyst
20 used may be in a range of 5 wt% to 200 wt%, 5 wt% to 100 wt%,
20 wt% to 200 wt%, or 20 wt% to 150 wt% based on the total
weight of the reactant.
[0062] In this case, the reaction temperature may be in a
range of 180ºC to 280ºC, 200ºC to 250ºC, or 210ºC to 230ºC.
25 [0063] The plasticizer thus prepared may provide a resin
PCT/KR2014/009979
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composition that is effective to both compound formulation
and sheet formulation by being included in an amount of 5
parts by weight to 150 parts by weight, 40 parts by weight to
100 parts by weight, or 40 parts by weight to 50 parts by
weight based on 100 parts by weight of a resin selected fro5 m
the group consisting of ethylene vinyl acetate, polyethylene,
polypropylene, polyvinyl chloride, polystyrene, polyurethane,
and a thermoplastic elastomer.
[0064] For example, the resin composition may be used in
10 manufacturing electric wires, flooring materials, automotive
interior materials, films, sheets, wallpaper, or tubes.
[0065] Hereinafter, the present invention will be described
in detail, according to specific examples. However, the
following examples are merely presented to exemplify the
15 present invention, and the scope of the present invention is
not limited thereto.
[0066]
[0067] 1.8 g of tetraisopropyl titanate as a reaction
catalyst was added to a reactant, in which 1.5 mol
20 terephthalic acid, 1.5 mol isophthalic acid, and 9.0 mol 2-
ethylhexanol were mixed in a five-neck round flask equipped
with a temperature sensor, a mechanical stirrer, a condenser,
a decanter, and a nitrogen injection apparatus, and the
reaction was performed for 5 hours while increasing
25 temperature to 220°C.
PCT/KR2014/009979
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[0068] After the reaction, an excessive amount of alcohol
was extracted under reduced pressure, and neutralization and
washing processes were performed using soda ash and distilled
water. Then, dehydration and filtration were carried out by
vacuum distillation5 .
[0069] As a result of analyzing the obtained composition
with a GC-Mass analyzer, it was identified that the
composition was formed of compounds respectively having the
following Chemical Formulae 1 and 2 and a weight ratio was
10 50:50.
[0070] [Chemical Formula 1]
[0071] [Chemical Formula 2]
[0072]
[0073] The same process was repeated except that a reactant,
15 in which 2.1 mol terephthalic acid, 0.9 mol isophthalic acid,
PCT/KR2014/009979
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and 9.0 mol 2-ethylhexanol were mixed, was used in
Preparation Example 1.
[0074] As a result of analyzing the obtained plasticizer
with a GC-Mass analyzer, it was identified that the
plasticizer included the compounds respectively havin5 g
Chemical Formulae 2 and 1, which were suggested in
Preparation Example 1, at a weight ratio of 70:30 (Chemical
Formula 2:Chemical Formula 1).
10 [0075]
[0076] The same process was repeated except that a reactant,
in which 3.0 mol isophthalic acid and 9.0 mol 2-ethylhexanol
were mixed while not using terephthalic acid, was used in
Preparation Example 1.
15 [0077] As a result of analyzing the obtained plasticizer
with a GC-Mass analyzer, it was identified that the
plasticizer was a compound having Chemical Formula 1 which
was suggested in Preparation Example 1.
20 [0078]
[0079] The same process was repeated except that a reactant,
in which 3.0 mol terephthalic acid and 9.0 mol 2-ethylhexanol
were mixed while not using isophthalic acid, was used in
Preparation Example 1.
25 [0080] As a result of analyzing the obtained plasticizer
PCT/KR2014/009979
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with a GC-Mass analyzer, it was identified that the
plasticizer was a compound having Chemical Formula 2 which
was suggested in Preparation Example 1.
[0081] The compound thus obtained and the compound obtained
in Preparation Example 3 were mixed in a weight ratio o5 f
70:30 (Chemical Formula 2:Chemical Formula 1).
[0082]
[0083] The compound obtained in Preparation Example 4 and
10 the compound obtained in Preparation Example 3 were mixed in
a weight ratio of 50:50.
[0084]
[0085] The plasticizers obtained in preparation Examples 1
15 to 5 were respectively used as experimental samples of
Example 1 to 4 and Comparative Example 3.
[0086] Also, the following products were respectively
prepared as experimental samples of Comparative Examples 1
and 2.
20 [0087] Dioctyl phthalate (DOP): LGflex DOP by LG Chem Ltd.
[0088] Dioctyl terephthalate (DOTP): GL300 by LG Chem Ltd.
[0089] The samples of Examples 1 to 4 and Comparative
Example 3 using the plasticizers obtained in Preparation
Examples 1 to 5 and the samples of Comparative Examples 1 and
25 2 using commercial plasticizers were prepared in accordance
PCT/KR2014/009979
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with ASTM D638 and in such a manner that 50 parts by weight
of a plasticizer, 40 parts by weight of a filler, 5 parts by
weight of a stabilizer, and 0.3 pats by weight of stearic
acid were mixed with 100 parts by weight of PVC at a
temperature of 100°C at 500 rpm for 2 minutes and at 1,305 0
rpm for about 10 minutes in a 3L super mixer. Then, roll
milling was performed at 170°C for 4 minutes to prepare 5 mm
thick sheets. After pressing was performed at 185°C while
being subjected to preheating for 3 minutes, heating for 3
10 minutes, and cooling for 3 minutes, 1 to 3 mm thick sheets
were prepared to prepare several dumbbell-shaped samples as
type “C” samples.
[0090] Each sample was subjected to the following physical
tests, and the results thereof are presented in Table 1 below.
15 [0091]
[0092] *Presence of Bleeding and Accelerated Weathering
(QUV): After irradiating the samples with ultraviolet (UV)
rays at a QUV oven temperature of 100°C for 200 hours, the
samples were taken out from the oven, and the presence of
20 bleeding was checked and ΔE was measured using a colorimeter.
[0093] *Hardness(ASTMD785): A hardness-tester (“C” type)
stylus was fully lowered down and a hardness value appeared
after 10 seconds was then recorded. Tests were performed on
3 positions for each sample, and the average hardness value
25 was then calculated.
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[0094] *Tensile Strength and Elongation Rate(ASTM D638):
Elongation rate and tensile strength at a breaking point of
each sample were measured after pulling the sample at a
cross-head speed of 200 mm/min using a test instrument, U.T.M.
The tensile strength was calculated by the equation: tensil5 e
strength (kgf/cm2) = load (kgf)/(thickness (cm) x width (cm)),
and the elongation rate was calculated by the equation:
elongation rate (%) = extension /initial length x 100.
[0095] [Table 1]
Item
Examp
le 1
Examp
le 2
Comparat
ive
Example
3
Examp
le 3
Examp
le 4
Comparat
ive
Example
1
Comparat
ive
Example
2
Preparation
Example No. 1 2 3 4 5 - -
Physical properties
Presence of
bleeding
absen
ce
absen
ce absence absen
ce
absen
ce absence presence
QUV (ΔE) 1.86 2.18 1.02 2.10 1.75 1.01 3.29
Hardness 88.5 90.0 88.0 89.8 88.7 88.0 90.7
Room
temper
ature
Elong
ation
rate
(%)
259.2 257.9 263.1 257.5 260.2 262.5 252.1
Tensi
le
stren
gth
(kg/c
m2)
184.5 185.4 180.5 185.0 184.0 180.7 190.8
10
[0096] As illustrated in Table 1, the performance of
Examples 1 to 4 were the same as or better than the
performance of Comparative Example 1, and Examples 1 to 4
showed improvements in all items, such as bleeding phenomenon,
15 light resistance, and tensile strength, in comparison to the
DOTP product of Comparative Example 2.
PCT/KR2014/009979
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[0097] With respect to the tensile strength, it may be
understood that tensile strengths of Examples 1 to 4, in
which the isophthalate and the terephthalate were mixed, were
improved by 5% or more in comparison to that of Comparative
Example 3 using only the isophthalate5 .
[0098] Also, it may be confirmed that all of the ester-based
plasticizers of Examples 1 to 4 had an amount of ether of
1,000 ppm or less which was measured using a gas
chromatograph system by Agilent Technologies (Agilent 7890 GC,
10 column: HP-5, carrier gas: helium).
[0099]
[00100] The samples using the plasticizers obtained in
Preparation Examples 1 to 5 and the samples of Comparative
15 Examples 1 and 2 using commercial plasticizers were prepared
in accordance with ASTM D638 and in such a manner that 80
parts by weight of a plasticizer, 2 parts by weight of
epoxidized soybean oil (ESO) as a second plasticizer, and 2
parts by weight of a barium-zinc stabilizer were mixed with
20 100 parts by weight of PVC at a temperature of 100°C at 500
rpm for 2 minutes and at 1,300 rpm for about 10 minutes in a
3L super mixer. Then, roll milling was performed at 160°C
for 3 minutes to prepare 5 mm thick sheets.
[00101] After pressing was performed at 185°C while being
25 subjected to preheating for 3 minutes, heating for 3 minutes,
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and cooling for 3 minutes, 1 to 3 mm thick sheets were
prepared to prepare several dumbbell-shaped samples as type
“C” samples.
[00102] Each sample was subjected to the following physica5 l
tests, and the results thereof are presented in Table 2 below.
[00103]
[00104] *Hardness(ASTMD785), Tensile Strength, and Elongation
Rate (ASTM D638): Hardness, tensile strength, and elongation
10 rate were measured in the same manner as described above.
[00105] *Migration Resistance: An initial weight (Wi) of each
sample was measured to 4 decimal places. The sheet (3 cm × 3
cm) was inserted between polystyrene plates in an 80°C oven
and maintained for 72 hours in the state of applying a load
15 of 1 kg. Then, the sample was taken out from the oven and
stored in a constant temperature bath for 4 hours or more.
Thereafter, a sample weight (Wq) was measured and migration
loss was calculated by the equation: (Wi-Wq)/Wi × 100.
[00106] *Heating Loss: An initial weight (Wi) of each sample
20 was measured to 4 decimal places. The sample was fixed with
a clamp in an 80°C oven, and the sample was taken out from
the oven after 72 hours and stored in a constant temperature
bath for 4 hours or more. Then, a sample weight (Wo) was
measured and heating loss was calculated by the equation:
25 (Wi-Wo)/Wi × 100.
PCT/KR2014/009979
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[00107] [Table 2]
Category Example 1 Example
2
Comparative
Example 3
Example
3
Example
4
Comparative
Example 1
Comparative
Example 2
Preparation
Example No. 1 2 3 4 5 - -
Physical properties
Hardness 82.0 82.5 80.0 82.3 81.8 80.2 83.5
Tensile
strength
(kg/cm2)
193.0 195.8 184.9 195.0 192.7 185.3 196.8
Elongation
rate (%) 360.2 357.1 364.2 356.8 358.5 365.8 352.1
Migration
resistance
(%)
9.9 9.7 10.0 9.7 9.8 10.1 9.4
Heating
loss (%) 1.5 1.4 1.5 1.5 1.5 4.6 1.3
[00108] As illustrated in Table 2, it may be confirmed that
physical properties of Examples 1 to 4 were the same as or
better than those of Comparative Examples 1 and 25 .
[00109] In particular, it may be confirmed that Examples 1 to
4 had a heating loss of about 1.4% to about 1.5%, but the
heating loss of Comparative Example 1 was rapidly increased
to 4.6%. That the heating loss rapidly increased as in
10 Comparative Example 1 may denote that the amount of the
ester-based plasticizer present in the sample was decreased
by the increased amount.
[00110] With respect to the tensile strength, it may be
understood that tensile strengths of Examples 1 to 4, in
15 which the isophthalate and the terephthalate were mixed, were
improved by 5% or more in comparison to that of Comparative
Example 3 using only the isophthalate.
PCT/KR2014/009979
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[00111] It may be understood that migration resistances of
Examples 1 to 4 of the present invention were decreased by
about 3% in comparison to that of Comparative Example 1, and
heating losses of Examples 1 to 4 were decreased by 200% or
more in comparison to that of Comparative Example 15 .
[00112]
[00113] In order to compare physical properties according to
10 carbon numbers of the end groups of the isophthalate and the
terephthalate, physical properties were measured under
different conditions as in Table 3. In this case, the
isophthalate and the terephthalate in the plasticizer were
used at a weight ratio of 60:40 and a sheet was prepared by
15 the same method as the above-described method of preparing a
sheet. The isophthalate and the terephthalate in Examples 5
to 10 were respectively dialkyl isophthalate and diakyl
terephthalate.
20 [00114] [Table 3]
Example/Compa
rative
Example
Comparative
Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example
10
Carbon number P:C6
TP:C4
IP:C8
TP:C8
IP:C9
TP:C9
IP:C10
TP:C10
IP:C7
TP:C7
IP:C6
TP:C6
IP:C5
TP:C5
One
pot/Blending (blending) (one pot) (one pot) (one pot) (one pot) (one pot) (one pot)
al
proper
Hardness 88.0 88.3 90.4 91.8 86.7 85.2 82.1
Tensile
strength 185.0 184.2 180.5 173.6 201.7 235.6 259.2
PCT/KR2014/009979
24
(kg/cm2)
Elongation
rate (%) 258.7 260.2 235.6 210.8 268.5 278.9 295.3
Migration
resistance
(%)
9.9 9.6 1.05 0.07 10.5 13.8 15.9
Heating
loss (%) 3.5 1.3 0.68 0.50 12.3 15.6 24.3
[00115] IP: isophthalate
[00116] P: phthal-type ester
[00117] TP: terephthalate
[00118] As illustrated in Table 3, with respect to Examples 5 5
to 10 of the present invention, stable physical properties
may be secured. In particular, with respect to Examples 5 to
7 in which the end groups of the isophthalate and the
terephthalate had 8 to 10 carbon atoms, it may be understood
10 that migration resistances and heating losses were
significantly decreased by 10 times or more in comparison to
those of Examples 8 to 10 using the esters having 7 or less
carbon atoms.
[00119] Also, in the case that the isophthalate and the
15 terephthalate were mixed, it may be understood that the
heating loss was improved by about 3 times or more and the
migration resistance was decreased by 9 times in comparison
to Example 4 in which the terephthalate and the phthal-type
ester were mixed.
20 [00120] Thus, the plasticizer of the present invention
including the isophthalate and the terephthalate showed
PCT/KR2014/009979
25
significant improvements in terms of migration resistance and
heating loss as well as environmental friendliness in
comparison to the plasticizer in which the terephthalate and
DOP were mixed.
[00121] Furthermore, in the plasticizer of the presen5 t
invention including the isophthalate and the terephthalate,
it may be understood that physical properties of the
plasticizer including the end group of the ester having 8 to
10 carbon atoms were significantly improved in comparison to
10 those of the plasticizer including the end group of the ester
having less than 8 carbon atoms.
[00122]
15 [00123] In order to compare physical properties according to
a mixing ratio of the isophthalate to the terephthalate, the
isophthalate and the terephthalate were used at a weight
ratio of 90:10, 80:20, 70:30, 60:40, 40:60, and 0:100, and
physical properties were measured by preparing sheets by the
20 same method as the above-described method of preparing a
sheet. The results thereof are presented in Table 4.
[00124] [Table 4]
Example/Compa
rative
Example
Example 11 Example 12 Example 13 Example 14 Example 15 Comparative
Example 5
IP:TP(weight
ratio) 90:10 80:20 70:30 60:40 40:60 0:100
PCT/KR2014/009979
26
Physical properties
Hardness 88.0 88.2 88.5 88.5 89.5 91.5
Elongation
rate (%) 261.3 259.4 257.9 258.8 256.5 252.1
Migration
resistance
(%)
10.0 9.9 9.9 9.8 9.7 9.4
Heating
loss (%) 1.5 1.4 1.4 1.4 1.4 1.3
[00125] As illustrated in Table 4, in the case that the
isophthalate and the terephthalate were used at a weight
ratio of 90:10, 80:20, 70:30, 60:40, and 40:60 as in Examples
11 to 15 of the present invention, hardness was significantl5 y
improved in comparison to that of Comparative Example 5 using
only the terephthalate.
[00126] In addition, the hardness was affected by the mixing
ratio of the isophthalate to the terephthalate. That is,
10 with respect to Examples 11 to 14 in which the amount of the
isophthalate was greater than the amount of the terephthalate,
the hardness was significantly reduced in comparison to that
of Example 15 and Comparative Example 5 in which the amount
of the terephthalate was greater than the amount of the
15 isophthalate. The decrease in the hardness was effective in
improving the productivity of the product, and it may be
understood that the effect of increasing platicization
efficiency was obtained due to excellent workability.
[00127] Also, the migration resistances and heating losses of
20 Examples 11 to 15 were the same level as those of Comparative
PCT/KR2014/009979
27
Example 5 and it was observed that the elongation rates were
increased.
[00128] The plasticizer of the present invention including
the isophthalate and the terephthalate had the same level of
migration resistance and heating loss and increased hardnes5 s
and elongation rate, and thus, the plasticizer of the present
invention may improve the productivity and processability of
the product.

CLAIMS
1. A plasticizer comprising isophthalate and terephthalate.
2. The plasticizer of claim 1, wherein a weight ratio o5 f
the isophthalate to the terephthalate is in a range of 1:99
to 99:1.
3. The plasticizer of claim 2, wherein the weight ratio of
10 the isophthalate to the terephthalate is in a range of 20:80
to 99:1.
4. The plasticizer of claim 1, wherein the isophthalate
has an end group independently selected from alkyl groups
15 having 1 to 12 carbon atoms.
5. The plasticizer of claim 4, wherein the isophthalate
has an end group independently selected from alkyl groups
having 8 to 10 carbon atoms.
20
6. The plasticizer of claim 4, wherein the isophthalate is
dialkylisophthalate.
7. The plasticizer of claim 6, wherein the isophthalate
25 has a structure represented by Chemical Formula 1:
PCT/KR2014/009979
29
[Chemical Formula 1]
.
8. The plasticizer of claim 1, wherein the terephthalate
has an end group independently selected from alkyl group5 s
having 1 to 12 carbon atoms.
9. The plasticizer of claim 8, wherein the terephthalate
has an end group independently selected from alkyl groups
10 having 8 to 10 carbon atoms.
10. The plasticizer of claim 8, wherein the terephthalate
is dialkylterephthalate.
15 11. The plasticizer of claim 10, wherein the terephthalate
has a structure represented by Chemical Formula 2:
[Chemical Formula 2]
.
PCT/KR2014/009979
30
12. The plasticizer of claim 1, wherein the plasticizer is
an ether-free plasticizer.
13. A method of preparing the plasticizer of claim 1, the
method comprising steps of5 :
adding both isophthalic acid and terephthalic acid to
alcohol to obtain a mixture;
adding a catalyst to the mixture to react in a nitrogen
atmosphere;
10 removing unreacted alcohol and neutralizing unreacted
acid; and
dehydrating and filtering by vacuum distillation to
obtain the plasticizer.
15 14. The method of claim 13, wherein, in the first step, the
isophthalate and the terephthalate are mixed in a weight
ratio of 1:99 to 99:1.
15. The method of claim 14, wherein, in the first step, the
20 isophthalate and the terephthalate are mixed in a weight
ratio of 20:80 to 99:1.
16. The method of claim 13, wherein the alcohol has an
alkyl group having 1 to 12 carbon atoms.
25
PCT/KR2014/009979
31
17. The method of claim 13, wherein the alcohol is used in
an amount of 150 mol% to 500 mol% based on 100 mol% of the
isophthalic acid.
18. A method of preparing the plasticizer of claim 1, th5 e
method comprising:
preparing an ester-based mixture including
terephthalate and isophthalate; and
obtaining the plasticizer by blending the terephthalate
10 and the isophthalate to include the isophthalate in an amount
of 1 wt% to 99 wt% based on a total weight of the ester-based
mixture.
19. A resin composition comprising the plasticizer of claim
15 1 in an amount of 5 parts by weight to 150 parts by weight
based on 100 parts by weight of a resin selected from the
group consisting of ethylene vinyl acetate, polyethylene,
polypropylene, polyvinyl chloride, polystyrene, polyurethane,
and a thermoplastic elastomer.
20
20. The resin composition of claim 19, wherein the
composition is used in a compound formulation or a sheet
formulation.
25 21. The resin composition of claim 19, wherein the
PCT/KR2014/009979
32
composition is used in manufacturing electric wires, flooring
materials, automotive interior materials, films, sheets,
wallpaper, or tubes.